Hydrodesulfurization of sulfate turpentine
by William Bruce Isaacson
A thesis submitted tp the Graduate Faculty in partial fulfillment of the .requirements far the degree of
DOCTOR OF PHILOSOPHY in Chemical Engineering
Montana State University
© Copyright by William Bruce Isaacson (1963)
Abstract:
Samples of crude sulfate turpentine were obtained from sulfate pulp mills in Montana, Oregon,
Washington, and Georgia. The sulfur content of the samples was found to vary widely with different
mills and also on samples from the same mills taken at different times.
The compositions of the samples were determined by gas chromatography.
The a-pinene content of the samples from Washington and Oregon was approximately 85% that from
Montana was 35% and that from Georgia was 65% The a-pinene fraction, 145-155 °C at 640 mm Hg,
was distilled from the crude sulfate turpentine using a precision distillation column at a reflux ratio of
10:1. The a-pinene fraction, containing 95% a-pinene was then subjected to a hydrodesulfurization
treatment to remove objectionable sulfur compounds present. The hydrodesulfurization was carried out
in a flow-tube reactor in the presence of Houdry "Series C" cobalt molybdate catalyst.
The effects of temperature, pressure, space velocity, and hydrogen flow rate on sulfur were
investigated. The reactor products were analyzed for a-pinene recovery as well as sulfur content to
insure a high yield of a-pinene in the desulfurized product. The optimum reactor conditions for
desulfurization and a-pinene recovery determined in this investigation were 400°F, 25 psig,space
velocity = 2.5 hr-1, and hydrogen rate of 5,000 SCF/bbl. Sixty to ninety percent of the sulfur was
removed from the a-pinene feedstocks With an 80% composition of a-pinene remaining in the reactor
product. Increases in the reactor pressure and space velocity tend to decrease the sulfur removal. An
optimum reactor temperature exists for each space velocity and tends to increase with increasing space
velocity.
Increasing the reactor temperature tends to decrease the recovery of a-pinene in the reactor product.
Increasing the space velocity tends to increase the recovery of a-pinene.
The hydrodesulfurization of the entire boiling range of crude sulfate turpentine did net appreciably
improve the odor. However, 28-80% of the sulfur was removed on the different feedstocks The
desulfurization ability of the catalyst appears to improve slightly with use of the catalyst. No
deactivation was noted for 600 volumes of oil/volume of catalyst. :HiDRODESULFTmiZATIQN OF SULFATE TURPENTINE
by
WILLIAM BRUCE-ISAACSON
f
A thesis, submitted .to the Graduate Faculty, in partial
fulfillment of the .requirements for the degree
■
or
DOCTOR OF 'PHILOSOPHY,
in
Chemical Engineering
Approved:
Headjl Major.Department^,—
Chairman ? -Examining :Coimj>tge
ean,"Graduate Diyision.
■MONTANA STATE.,COLLEGE
,Bozeman* ■Montana
.Uuly v .196.5
RESTRICTED STASiJ
<2 <3 / = -
s Z
Ii
-VITA
The author , William Bruce Isaacsony -was torn, in Minot , MOfth
_ ■ Dakota on December 4, .1937,,.. the son oi* Mr, and Mrs. Franklin 6. Isaac­
son. -He is married to the .former Brigitta Brauner of Wlm,.,.Germany.
•Hr,. Isaacson attended elementary.schools in Minot, ,North Ddkota
and Worth Mankato,,-Minnesota,-.anh, he was graduated .from Minot ^igh
School in 1556- -In. September 195 6.,.he enrolled in the State Teachers
College in Minot,-North Dakota.in. the Pre-Engineering .Curriculum. • He
transferred to Montana State College in Bozeman,, Montana in September
1958% and received .his ■Bachelor of Science in. Chemical Engineering degree
in ^une I960. .,In.September i 960, .Mr, Isaacson enrolled...in. the-Graduate
Division at Montana State College to work, toward, the degree of Doctor
of Philosophy in Chemical Engineering:
•Mr. Isaacson has the following .work experiencet
■ Laboratory- Technician,,Westland Oil-Company..Refinery, Williston,
North Dakota,-May.1958 to September 19 58,
Student Chemical Engineer, Research and Development Department ,
Standard Oil Company ( l n d . -Mandan, Nor 6h .Dakota., June 1959 to
September 1959*
. Technologist, ,Shell Chemical Company., Torranpey California,
June i960 to September i 960.
Teaching Assistant.,.- Chemical Engineering.Department^ Montana. State
College, Bozeman, Montana, September i 960 to June 1961.
Research. Assistant., Chemical Engineering Department., ,Montana. State
College, Bozeman, Montana* September I 96I to September I.962.
Since September l962,,Mr.-Isaacson has been employed as. both a. Teach­
ing: Assistant and Research Assistant, while pursuing his graduate studies
at Montana State College.
Iii
. ACKN.OWLED G3MENT
The author wishess to thank .the -entire staff of the Chemical
.Engineering•Department of. JMpntanavState C o l l e g e a n d in .particular
Dr'* Lloyd Berg who directed this research* ,for their encouragement *
•suggestions* and Criticisms which led to .the successful completion of
this 'project.*
■The author also wishes .fo acknowledge the Engineering..Experiment
Station of ■Montana State College ..for their financial support given: this
.project and. the pulp a n d paper .companies who have supplied the raw
.materials and. other valuable information.
•1#
■TABLE -OF CONTENTS
Eage
A b s t r a c t .................... ;
....................................
I n t r o d u c t i o n , .............................. :
Research, Objectives
x
........................ I
.
g
Equipment and Experimental, P r o c e d u r e .................... :
A. ■ M a t e r i a l s .........................................
B, ■ Eiquipment
.
7
7
.
8
0 , ■ Operating , P r o c e d u r e ........................................ 10
D. . -Analytical P r o c e d u r e s . .................................... 11
:■
Thermodynamic feasibility S t u d y .................................... 13
. R e s u l t s .and . D i s c u s s i o n ........................................
A.
■ B»
Qi
. D.
E.
’F .
15
• C o m p o u n d - I d e n t i f i c a t i o n . ................................ .15
.Distillation, of the a-Pinene F r a c t i o n .............. .16
■ Preliminary. DesUlfurizatipn. Runs
. .
.
.• . • .
.
17
Extended Runs for Line-Out P e r i o d . .................... 19
20
-Verification of-Reactor F e e d and Products . . . .
Effect o f ■Temperature* Pressure* Space Velocity, and
•Hydrogen Rate on. Sulfur Removal . . ' .
.
G.
Effect of Variables o n C o m p o s i t i o n .................... '23
H.
Sulfur Removal.on Different a-Tinene-Fractions
1.
Sulfur R e m o y a l .on Crude.Sulfate Turpentine Samples .
■ I.. ■ Catalyst. Life
24
. . .
..........................
21
.
25
25 I
■V
TABLE•OF CONTENTS.(continued)
,P&geh
ConcLuSions
•
•
.
.
;
................ ... ■ .
.
.
...
26
Suggestions for Future W o r k ...................................... 29
'A p p e n d i x ............. :..........................................
Literature C i t e d ..................................
3.1
86
•VlLIST QP TABLES
■Page
Chemleal Compeimds
Table U
Themnodyriamld.. D a t a ..................................... 3.7
Table. Ill
Aetlylty O e e f T l c l e n t s .............................
■ Table IV
•
■ ' ............................
32
Table I
.Sulfuii Content of Crude Sulfate Turpentine •
. . .
Table V
Crude Sulfate Turpentine Compositions
Table VI
Distillation Data, ,for Crude Sulfate
Turpentine from T0I e d o ,. O r e g o n ..................... ^9
Table VII
Distillation Data.for Crude Sulfate
Turpentine from lies sup y ■Georgia
■Table VIII
Table IX
Distillation.Data .for CrUde Sulfate
Turpentine.from Missoulay Montana
.Distillation-Da,ta for Crude Sulfate
•Turpentine fpom Springfield,*, Oregon
Table X
.............
^7
^
................... 51
................
. . . . . .
53
55
Distillation.Data for Crude Splfate
Turpentine from. Eyerett,* ,Washington ................... 57
TaTle XI
Preliminary Desulfurization D a t a ..................... 59
Table XII
,Data.for Runs 'Using .20^-H2S^SO^..H2
Table XIII
Table XlV
Table XV
Table XVI
'
...................60
Extended Run o n Non-Sulfided. Catalyst
■at High. P r e s s u r e ' ...............
6l
Extended-Run on Non-Sulfided Catalyst
at- Low-Pressure......................
63
.Extended Run on Sulfided Catalyst at
Low. P r e s s u r e ...................................... '64
.Effect of Temperature on Sulfur. Removal,............ 69
•
■ V-ii
•LIST, OF TABLES - (.coixtlnued).
Kage
Table XVII
-Table XVIII
.Effect of Pressure on Sulfur Removal..................71
Effect of Space Velocity. on Sulfur Removal.
.
.
. 75
Table XIX
EffebU- of HydUogeU Rate ..on, Sulf u r 'Removal
. . . .
Table. XX
Cc^.os.ltldri.of•.Reactor P r o d u c t s ................. ...
Table XXI
Sulfur Removal, on. Different
Table XXII
Sulfur' RempVal on Crude Sulfate Turpentine
a.-Finene Feedstocks
.
. . . .
. Table .XXIII. . Catalyst L i f e ....................... ‘...............
Table X X I V '
75
77
. 82
83
84
Properties of Hpudfy llBeries. C ir Cobalt
•■■Molybdate Oatalybf,.. . ...............................85
.Fill
LIST OF FIGURES
Page
Figure I
.Figure .2
Flow Diagram. Fpr Topical Sulfate
Turpentine Recovery System.
!
............
Schematic Flow, Diagram of ■Hydrotreating Upit
.
.
34
•
•
45
Figure 3-
.Detailed Diagram.of R e a c t o r ...................
.
.
46 -
•Figure .4
■Distillation•Plot for Crude. Sulfate
Turpentine..f rojn. Teledp,.,,' O r e g o n ................
.
.
50
Distillation Plqt for Crude Sulfate
■•
Turpentine from ,Jessup;-,/ G e o r g i a ............
•
•
52
•, •
54
■ Figure 5
■ F i g u r e ■6
Figure 7
Distillation Plqt for Crude ..Sulfate
-TUrpentine from Missoula.-,,. Montana,............
Distillation Plot for Crude Sulfate
Turpentine from Springfield,, Oregon, . .:
.
. • 56
Distillation Plot for Crude Sulfate
Turpentine, from. Everett.Washington...........
.
.
0
Extended Run..on Non^Sulfided Catalyst
at High-Pressure
.
.
. . '.
.
.
62
-Figure.10-
Extended Run at ■Lqw-.. Pressure..................
.
.
65
Figure 11
Infrared Spectrum,of Known a-Pinene Sample. .
.
.
66
Figure 12
; Infrared Spectrum of. .appinene Distilled from
.Crude Sulfate Turpentine .(Reactor Feed) . .
' Figure .8
■Figure 9
.
...
67
/Figure 13
-Infrared. Spectrum, of a F i n e n e Reactor Product. .
.
. . 68
" Figure 14
Temperature Effect on Sulfur,Removal ..........
.
.
70
Pressure Effect on Sulfur Removal ............
•
•
72
-Spade Velocity Effect on Sulfur Removal .
.
.
74
Figure 1.5.
F i g u r e 16
.
Ix
LIST OF-'FIGURES (continued)
. Page
Flgtare 17
Figure
18,
Hydrogen Rate. Eff ect- on Sulfur R e m o y a l .............. 76
-Chromatogram for a - Finene.F e e d s t o c k .................78
■Flghre 19 -■ Chromatogram for Reactor Froduct at.
400.°F:>..25.psig.,. SV, = ,2 .5. •'
F i g u r e .20
...
.
.
.
.
.
.79
Chromatogram for Reactor Product at
' W pFy. 25 p s i g y SV. -.
-Figure 21
.
1.25 .............................. 80
Chromatogram, for Reactor Product at,
40.00Fy .5.OO psig,, SV.,=,'2.5.
. '.
.s ........... .81
X
ABSTRACT
Samples of crude sulfate turpentine were obtained from sulfate
pulp mills in Montana*. Oregon*, Washington,^- and Georgia. -The sulfur
content of the samples was found to rary 'widely with,different .mills. And
also on samples.from the same mills .taken at different times.
•The compositions of the samples were determined by gas chromato-’
graphy. - The a-pinene'content of the samples from. Washington and. Oregon
was approximately.85^ * .that from Montana was
and that from Georgia
was 65/ 0.
The a-pinene fraction*.145-155'°C at 64-0.mm Hg*.was distilled from
the crude sulfate turpentine -using a precision distillation column at a
reflux ratio of 10:1, ■The a-pinene fraction, containing, '95$. a-pinene was
■then subjected to a hydrodesulfurization treatment to remove objection­
able sulfur compounds, present.
The by dr odes ULf urlz at Ion was carried out
in a flow-tube reactor in the presence of Houdry "Series C" cobalt, mol­
ybdate catalyst.
•The effects of temperature*.pressure *, space velocity*, and hydrogen
flow pate-on sulfur were Investigated.
The reactor products were analyzed
for a-plnene recovery as well as sulfur content to insure a high yield of
a-pinene in the desulfurized product. The optimum reactor conditions
for. desulfurization and a-pinene recovery, determined in, .this investi­
gation w e r e -iLOO0H^ ,25 psig*. space velocity = 2.5 hr”1*, a n d hydrogen rate
■of 5*000. SCP/bbl. '. Sixty to ninety percent of the sulfur was .removed
from the a-pinene feedstocks With a n 8.0$ composition of a-pinene re™
.malning in the reactor product. Increases in the reactor pressure and
space velocity tend to decrease the.sulfur removal. ■ An optimum, reactor
temperature exists for each space velocity and tends to increase with
increasing Space velocity.
Increasing.:the reactor temperature tends to decrease the recovery
of a-pinene in-the reactor product, ■ Increasing the space Velocity tends
to .Increase the recovery of a-pinene.
ThehydrodesulfurizatlQn-Of the entire boiling, range of crude
sulfate turpentine- did, not appreciably, improve, the odor. .However*
287-80$ o f .the sulfur was removed.on the different feedstocks.
The desulfurization ability.,of the -catalyst appears to improve
slightly, with.use of the catalyst. -No deactivation was noted for 60.0
Volumes of oil/volume of catalyst.
•.INTRODUCTION
Tfefe problem, of controlling, and, reducing.water and atmospheric
pointion in the United States is becoming ■increasingly important,
.Effluents from sulfate (of kraft) -pulp,mills are ,major contributors
to the polution'problem.
ThO release .of foul odors has been a major
defect of the kraft pulping process ever since its.development in
Germany more than
years ago, -The odors are liberated, at several
points in. the process which are usually widely separated .,in the mill*
thus making the problem, of containing,and controlling these odors
difficult (3 ).,
The furnace.flue gases.generally contain a relatively,small.con­
centration of the .malodorous substances
h o w e v e r t h e total volume .of
discharge is so great that a considerable nuisance may result.
.Condensates from, the multiple-effect evaporator on t h e .nNlack
liquor" recovery system may contain a considerable amount of the foulsmelling compounds.*., thus .giving rise-to a secondary nuisance.
The gases liberated.in relieving and .blowing the.digesters are
a major source fop' the foul odors, associated with the .kr’aft mill.
•The
.major.offenders are organic sulfur compounds,* the principal malodorous
substances being hydrogen .sulfide*, methyl .mercaptan.^ ..dimethyl sulfide,
■and dimethyl.disulfide•(3). ■ Control.of these gases is particularly
..difficult pecause..their, fate -of release is subject to large fluctuations
inherent from the batch digestion process.
-2~
• If the .gases evolved.from the digester relief valve are candensely,the material■obtained Is called crude sulfate turpentine.
A
typical flow diagram for the recovery of this material Is shown In the
Appendix in Figure I.
The crude sulfate turpentine has a .foul odor
due to the sulfur compo,unds present.
This research project Is concerned
with the.desulfurization of the a-plnene fraction (approximately 85 per■CBiit) obtained from crude sulfate turpentine samples, from five sulfate
pulp mills.
."Mass spectrometer examination of the volatile components in. the
condensate from the kraft pulp digester blow gas has confirmed the
presence of hydrogen sulfide^ methyl mercaptan, .dimethyl sulfide, and.
dimethyl disulfide, and has shown, that corresponding ethyl compounds
_
and other sulfur^containing derivatives are not present in substantial
concentrations"
(15)..
The same sulfur compounds have been reported
present in the .CpUde sulfate turpentine by EfisheV, Prokhorov, and.
Matyushkina (13) and also.by.Enkvist (14).•
• The amount of loss ,of volatile organic sulfur compounds associ­
ated with the digester relief and blow as reported by Bergstrom and
Trobeck is approximately two pounds of sulfur per ton of pulp produced
(4).. . Pulping of Douglas-f,Ir produces one to five pounds of sulfur per
top of pulp produced.of the same type of organic sulfur compounds, de­
pending -upon the pulping conditions
(5). ■ The most critical factor in
fixing the amount of t%is material produced is the cooking-temperature.
-3■ More sulfur compounds are produced at the higher temperatures.
Due to
the high vapor pressure of these compounds
they readily escape into the
atmosphere during relief from the digester.
.Some of the materials are
partially condensed with the steam, and appear in the digester relief
condensate (crude sulfate .turpentine).
Some sulfur analyses of samples of digester relief gases by
Felicetta,..Peniston„ and-McCarthy have shown the following distri=*
but ion (1.
5 ):
. H2S
CH3SH
.(CE3 )2S
(CH3 )2S 2
Sample I
131
5240
7350
4095
Sample 2
138
. 4880
70,0.0
3870
(concentrations in parts p e r .million by volume)
Most- Southern kraft mills obtain some reduction in the emission
of odorous compounds from the digester gases through the recovery of
the cru.de sulfate turpentine. ■ The woods used, by the -Southern, mills
yield up to four 'gallons, of crude sulfate-turpentine per ton 6f pulp
produced, and make the recovery.of.this material for refinement econ*
omically. favorable.
■The yield of turpentine obtained from, the Northern
and Western, mills is somewhat lower * -approximately. 1.5 gallons per ton
of pulp produced*.and recovery for refinement is seldom practiced.
The
type of trees processed*.the -operating conditions p .and the-efficiency
of the recovery., operation determine the yield, of the turpentine obtained..
Current practices of recovery and disposal of crude sulfate tur­
pentine from Western pulp mills vary..with different locations and with
different mills.
some.mills.
Burning as a partial fuel requirement is practiced in
Others haye dumped, this material into the ocean where
location permits.
Repeated vaporization into the atmosphere has been
tried., as well as disposing into settling ponds.
In one casey.no re-
-covery system is used and all relief gases and. turpentine emitted from
the digesters are discharged into the atmosphere.
Recovery of the crude sulfate turpentine is becoming of greater
importance as a stable market for the material has developed:, •and, also
as polution restrictions are tightened.
An interest in individual pure
terpene hydrocarbons has also developed in the last few years and new
sources of the basic terpenes are being sought (33).
■Once the crude sulfate turpentine has been recovered^.the problem
then becomes that of desulfurization and purification to .provide a pro­
duct that will meet with public acceptance and-also haye the same desir­
able chemical and physical properties associated with pure gum spirits
of turpentine.
Many methods have .been employed to accomplish, these
tasks with steam distillation and/or chemical treatment.
Treating pith
hypochlorite or ethylene-diamine to further reduce the sulfur content
appear to be the most common (6.y J y .9..,.13-,- 17*. 20,. 25*,,27.*- 32>: -34).
-This research project is an-attempt to desulfurize .the crude
sulfate turpentine and also the a-pinene .fraction of the crude sulfate
-5-.
turpentine by a .method.not. previously ,reported jn. the.literature.
Kie
process proposed..is slmlJ,ar to. that used.In. the petroleum. Industry to
desulfurize various petroleum .fractions.
The oil,., in this ..ease -the
turpentine, is reacted with hydrogen gas at elevated temperatures and
pressures in the presence of a-Cobalt molybdate Catalyst.
-The raercap-
t a n s s u l f i d e s a n d disulfides react ..with, the hydrogen, to form, the
hydrocarbon and. hydrogen sulfide which is removed, by. bubbling through
a caustic solution.
■The .reaction.-is carried.out in a tubular~flow
reactor.. •The reactor conditions
however,, are considerably,, milder
than those employed in. the petroleum industry due to the structural
properties of the terpenes and side reactions, not prevalent with
compounds occurring in petroleum.
RESEARCH OBJECTIVES
The main objectives of this research were to determine the a•pinene content of samples of crude sulfate turpentine.obtained, from
kraft pulp mills .from five locations; to fractionate out the a.~pinene
boiling fraction and subject it.to a hydrodesulfurization treatment
to remove the ohjectionablei .sulfur compounds present;, to determine
the optimum operating conditions for the hydrodesulfurization; and to
maintain a high yield.of a—pinene in the hydrotreated-desulfurized
reaction product.
The.hydrodesulfurization was to be carried out in-a flowrfcube
reactor and the effects of the following variables on .desulfurization
and product rearrangement were ;to be investigated:
.I.
Temperature
2. .Pressure
5.
Space. Velocity
4-.
Hydrogen Blow. Rate
The above objectives.were realized insofar as time and available
equipment allowed. ■ The research, was meant to be both fundamental and
applied in nature y with the hope that the results could be applied,
toward commercial .utilization,-
EQUIPMENT AND EXPERIMENTAL, CONSIDERATIONS
A.
Materials
Feedstock:
The .crude sulfate turpentine used for this research
project was obtained.from the following pulp, mills;
:Waldorfw-Hoerner Pulp •Mill*.
■Missoula* ■Montana
Georgia-Pacific Paper Company,-Toledo *.Oregon
Weyerhaeuser Pulp .Mill y .Springfield,.
.Oregon
Weyerhaeuser Pulp Mill,* Everett, .Washington
Rayonier Pulp-Mill*, Jessup*- Georgia
The a-pinene Content of the various, samples.was .determined by means of
gas chromatography.
The a-*pinene fraction,. 145-155°C at 64-0 ram Hg
pressure,, was distilled using a packed ..distillation column described
below.
The a-pinene fraction was then washed with a ten percent
solution of sodium hydroxide to remove dissolved hydrogen sulfide and
mereaptans.
The caustic wash was followed by two water washings to
remove trace amounts of caustic. ■ By this means it was possible to
determine the desulfurization due to the hydrotreating.
The sulfur con­
tent of all reactor feed stocks was determined at this point.
- Catalyst and Catalyst Supports:
The -catalyst used. for. the hydro­
desulfurization was a Houdry "Series C" cobalt molybdate catalyst,
.Pre­
vious investigations at Montana State College on hydrodesulfurization
of petroleum, distillates using.the same catalyst have shopn it to be
very effective for.removing sulfur (21* ,29).
This.catalyst is a typical
hydrodesulfurization catalyst and is used extensively in the petroleum
-8
industry.
-
The physical and chemical'properties of the catalyst are
given in Table XXIV.
•The amount of catalyst used, for each run was 12 cc (10 grams).
The catalyst was diluted with 1/8rin, alundum pellets in order to keep
the volume of the reaction zone of approximately 50 cc in the reactor.
The catalyst bed was supported .on. the top and bottom in the reactor by
l/4~in. low surface area alumina pellets.
-,.Hydrogen Gas :
The .hydrogen .used .for the desulfurization, was pur-
.chased in high pressure cylinders from-HR Oxygen and Supply Company in
Billings ^.Montana.
Trace amounts of oxygen and water w.ere removed, by
passing the gas through a "Deoxo" unit and a drying unit containing
Drierite.
■B.
Equipment
Distillation Equipment:
The distillation column used to,separate
the a-pinene fraction from the crude sulfate turpentine was a. .four-foot
glass column, ,1^3/4-in..in diameter.
The column was packed with l/8.-»in.
.stainless steel helices '(Eenske rings)..
The column was wrapped, with
aluminum foil to reduce heat-losses and enclosed .inside another.glass
cylinder 3-in. in didfiieter arid four feet in length.
>
•
The inside column
was provided with ground .glass joints at the top and bottom to insure
leak-free connections with.the stillpot and the condensing head.
Auxiliary equipment for the distillation column included a Corad
condensing head,- .stillpots ranging in size from one liter to fifty
-9•liters
Grlas-Col heating mantles ^ and Powenstats .
.Reactor Equipment:
■ shown in Figure 2.
A schematic flow diagram-of the reactor is
The reactor operates as a continuous-flow>.fixed-
bed, .integral reactor.
•The turpentine feedstock is pumped from the
reservoir to. the top of the reactor where it is joined by the purified
hydrogen just prior to entering the reactor.
•The turpentine and hydro­
gen then pass down, through, the pre-heat zone* catalyst zone, and effluent
zone together.
The reacted products then pass through a concentrie-
-pipe water cooler and.through the pressure regulator.
The gaseous and
liquid products then pass through a cooling coil in an ice bath and
then into a receiver flask where the liquid product is collected.
-The
gases are bubbled through a caustic solution and vented.to the atmos­
phere.
.Reac t or Sp ec if ic at ions :
The reactor was made from 1-in.- OD,,
■schedule 8 0 , .stainless steel seamless.pipe,.30 inches in length.
The
bottom of the reactor was silver soldered to a flanged union to permit
ease of removing to change catalyst.
-The top of the. reactor was p.ef-
.manently connected.to a high pressure cross with, a 1500 psi rupture
disc inserted, in one side as a safety, precaution.
.The reactor was
covered with a layer of asbestos tape and then wrapped with four ceramicbeaded nichrome heating coils.
A l-l/2-in. layer of insulating cement
was placed-over the heating ,coils.
•A 1/4-in. OD stainless steel thermowell sealed at one end. was
passed down through the center of the reactor.
Four iron*,const ant an
thermocouples were placed .inside the thermowell for measuring the tern^
perature at various positions.
A diagram Indicating .the positions of
the thermocouples,, heating.coils.* and.catalyst zone is shown in. Figure 3, .
Reactor.auxiliary equipment included the following;
-a Lapp Pulsa-
■feeder pump j ■a Brooks armored high, pressure rotameter> a -Grove (Mity.-rfflite)
back pressure ,regulator;,four 110-volt Powerstatsj.a IOQO ml.graduated
feed reservoir with a I 5 ml burette attached for measuring reactor feed
rates 5 a Leeds and Ndrthrup indicating potentiometer; three Marshall­
town test pressure gauges; a Dohor Purifier 5 .a.Matheson hydrogen,
regulator.
■All of the tubing used.on the unit was type 302 stainless steel,
.l/8.-in. OD tubing.
C.
Various Hoke valves were also used.
Operating Procedure
:Reactor Rrepapat jon;
In preparing for a run^ ,the reactor was
loaded with catalyst, purged with hydrogen.to remove the air, .then,
pressurized and tested fop leaks. 'The reactor heat was -.turned, on and
the temperature, adjusted to. approximately the desired operating tempera­
ture.
The hydrogen was turned on and metered through a .rotameter. •The
flow rate was adjusted.by means of a needle valve.
The feed pump was
then turned on and the flow adjusted.by means of measuring the volu.metric flow rate from t h e -15..ml burette. • The temperature was recorded
JJLevery half, hour1 and the Powerstats adjusted-when necessary.'
The reacted
liquid products were collected, in the flask below the Mity-mite pres­
sure regulator.
Before some of the runs y the catalyst was pre-sulfided. t.o insure
maximum activity. - The pre-sulfiding .was accomplished, by passing a ZQf0
H2 S - 80$..H2 mixture over the catalyst until, half as many grams of sul­
fur as ghams of catalyst had, been passed through the reactor. . This
procedure is the same a s .that followed by.Kiovsky (21).
:Sampling:
The .unit was allowed, to .run at steady state and samples
were taken at two-hour intervals, after the lineout period.. .Each sample
was analyzed for.total sulfur and terpene,distribution by the methods
described below.
D. •Analytical. Procedures
1.Sulfur Analysis;
The total,.sulfur content of the crude sulfate
turpentine samples., .the a-pinene reactor feed. ■stocks r , a n d .the reactor
products was determined by the Quartz Tube Combustion Method;-, ASTM
,Designation; :D I ^ l -*58 T ,(2). •The samples of reactor feed and product
were washed with a. ten percent solution of sodium hydroxide to remove
hydrogen sulfide and mercaptans. • The .caustic wash was followed by two
water, washings.
Two determinations .were .run on each sample and the
results averaged.
. Qas,, Chromatograph Analysis:
The. compositions of the samples were
determined by.means of an. Aerograph gas chromatograph manufactured by
the Wilkens Instrument and Research Company; •The column used was a
!/1Jr In. stainless steel tube, six feet in length-, -packed with Carbowax
1J-OOO adsorbent on Chromosorb C-^-8560 supports (35).
AMinneapdlis-
•Honeywell recorder was used to record, the chromatograms.
The column
temperature was h e l d •constant at 90°C and the helium flow rate of 35 Ce
per minute was employed.
A 2 ul sample was injected into the Chromato^-
graph for analysis.
-The characteristic peak areas were determined by means of a K&E
compensating polar planimeter.
-.Infrared Spectrophotometer-:
Infrared spectrums of Various samples
were run by. the Chemistry Department of Montana.State Collegfe on a
Beckman Model IR1J-.Spectrophotometer.
THERMODYNAMIC FEASIBILITY STUDY
In order to establish the feasibility of the desulfurization
reactions >,a •thermodynamic study- was conducted,fo,r five possible re­
actions occurring in the reactor.
The sulfur compounds chosen for the
study are those having .been identified, as present in the. crude sulfate
turpentine.
■1.. ■ Methyl Mercaptan +!-Hydrogen -Se-Methane + Hydrogen Sulfide
CH3SH
Ih 2
I
+
--- >
2. .Dimethyl Sulfide + Hydrogen —
CH 3SCH 3
3.
.2H 2
+
H2
+
5.
.+
3H2
:H2S
Methane +-Hydrogen Sulfide
+
"
R2S
Ethane.+ Hydrogen Sulfide
--- >* C2Hg .+
■4. . Dimethyl Disulfide +-,Hydrogen —
CH 3SSCH 3
+
2 GH 4
I
Dimethyl Sulfide + Hydrogen, —
CH 3SCH 3
.CH4
.H2S
Methane +, Hydrogen Sulfide
--- >■ 2 CH4 +
-HH2S
Dimethyl- Disulfide + Hydrogen — >-E thane.+.Hydrogen Sulfide
OH 3SSCH 3
+
-HH2 ■ ---- 5- C2H 6 +
H H 2S
In all cases the reactions,-were .considered ,to go to the. hydrocarbon,
and hydrogen sulfide.
-The -conditions for the investigation were 3Q0°F to
and.,from
one atm to twenty atm^.. the range of conditions of the experimental -work.
The -complete thermodynamic study with tabulated results is included in.
the Appendix.
-14• All .of the reactions appeared to be very favorable over the range
of conditions investigated.
The conversion in every case was greater
■than 99.9 percent.
Experimental data indicated-a reaction between hydrogen sulfide
and a-pinene,. thus tying the sulfur a n d .terpene together forming a thlo^
...terpene.
■Thermodynamic data for terpenes are .very limited and that for
.thioterpenes does not exist.
Estimation methods also, fail to lend them­
selves for thermodynamic values f o r .thioterpenes.
Therefore, a thermo­
dynamic feasibility investigation for reactions between hydrogen sul­
fide and the tefpenes could not be carried, .out.
RESULTS M D DISCUSSION
A.
Compound Identification
The chemical structure, boiling .pointr and. nomenclature of the
compounds used in this discussion are given in Table I for easy
reference.
1The total sulfur content of samples of crude sulfate turpentine
was determined using the method described under Analytical Procedure.
More than one sample was obtained from three of the pulp mills.
results appear in Table IV.
The
It is apparent .from the results that the
sulfur content yaries widely with different pulp mills and also on
samples from the same pulp mill. ■The amount of sulfur present is
dependent upon the procedure and equipment used for the digester relief,
and the efficiency of the condensation of the volatile vapors, see
Figure I.
Therefore, deviations obtained in the sulfur analysis on
different samples can be expected.
■The compositions of the samples of crude sulfate.turpentine from
the different locations were determined, by use of gas Chromatography.
The characteristic peaks obtained in the chromatograms were identified
by injecting known samples of pure terpenes along with, the unknown sam­
ple. into the chromatograph and observing the location of the pure terpqne.
The identity, retention order^ and retention time of all compounds
present in the crude sulfate turpentine were identified by this pro.cedure.
The principal compounds present in the crude sulfate turpentine
were a-pinene,.cairiphene, b-pinene,,dipentene, and in the Missoula,
•Montana turpentine,.delta--3^carene. • The relative amounts of each. conM
■ponent present were determined, .on the principle that the area undef the
chromatogpam peak is proportional to the amount.of that substance prer-sent i n •the sample (35).
Table Y shows the average weight percentage
composition of the samples.
The composition of the turpentine is de­
pendent upon the types of trees Used in the pulping process
(28).
The
crude sulfate turpentine from M i s s o u l a M o n t a n a has a high, content -of
delta-3 ^carene., -The delta-3-car ene is characteristic pf ponderosa pine
Yhich is used, extensively.,in the MisSoula, mill.
The sample from Jessupy,
Georgia, has a, higher content of b-pinene than the samples obtained
from, .the'Western.miilp.
-This is. Characteristic of. the Southern, pines.
The 'samples from Oregon and Washington.contain approximately 85 .percent
a-pinene Yhich is a result .of the Douglas fir which, is processed, in
that area.
B.
hlstillation of the, a,-Plrene- Fraction
Next,.one-Jiter samples, of the crude sulfate turpentine from the
five locations were distilled, in a precision, distillation column, at a
reflux ratio,.of 10 :1 . ■The temperature was noted at 10 cc.intervals and
samples.were ,taken at 20 cc intervals. ■ The samples were analyzed for
composition using gas chromatography to see the separation attained,.
Tables VI through X contain the distillation data and/Figures. 4 through
■8 are the plots of volume percent distilled versus temperature (0O) for
the five samples.
The a-pinene boiling plateau is readily apparent on .
the plots p /being approximately, at 148-150/C at 640 m m Hg.
-17-■
TheCPHial decomposition of the terpenes occurred, at temperatures
in excess of 16^°C.
-This was noted by a. dip in the temperature;^, the
formation of water I n -the distillate,, and. the darkening •of the liquid,
remaining in the stillpot.
/Approximately 50 percent of the total charge to the stillpot dis­
tilled between',145-1550-C at. a reflux ratio of 10}I, with, the exception
of the Missoula sample which,was lower due to the lower a-pinene con­
tent. .Large- samples.were then distilled from, a SO^liter stillpot and
■the 145-1 550C.fraction was collected.
.This material was. then..-washed,
with a. 10 percent solution of S-o.dium, hydroxide t.o Pempye Pissolyed
hydrogen sulfide and. mere apt ans..
two water washings.
Kie caustic washing was followed, by
This material was then used as.reactor feedstock
for the hydrodesulfurization treatment.
C. ■Preliminary Hydrodesulfurization Runs
The.first attempt to hydrodesulfuplze, the a-pinene.fraction in
the flow-tube reactor was ,carried.out at conditions similar to that
employed in the petroleum industry for the desulfurization of petyoleum
distillates.
The conditions selected wepe;
reactor temperature,-,YQO0T1^
reactor'pressure,. 250 psig;.space velocity, .10 hf^1; and hydrogen flow
rate of 1000 SCF/pbl.
(Space velocity is. defined, as volumes of oil. p e r '
hour per .yoliume of catalyst).
The chromatogram, of the reactor product
showed that most of the a-pinene had. been destroyed.
■Therefore, it was.
decided to decrease the. temperature of.the reactor by 5O 0F increments
until, a. ,fair yield of a-pinene was recovered in the reactor product.
-18
This temperature was 550°F,
The sulfur removal data for runs at 1J-OO0F to 550°F are contained
in Table XI.
The results indicate that as the temperature increases in
this interval,.the amount of sulfur removed decreases.
This is contrary
to hydrodesulfurization reactions occurring in petroleum fractions and
indicates the possibility of side reactions or interference in desul­
furization caused by the teppene rearrangement.
■The effect of space velocity on desulfurization was investigated
next by passing a-pinene feedstock with differing sulfur* level oyer the
catalyst at space velocities of 10, 5 y and 2.5 h r ^ 1.
The results of
this studyy also appearing in Table Xl-,. indicate that a. high space vel­
ocity favors the removal of sulfur and also that as the amount of sulr
.fur present in the feedstock increases, the percentage sulfur removed
decreases.
This is also contrary to reactions of hydrodesulfurization
for petroleum distillates.
. After examining. Table XI further, it was decided that possibly a
reaction was occurring between the hydrogen sulfide formed from the
hydrodesulfurization reaction and the terpenes.
To investigate this
possibility, a set of runs was performed on the a-pinene feedstocks
using a synthetic mixture of 20% hydrogen sulfide and 80% hydrogen
rather than pure hydrogen.
.The results of this study, .Table XII,
clearly indicate a reaction between the hydrogen sulfide and one of the
terpenes present in the reactor.
All of the reactor products contained
-19-raore sulfur than was present in the reactor feedstocks .No attempt was
made to identify the reaction product between the hydrogen sulfide and
.the terpene; however, a search of the literature indicated a.reaction
between .sulfur and a-pinene to form a thioterpene.with a sulfur■bridge
replacing the double bond (31),.
.This is one possibility for the side
reaction.
.D.
Extended.Runs for Dine-Out Period
In order to find the time for the reactor to reach steady state
■after•start-up,.a series of extended runs-was.!conducted both at high and
■.low.'pressures.
Table XIII contains the data for the extended run on
non-sulfided catalyst at .250- psig reactor pressure.
Figure 12 is a
plot o f these data. . It is. apparent from the. plot that steady state is
reached after seven hours on stream at constant reactor conditions.
,While the manufacturers tilaim.that the catalyst used .for the
investigation has. been pre-sulfIded-,- Kiovsky has shown.that their -claim
is incorrect- (21).
.He found better -conversion was obtained by pre­
sulfiding the catalyst using a 2Q% hydrogen sulfide and.8
hydrogen
mixture. .In order to determine the effect of .pre-sulfiding the catalyst
.for this study,.a line-out study for .two runs was carried out; one on
pre-sulfided catalyst and the other on non-sulfided catalyst.
Thesul-
.Tiding procedure-was the same as .that.followed by.Kiovsky.
.Table -XIV contains data.for.the extended run o n •the non-sulfided
catalyst at a.reactor:pressure of 25 psig. ■ The line-out time at this
-.20- pressure and at reactor temperature of -M-OO0F and ■space ■velocity of
2.. 5 hr "1 is approximately four hours. •Table XV. contains the data for
the exact same run,,but on the pre-sulfided catalyst.
out time, is approximately 18 hours.
-Here,the,line-
However, a. greater'percentage of
the sulfur,is removed,,see Figure.13.
The reason for the total sulfur
■content to be greater than.the sulfur content of the feedstock,on the
initial sample .from t h e ■run on.the pre-sulfided.catalyst.is due to the
reaction between the terpenes and the excess, hydrogen sulfide from.the
pre-sulfiding operation. .It was also determined that once a batch of
catalyst had been-pre-sulfided,. it was not necessary to pre-sulfide the
■catalyst for another run on the same catalyst. -The pre-sulfided.catalyst
was used for the remainder of the runs carried out in this, investigation
without loss of the activity, observed.
E . -Verification of Reactor.Feed and Products
The positive identification of the reactor feedstock and reactor
■product as a^pinene was made by. means of analyses.of these samples by
infrared spectrophotometer.
The spectrums of these samples were com­
pared with the spectrum of a known sample of a-pinene.
.The spectrums
appear as. Figures.11,.12, a n d .13. -The spectrums of the reactor feed
and reactor product are almost identical with that of the known sample
of a-pinene.
.This.verifies the a-pinene peak produced on the chromato­
grams as a-pinene and not that of some other terpene that has,the same
retention time as a-pinene.
-21F.
Effect of Temperature, Pressure,Space .Velocity,.and Hydrogen Rate
on Sulfur Removal
Next, ,the effects of temperature,.pressure,, space velocity, ,and
hydrogen rate on the sulfur conversion were .Investigated.
A single
feedstock from Springfield,■ Oregon-was used-for these runs so that an
easy comparison could-be made.
<
.Table XVII and Figure 14 show the effect of temperature on the
■sulfur■removal at different space velocities.
A run at space velocity
(SV) o f '1.25 hr-1 was performed at 400°F and 25 -psig. - However, the
yield of a-.pinene in the product was only- 42#.as compared -with 82# at
a space velocity of 2.5 at the same conditions. ■Therefore, a space
velocity of 2.5 was considered as the lower limit for the recovery of
a high yield of a-pinene in the reactor product. .The curve obtained
at SV = 10.0 appears to ,be headed for a minimum above 500°F.
Since
temperature as well as space velocity has an effect on the composition,
the yield of a-.pinene at SV.= 10.0, 500 0F, -and 25 psig is less ,than
that at SV = 2.5, .400°F, and 25 -psig." .Also, the sulfur Is .three times
as great at SV.= 10.0. .Therefore, ,no runs were made to continue this
line to its minimum value. .Duplicate runs were made for all tempera­
tures at SV.= 2.5 to verify the line. . Deviations of ,10-.15 -ppm sulfur
are -considered .within the limits of reproducibility of the analytical
procedure used. •The sulfur content of the reactor -product at 400°F,
SV.= 2.5,- and 25 psig was approximately 55-70’PPm with a conversion of
approximately 85#.
v
-22The effect o.f pressure was ,investigated by a. series.of runs with
only the-pressure.varied and-all other variables held constant: -The
data,from-these runs .are:reported.in Table•XVII and-plotted in Figure
■ 15. .Duplicate ,runs-were'performed,for -this study.
.The plot shows a
. gradual, decrease in sulfur removal with increase in reactor pressure.
■One run--was carried,,out at a reactor pressure of $00 psig. -The reactor
-product contained- only' 1 %
of a-pinene and 42$. p-inane, thus indicating
;hydrogenation of the double bond.present in the a-pinene.
.No further
• investigations'were carried out at t&is elevated pressure.
- The effect.of space velocity on sulfur removal was studied with
all other variables held constant.
.The space velocity was varied from
SV;= 1 . 2 5 -to 15 .O -hr-1. -The data for these runs are given in. Table
XVIII and plotted,in Figure 16.
The data.indicate decreasing.sulfur
removal with,increasing-space velocity. .This.-is in direct conflict
with the data obtained, in the preliminary desulfurization runs. .How­
ever, it.is noted that the sulfur content of the-feedstocks was not con­
stant in the preliminary, runs.
With increasing sulfur content in the
feed, ,more hydrogen -sulfide.could be:-produced by.the desulfurization
reaction,.thus resulting,in-a greater chance to combine with the ter-penes.
Another influencing factor could be the change of. phase occur-
,ring in the reactor.
At 2$0 psig the.terpenes pass through the reactor
largely-in the liquid-phase.
At 2$ psig,.the terpenes pass through the
reactor in the'Vapor state and-hence-the -residence time, is greatly
reduced.
-23•The effect of hydrogen flow rate was determined previous to the
temperature, pressure,and space velocity studies. .Hydrogen rates of
2500, 5000, and 10,000 SCH/bbl were employed for three runs at 4dO°F,
■and :250 pslg.
.The conversion (sulfur original - sulfur f Inal/sulfur
original).was calculated and:plotted In Figure 17.
- ported-.In ■Table ■XIX.
These data are re-
-The conversion asymptotically approaches a con­
stant value at approximately 5000' SGF/bbl.
-This, hydrogen flow rate was
used for all runs in the optimization study,.
•G. .Effect of Variables on Composition*
•
The effects of temperature,■pressure and space velocity on the
composition of the reactor products were determined by means of char­
acteristic peak areas.produced.in chromatograms of the products. .The
results are given in-Table XX.
• The a-pinene content of the feedstock was '95' percent.
An increase
in temperature tends to decrease the a-pinene content and.increase the
camphene content.
At 400°F, .25 pslg, and SV.= 2.5)-dipentene appears
and tends to. increase with increasing-temperature.
At 500°]?, .25 pslg-,
■and SV = 2,5,.the a-pinene content has -decreased from 95# to 39#,-the
camphene content has increased from 3# to ..38#, the -b-pinene has de.creased -from 2# to 0#, -and .dipentene has increased from 0# to 18#-.
Pressure appears to decrease the yield of a-pinene slightly in
the-range of 25-250-pslg. . Since a .change of-phase is encountered in the
reactor between these-limits■the slight discrepancy-in the trend.in-
•-.24dicated. in the pressure effect in- Table XX is entirely possible.
.At a
reactor pressure of 500 psig,■a- 19$ .yield of a-pinene was .obtained.
■However,.more significant is the 42$ yield of p inane.
Increasing the space velocity tends to increase the. ..recovery of
a--pinene and decrease the .yields of the other terpenes present in sub•stantial amounts.
•It was noted that reactor.compositions also change slightly with
catalyst life.
.The'longer the catalyst has been in u s e , .the greater
■the recovery of a-pinene. -The compositions reported ;in- Table XX were
from samples taken from- a catalyst which had approximately $00 volumes
of oil per volume of catalyst passed over the catalyst.
Duplicate runs
made after this catalyst use do not change the composition significantly.
Chromatograms .of the reactor feedstock and reactor products at
400°?,.25'P'Sig, S V = 2.5; 400°?, 25 psig, SV = 1.25; and 400°?, 500
psig, .SV = 2.5 are shown as,Figures 18, .19, 20, and 21.
.H. .Sulfur Removal.on Different a^Plnene Fractions
The .a-pinene fractions distilled ,from the other four samples of
crude sulfate turpentine were desulfurized using the best conditions
obtained from.the previous studies.
and SV = 2,5.
.The conditions were 400°?, .25 psig,
The results appear-in Table XXI. - The sulfur content of
the feedstocks vary with location and also with different samples from
the same location.
The same was shown with the sulfur content for sam­
ples. of crude sulfate turpentine in Table IV.
.The conversion obtained
■-25“
was greater than 65$ . i n all samples and as high as 91$.in the sample
from Toledo, Oregon.
Conversions will vary depending upon thfe concen­
trations of different sulfur compounds present *
-I. . Sulfur Removal on Crude Sulfate Turpentine Samples
Samples of untreated crude sulfate turpentine from the different
pulp mills were passed through the reactor at the optimum operating
conditions determined for the a-pinene desulfurization. .The results
appear in Table .XXII.
Conversions varied from 28$ to 80$.
All samples
still retained the undesirable odor after the desulfurization treatment.
J. .Catalyst■Life
The catalyst used throughout this investigation was Houdry '"Series
C" catalyst.
The properties of the catalyst.appear in Table XXIV.
.The
life of the catalyst was checked by repeating the same run at different
volume of oil per volume of catalyst life ratios. - The results for
three trials are given in Table XXIII.
-It appears that the desulfuri­
zation ability of the catalyst improves slightly with use up to approxi­
mately 600 volumes of oil per volume of catalyst life.
<were obtained.
No further data
CONCLUSIONS
. The sulfur content of crude sulfate turpentine varies widely
with samples from different pulp mills and also with sa.mples from the
same pulp mill taken at different times.
The main sulfur compounds
present in the crude sulfate turpentine are hydrogen sulfide, methyl
mercaptan, dimethyl Sulfide, and dimethyl disulfide.
■The terpene composition of the crude sulfate turpentine varies
with location.
The samples obtained from Washington and Oregon contain
approximately 85$ a-pinene, that from Montana contains approximately ...
35$ a-pinene and 40$ delta-3-carene, and the sample from Georgia con­
tains approximately 65% a-pinene and 20% b-pinene.
The composition
is dependent upon the type of trees processed in the pulp mill.
Atmospheric distillation of the crude sulfate turpentine at a
reflux ratio of 10:1.will yield a ^Of0 fraction boiling from-l45--155°C
at 640 mm. H g 'Which contains 95$ a-pinene.
lower for the Montana turpentine.
■This fraction is slightly
Thermal decomposition of the tur-
-pentine is encountered.near'l65°C.
.Sixty to ninety percent of the sulfur remaining in the a-pinene
fraction can be removed by hydrotreating this material in a flow-tube
reactor in the presence o f 'Houdry "Series C" catalyst.
At a hydrogen
rate of 5000 SCF/bbl,. the optimum reactor operating conditions which
will remove the most sulfur and at the same time retain a high yield
of a-pinene in the reactor product are 400°F,.25 psig, SV = 2.5 hr-1.
“27A reaction occurs between hydrogen-sulfide and a-pihene to form
a thioterpehe.
.No--identification of this compound was made.
.An increase.in reactor-pressure tends to decrease the SUlfur
-removal.
.Ah.increase.-in -space velocity- tends to decrease the Sulfur
removal. .Ah .optimum-reactor .temperature for a .given pressure and space
velocity exists and tends.to increase with space velocity.
An' increase in temperature tends to decrease the recovery of a- pihene in the reactor product.
The amounts of camphehe and dipentehe
increase in the reactor product as -the temperature I S .increased.
.In the range of 2-5--250 psig, an. increase in the reactor -pressure
tends to decrease the -recovery of a-pihene slightly.
-However, hydro­
genation of the double bond ,in a^pinene occurs at .500 psig> and a 42%
yield.of p inane is obtained.
- Increasing ,.the space velocity tends ■to increase the recovery of
a-pinene in the reactor product.•
• Hydrodesulfurization of the entire boiling :range of crude sulfate
turpentine does not improve the odor of the material. ■ H o w e v e r 28-80%
of the sulfur-was.removed.
.The.catalyst has a greater activity after it is-pre-Sulfided-using
'a mixture of 20% hydrogen sulfide and 80% hydrogen.
Once the catalyst
has been sulfided-it•is not necessary to sulfide it for subsequent runs
'0
-2 8 ■on the same catalyst.
The desulfurization ability of the catalyst
seems to improve slightly with use. -No deactivation of the catalyst
was. noted for use of 600 volumes of oil per volume of catalyst.
■SUGGESTIONS' FOR. FUTURE STUDY
•Throughout this research,project, many-interesting phenomena were
observed which could be investigated.further.
A most interesting investigation would be a study on the hydro­
genation of a-pinene to p inane,.accompanied.with desulfurization.
A
4 2 $ -yield o f 'pinane was obtained under 35 atmospheres pressure at 4.00°F
in the reactor effluent.
.Since this project was concerned primarily
with a-pinene, ,no further -investigation on hydrogenation of a-pinene
to p inane was carried out.
Another investigation could be undertaken to produce other ter•penes such as camphene and dipentene from the destructive hydrogena­
tion of a-pinene.
Separation o f 'the individual pure terpenes from the crude sulfate
turpentine would be of value.
.Delta-3-carene has recently been -sepa­
rated by McCumber from the crude sulfate turpentine from Missoula,
Montana. (26) . .The next separation should be that of b-p.inene or di­
pentene.
I
.An improved method of sulfur analysis should be used for further
work on desulfurization.
Several other methods requiring.expensive
equipment have been reported in the literature (I, ,10, 15).
Possibly
gas chromatography could be used for the sulfur analysis .in addition
to the terpene analysis.
-30■ Investigation into hydrodesulfurization of the entire boiling
range of crude sulfate.turpentine could be exploited ,further than is
set forth in this research project.
APPENDIX'
-32Table I.
Compound
Chemical Compounds
Structure
Bolling Point
Alpha-plnene
156°C
Beta-plnene
162°C
Dlpentene
178 °C
Plnane
169°C
Camphene
I 59°c
-33 t
Table I. (Cont.)
Compound
Chemical. Compounds
Structure'
Methyl Mercaptan
H
-H-C-S-H
H
Dimethyl Sulfide
% •JH-C-S-C-H
H .H
Dimethyl Disulfide
H
H
H-i-S-S-d-H
H
■H
Boiling-Point
5.8°c
.
380C
IlT0C
H
T 0C
Cyclone
Separators
Relief
Valve
Condenser
Vents
Digester
Turpentine
—
Wood Chips
&
To Black Liquor
Sump or Blow Tank
Water
White Liquor
Steam
To Ditch
Pulp & Black Liquor
Figure I.
To Turpentine
Storage
Flow Diagram for Typical Sulfate Turpentine Recovery System.
-35-Thermodynamic Study
A thermodynamic study of the.following overall reactions was
performed at six temperatures and four pressures.
The five reactions
were:
1. .Methyl Mercaptan +.Hydrogen—
CH3SH
2.
+
H2
Methane +.Hydrogen Sulfide
--- CH4
+
H2S
Dimethyl Sulfide +.Hydrogen — 5-Methane +-Hydrogen Sulfide
CH3 SCH3
+
SH2
-- > - ZCH4
+
H2S
3. .Dimethyl Sulfide + Hydrogen---HEthane + Hydrogen Sulfide
CH3 SCH3
4.
H2
--- ^ C2Hg
+
-H2S
Dimethyl Disulfide + Hydrogen — HMethane + Hydrogen Sulfide
CH3 SSCH3
5.
+
.+
3H2
--- ZCH4
+
ZH2S
Dimethyl Disulfide + Hydrogen — H-Ethane +■Hydrogen Sulfide
CH3 SSCH3
+
ZH2
--- C2 H6
+
ZH2S
The data required.for the calculations- are given in Table I.
The source for the data.is given in the footnotes.
Since no data were
available for some of the compounds, methods of estimation were used.
.When more than.one method of estimation was used, the .results were
averaged.
-36The equations used for the calculations are as follows:
A H ° o = AH°
Ac0
.
- AH:
298 (products,)
298 (reactants)
__ O 0
^298
_Q°-
^298 (products.)
Ap; =
^298 (reactants)
- T A S °98
K
= e- A F 7 RT
^eq
In' order to account for deviations from-ideality, the activity co­
efficients were calculated from
Then
■where A N = moles of products - moles of reactants
-37Table II.
Compound
'T0 (oK)
.Thermodynamic Data
Pc (ATM)
Source
^298
Kcal/Mol
^298
Source
EU/Mol
305.3
48.2
(11)
-20.24
33.1
■12.8
(19)
0
Hydrogen Sulfide
373.2
88.9
(23)
- 4.82
49.15
(23).
Methane
190.8
45.8
• (U)
-I7.89
44.50
(23)
Methyl Disulfide
617.0
53.1
(30)
- 5.75
80,54
(8 )
Methyl Mercaptan
470.0
■54.6
. (19)
- 5.47
60.16
(8)
Methyl Sulfide
503.1
54.6
(19)
68.32
(8)
Ethane
Hydrogen
8.98 '
54.85
(23)
■ 31.21
(23)
-38TaBld III.
Activity Coefficients
In ¥ -=
9
Tcp
128 P%T
Compound
Temp- °F
300
350
C p H,
400
450
500
550
300
35P
H2
H 2S
5
0.998
0.998
0.999
0.999
1.000
1.000
0.989
0.991
0.993
0.995
0.996
0.997
1.009
1.005
10
0.978
0.983
0.986
0.990
0.992
0.994
20
0.956
0.966
, 0.973
0.979
0.984
O.988
400
450
500
550
1.000
i .000
1.000
1.005
1.004
1.004
1.004
1.017
1.010
1.009
'1.009
.1.009
1.008
300
550
0.998
0.997
0.997
0.996
0.995
0.994
1.029
1.023
1.019
1.016
1.013
1.011
1.059
1.047
1.039
1,032
1.026
1.022
.1.000
0.998
1.000
1.000
1.000
1.001
1.002
0.997
0.999
1.000
0.796
0.833
0.855
0.869
0.897
0.913
0.634
0.693
0.732
400
450
300
350
CH 3SSCH 3
I
1.002
1.001
1.001
500
550
CH 4
Pressure,.ATM
400
450
.1.000
500
550
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
30Q
350
0.977
0.982
0.984
0.987
0.989
0.991
0.894
0.912
0.925
0.937
9.948
0.955
400
450
500
550
1.000
1.000
■1.035
1.020
1.020
1.018
1.017
1.016
.
1.126
1.096
1.080
1.065
'1.053
1.044
I..002
1.003
1.003
0.772
0.807
0.833
-39Table III.
Compound
Temp 0P
300
350
CH3SH
400
450
500
550
300
350
CH 3SCH 3
(Confc.)
400
450
500
550
Activity Coefficients
Pressure, ATM
10
20
I
5
0.991
0.993
0.994
0.995
0.996
0.997
0.955
0.963
0.970
0.975
0.980
0.983
0.913
0.928
0.940
0.951
0.961
0.966
0.833
0.861
0.884
0.904
0.923
0.933
0.985
0.991
0.992
0.994
0.995
0.996
0.929
0.954
0.961
0.969
0.974
0.978
0.862
0.911
0.924
0.938
0.949
0.957
0.830
0.853
0.871
0.901
0.915
0.744
-40. Thermodynamic' Study Continued
CH 3S H (g)
Reaction I:
+ 'H2 (g) — >- CH 4 (g)
-17,890 + .(-4820)
-5470
A H,
298
H 2S(g)
+
"
A H° g = -20,540 cal/mol
60.16
'298'
+
21.21 — > 44.50
+
49.15
A S°9g u 2.28 EU/mol
^^^298
^ Ff ^ 9 8
-20,340 - (298)(2 ;28)
298
A F* g =.-21,020 cal/mol
af
/r t
•K eq = e
( t CH4 ) ( if H 2S)'
( t CH 3SH)(tf H2 )
Keq
Ky
Temp 0F,
a
S
H
-
300
350
400
450
500
550
_
^eq
"
Ky
A 'F6 cal/mol
(I - &)f
K eq
2.42 x 10 ^
-21,982
5.01 XT. ioio
-22,045
-22,109 . ■1.51 X IoJ0
4.26 x 10%
-224170
-22,240
1.38 X 10%
5.01 .x.10°
-22,300
Ky
1.002
1.002
1.002
1.000
1.000
1 .000"
kN
2.41
5.00
1.50
4.26
1.38
5-01
Conversion
x 10^
99 .99
x IQlO
x IQlO
x 10?
>
(Conversion greater than 99-99 percent for-pressures of 5, ..10, and
20 atmospheres. Data not shown.)
-41Thermodynamic Study Continued
CH3 SCH3 ..+ 2Hg— 5--2CH4
Reaction 2:
-8980
h298:
*
+ HgS
0 -- >-( 2 )(-17 ,890)
+
+
-4820
4 H °98 = -31,620 cal/mol
3°
=
68.32
(2 )(31.21)
+
(2 )(44.50)
+
49.15
J S“nQ = 7 . 4 1 EU/mol
'298
P‘
t S 411Z9S -
j
t
4 s Z9S
4 f Z9S m - 3 1 - 620 - (T-W)(Z9S)
A Fgng =
-53,710 cal/mol
Keq , e-' 4 ^
K
=
(
H 5S )
(% CH3SCH3)(X h 2)2
*
X\|T —
CH4 )2 (
Ke 9
---------
—
K eq
---
K%
■Temp 0F
Ky
4 F 0cal/mol
_
—
^
----------------
(I - .x) (2 - -2x) 2
k K
K eq
kN
Conversion
18
300
.I atm
a
td
H
350
400
450
500
550
-34,730
-34,940
-35,140
-35,340
-35,560
-35,760
1.23.x
1 .12'x
I >55 x
2.40 x
4.26 X
' 1.02 x
I I
1.013
1.011
■ 1.010
1.009
.1.008
.1.008
1.22 x
X
.1.11
1.54
2.38
4..23
-x
X
x
1.01 x
(Conversion greater -than 99-99 percent for. pressures of 5
20 atmospheres. Data not shown.)
>
10, and
99.99
y?
-42Thermodynamic Study Continued
■Reaction 3:
+ Hg —
-898O
'H
A
CH3 SCH3
298'
+
CgHg
O —
+ HgS
-20,240
+
-4820
^ ^!98 = "1^ jOS o cal/mol
68.32
+
31.21
54.85
+
49.15
4 rS °98 = 4.47 EU/mol
0
TAS
298
A F*.9g = - 16,080 - .(4.47) (298) = -17,411
K
eq
■ft
,
e - a p ^ RT ■
-
(.Y C.^g) (KHgS)
------------- :
--
)
(V CH3 S1CH3)(Y Hg)
■I atm
(I - x )2
Temp 0P
A P° cal/mol
300
350
-I? ,970
-18,090
-18„210
400
450
500
' 550
-18,340
-18.,470 .
-18)590
K eq
t
^"N
Conversion
2.09 x- 10,
1.001
6.91 x-io:
2.46 x. 10!
9,55 x. 10,
I..000.
2.09 x .IO?
6.91 X-IOq
1.000
1.000
0.999
9.55 x IOj
3.99 x ipf
3.98 xio,
1.90 x :10
0.999
99.99
2.46 x IQP
1.91
X
10'
.
T
(Conversion greater than. 99*99 percent for pressures of 5,-10,-and
20 atmospheres.
Data not shown.)
-43Thermodyhamic Study' Continued
CH 3SSCH 3
Reaction 4
A ' E29.8:
“575Q
3H 2
+
SCH 4 ■ + 2H2S
0 — ^ (2 ) (-17,890)
’+
(2 ) (-.4820)
+
•4H° 0 ='-39,570 cal/mal
80.54
S^98:
(3) (31.21) -^.'( 2 ) (44 .50)
+
+" (2 ) (49.15)
/lS”g8 = 15.13 EH/mol
T4S
298
A ' F °g8 = -39)580 - (15.13)(298)■= -44,080 cal/mol
K
.
. - A l fM
I ~<0H4)g ( l^ H gS )2
( X CH 3SSCH3){
p’
rN
_ Kgq- = K*
■Temp .°F
a
ta
H
300
350
400
450
.500
550
H 2)3
, K*
A F0cal/mol
-45,970
'.46,380
-46,950
'-47,210
-47,650
-48 ,070
4
l6x'
.(l.-:x) (3 - 3x) 3
K eq
■K X
■24
.1.00 x;10,%
4.17 X=IO^
4.17- x / i q ^
•3.62 x a o ^
.4.26 x IOl-O
7.07 X 1JOis
1.012
. 1.009
..1.007
■1.005
■1.001
0.996
■K M
9,88 x.lo23
Conversion
99.99
4 . 1 3 -x I O ^
4.14 x IO21
3.60 x IO2O
4.25 X l O ^
7 . 1 0 -'X-IOis
>
(Conversion greater than 99-99 percent for-pressures of 5 ■10, ■and
20 atmospheres. Datajnot shown.)
•r
.-44Thermodynamic Study- Continued
■Reaction.5 :
-CH3SSCH 3
-5750
.A H° 9g:
H H 2 — S-C2Hg
+
+
-O -- ?- -20,240
SH2S
,+
(2 )(-4820)
A E 298 = -24jl30 cal/mol .
80.54
I■
^298=
(2) (31.21)
+
54,85
+
(2) (49.15)
A Sj 98 = 10.09 EU/mol. '
P0 „ = -24 -,130 ■- (10.09) (298) = -27,138 cal/mol
A F'
298
- A F°/RT
%eq =
e
U
CaHg) C ^ H 2S-)2
(t
CH3SSCH3 ) (
K.
.Tf
jxN "
5.
.
11
£>
H2)
i1 -- x) (2 .-
H
-Temp- 0F
300
=350
S
-P 400
cti
iH 450
500
550
■F cal/mol
-28,390
-38,670
-28 ,450
-29,220
'-29,520
-27,790
4x 3 '
K-e'q- 'r- '
'
r %
K eq
14'
6.15
.1.00
2.14
•5.50
- 1.41
7.57
Zx)^
-X'.10
x .10^'
.. - 1.008
x ,103-2
'1.005
--X.-.1 0 ^
x.-lO12
X-. I O 1 *
1.010
1.003
1.001
0.996
Conversion
6 .0-9 Xiio^
9 .94-x ..IO^
2.13 %'ioT;
5.48 x-lb
.1.41 X.:10^2
7.60
X
IOiu
,99.99
Y
(Conversion, .greater-than. 99-99'Percent for-pressures of 5 , •10, and
;2 0 ;atmospheres. .Bata not shown.)
To Temperature
H O Volt Line
Indicator
Figure 2.
Powerstats
T--
-45-
Schematic Flow Diagram of Hydrogenation Unit
V j - r v i - f v
0 P
1 DH- HCD O
P
H- Cf
U-I-
CD S ’
oq
Cooler
-Cold H2O
O
<-i
HD
P
I
Reactor
Pressure
Controller
Stripping
Flasks
Sample
Flask
Ice
Bath
-46-
Figure 3.
Detailed Diagram of Reactor
. Table-IV. .Sulfur Content of Crude Sulfate Turpentine
S o u r c e _____________________
Sample No,
Waldo r f - H o emer; ,Missoula,.Montana
Weyerhaeuser; .Everett, Washington
Weyerhaeuser; Springfield, Oregon
.'
.Sulfur.-ppm
I
540
!2
3290
.1
2
1710
1 2 ,800%
. .1
1360
•2
■2400
Georgia Pacific;.Toledo, Oregon
.I
5860
Rayonier, Inc.;,Jessup,fGeorgia
I
I
365
Tatile V.
■Crude Sulfate. Turpentine Compositions
0)■
ti
0)
0
•rl
0)
Cd'
I1
c
ti
o
Waldorf-Hoerner, . ■
.Missoula,,Montand '
.54.0
1.0
Weyerhaeuser,
Sphingfield:, Oregon
84.0
Weyerhaeuser,
Everett, Washington
~
Source
•1 'i l.
«(D
£.
0)
£
•H
Pt
42
CD '
£
■
I
KY
cti:
-p
H'
Q)
rD
«8 CO
CU 0
)
■s
£
<D
£ '
Ig
rti -P.
,unidentified
■Composition, Weight %
,'9.6
41.5 • 12.0
•2.0
2.9
■5.5
■T
9.6
85,8
2.4
5,5
'T
,8.5
Georgik Pacific,
. Toledo,.Oregon
87.6
2.2
.5,6
6.6
—
Rayonier,.Inc.,,
.Jessup,, Geohgia
64,7
1.0
.19.1
9.5
5.0
--
-49Table.VI. .Distillation Data for Crude Sulfate Turpentine
from Toledo,.Oregon
Sample Size: ■1000 ml
Reflux R a tio: 10:1
Barometric Pressure '= 640 mm Hg
■■Volume % .Distilled
Temp °C
IBP
>5
■2
•138
4
.149
j 6"
■8
.10
.12
14
■150
■150 ■
.150
1$0.5
,16
150.5
150.5
■18
■ 150.5
20
22
150.5
150.5
■150.5
■24
26
28
150.5
150.5
Volume % Distilled
'30
32
34
36
38
40 .
42
44
46
48
50 '
52
54
56
58.
Temp 0C
150.5
150.5
■ 150.5
150.5
151
151
..151
■ 151
— — —
“ “
—
— —
154
160
16?
Decomposition Starts
210
200
190
180
170
/
Z
O
Temperature
0
160
CU
150
U
CU
g1
140
r
-50-
U
S
CU
Eh
130
120,-.
H
(Barometric Pressure = 640 mm Hg)
O
100
90
0
1
I
1
10
I
20
I
I
30
1
I
40
I
I
I
50
I
60
I
I
70
I
I
80
Volume Percent Distilled
Figure 4.
Distillation of Crude Sulfate Turpentine from Toledo, Oregon
I
90
-51Table VII. ;Distillation Data for Crude Sulfate .Turpentine
■from-Jessup,■Georgia
Sample Size: 1000.ml
Reflux Ratio;
10:1
Barometric Pressure:
636 mm-Hg
V o l u m e •% ,Distilled
.T e m p ■°C
Volume % Distilled
■Temp 0C
IBP
.'118
2
•146
4
.150
150
•150
■42
44
46
48
50
52
54
56
.58
60
150.5
150,5
151
■ 151
.151
■151
152
153
"154
.155
62
64
• 158.5
6
.8
■10
■12
14
•16
18
20
22
150.5
■24
26
I.5O .5
150.5
150.5
66
.68
,150.5
150.5
72
28
•30
32
,
:150
•150
150.5
■150.5 ■
■150.5
.150.5
34
■36
■3.8
40
.150.5
150.5
150.5
150.5
70
74
76
78
80
156.5
159.5
160
.160,5
■l6l
•162.5
164
166.5
De c o m p o s i t i o n
Starts
Temperature
l80 -
140 -1
(Barometric Pressure = 6)6 mm Hg)
Volume Percent Distilled
Figure 5.
Distillation of Crude Sulfate Turpentine from Jessup, Georgia
-53Table VlII.' ,Distillation Data.for Crude Sulfate Turpentine
from- Missoula,Montana
Sample Size: -1000 ml
Reflux Ratio: :10:1
Barometric Pressure: 640.7-mm-Hg
Volume % Distilled
IBP
.2
4
6
8
•10
12
14
16
18 ■
20
22
24
26
28
30
•Temp °C
. 134
■ ,.146
:147
' .149'
-149.5
: 150
158
!■150
150.5 ■
150.5
■ 151.
1.51
151.5
■ 152
153
.154
Volume
',Distilled
32
34
•Temp 0C
,
'1:55
'156.5
1.57
36
38
■40
42
44
■46
48
50
' 52
54
56
.58
60
62
64
159
160.5 '
162
163,5
164
.
■
164.5
165
'165
■ I 65
' 165
■'■165
165
".165.5
Decomposition
Starts
-46-
Temperature
(Barometric Pressure = 640 mm Hg)
Volume Percent Distilled
Figure 6.
Distillation of Crude Sulfate Turpentine from Missoula, Montana
-.55Table IX.
Distillation Data for Crude Sulfate Turpentine
from Springfield, Oregon
Sample Size: 1000 ml
Reflux Ratio: 10:1
Barometric Pressure: 637-5 mm Hg
Volume % Distilled
Temp °C
IBP
47
145
2
.150
150
150
150
4
6
8
10
.12
. 150
14
■■150
16
18
20
22
150
1.50
24
26
28
30
150
.
1.50
.150
150
150
1.50
Volume % Distilled
32
34
36
38
40
42
44
46
48
. 50
52
54
56
Temp 0C
150
151
151
151
151
151
151
. 151
151
1.51
152
■152
' 153.
156
Decomposition
Starts
58
60
6
■ '
210
200
-
190
180 "
170
o
160
150 140
130
-56-
Temperature
o
\-
120
(Barometric Pressure = 637.5 mm Hg)
HO
100
J---- 1
---- 1
____ I____ 1
____ I____ I____ I
____ 1
____ I
____ 1
____ I
____ 1
____ I
20
30
40
50
60
70
80
90
Volume Percent Distilled
Figure 7.
Distillation of Crude Sulfate Turpentine from Springfield, Oregon
90
■57
Table X. .Distillation of Crude Sulfate Turpentine
from Eyerett, Washington
>
Sample Size: ■1000 ml
Reflux Ratio: 10:1
Barometric Pressure:
644 mm Hg
Volume % Distilled
IBP
■2
4
6
8 .
10
12
14
.l 6
18
20 ■
22
24
26
.28
30
■32
■54
36
38
-Temp- 0C
6l
•l 4 l .
:146
■ 146
-146.5 '
147
■147
147
■ 147
147
147
147
■ 147
■147
•147
. 147
147
■ 147
■ 14,7
147
•Volume $ 'Distilled
■40 .
■42
■ 44
46
. 48
50
■52
54
56
58
■■Temp °C
6o
147
. 147
'147
."147
147
148
l48 .5
149
151.
■ 153
1 5 7 .5
62
'161
64
••164
1-66.5
66
68
70
72
74
76
78
'168
171
. 173.5
180
185.5
Decomposition
Starts
Temperature
-58-
(Barometric Pressure = 645 mm Hg)
Volume Percent Distilled
Figure 8.
Distillation of Crude Sulfate Turpentine from Everett, Washington
-
Table XI.
59
-
Preliminary Desulfurization- Data
Temperature Effect
Temp
(0F)
400
450
Pressure
(psig)
25Q
250
500
250
550
250
SV
(hr-1 )
10
10
10
■ 10
Sulfur (ppm)
Feed
Product
580,
5&0
.580
580
200
320
430
430
Conversion
.' %
65.5
44.9
22.4
22.4
Hydrogen Rate.= 1000 SCP/bbl
Space Velocity Effect
450
4.50
450
290
230
290
SV
I
H
Pressure
(psig)
%
Temp
(0F)
'10
5
2.3
Sulfur (ppm)
.Feed '
Product
Conversion
#
980
320
44.9
I 6OO
1200
1900
29.0
2100
. Hydrogen Rate = 1000 SCP/bbl
o
9-5
.
-SoTable XII.
Data For Runs Using 20^-H 2S-SO^-H 2
Reactor Temperature: 550°F
■Reactor Pressure:
250 psig
Space Velocity: 10 hr "1
H 2S-H 2 -Rate: .1000 SGF/bbl
Sample
a-Pinene-Feed, Springfield, Oregon
Reactor Product
a-Pinene Feed,,Missoula, ,Montana
Reactor Product
a-Pinene Feed, Jegsup,•Georgia
1
Sulfur,,(ppm)
510
■ 10,800
-150
9,450
190
Reactor Product
13,100
a-Pinene Feed, Springfield, Oregon
' 1,570
Reactor Product
11,900
a-Pinene Feed,-Toledo,.Oregon
Reactor Product
720
11,900
■6lTable XIII.
Extended Run on Non-SulfIde.d Catalyst at High- Pressure
Feedstock: a-Plnene, Springfield, Gregop
Reactor Temperature: -UOO0F
■Reactor Pressure: 250 pslg
Space Velocity: 5 h r -1
Hydrogen R a t e : 5000 SCF/bbl
Sulfur Content of -Feed: .510 ppm'
A-BdlfUl1 (ppm)
Conversion
0
510
0.0
1.5
300
■Ul.U
5 -
-195
62.3
4
■165
.67.4
5
-175
6 5 .3
7
200
61.0
11
:90
6 3 .3 .
18
■175
6 5 .3
26
180
6 4 ,3
Hours on Stream
„
550
Total Sulfur, ppm
Feedstock: a-Plnene, Springfield, Oregon
Reactor Temperature: 400°F
Reactor Pressure: 250 psig
Space Velocity: 5 hr -1
Hydrogen Rate:
5000 SCF/bbl
I
rvi
1
0
150 -
100
-
50
-
0 _______ 1______ I_______ I______ I _______ I_______ 1______ 1________ 1_______ 1_______ 1_______ 1_______ 1_____ 1_________|_
0
2
4
6
8
10
12
14
16
18
20
22
24
26
28
Hours on Stream
Figure 9-
Extended Run on Non-Sulfided Catalyst at High Pressure
-63- Table. XIV.
Extended Run on Non-Sulflded Catalyst at Low Pressure
Feedstock: .a-Plnene, Springfield,:Oregon
Reactor Temperature: 400°F
Reactor^Pressure: .25 psig
Space Velocity:
2.5 hr -1
H 2 R a t e : 5000 SCF/bbl
Sulfur Content of Feedstock: 510 ppm
Hours On Stream
Sulfur (ppm)
Conversion
2
.140
72.5
3
120
76.5
■5,5
140
72.5
• 7.5
130
74.5
9.5
130
.74.5
11.5
1)0
74.5
13.5
•155
69.7
■
-64Table XV,
Extended,Hun .on Sulfided Catalyst' at Low Pressure
Feedstock: .a-Pinene, Springfield,.Oregon
Reactor Temperature: -HOO0F
Reactor Pressure: :25 psig
Space Velocity.: 2.5 hrrl
H 2 Rate:
5000 SCF/bbl
Sulfur Content of Feedstock; :510 ppm
■ Hours,.on Stream
2
■4 .
Sulfur (ppm)
Conversion
590
.215 -
57.9
6
.160
. .68,7
8
130
7^.5
19
90
82.4
24
.70
8 6 .3
28
. 65
87.3
32
70
.8 6 . 3
a-Plnene
240
*
160
-
120
-
Non-sulfided
-65-
Total Sulfur (ppm)
Reactor Pressure -- 25 pslg
SV -- 2.5 hr "1
Catalyst
14
16
20
22
26
28
32
34
Hours On Stream
Figure 10.
Lineout Time for Sulfided and Non-Sulfided Catalyst at Low Pressure
36
W AVELENGTH
IN
M IC R O N S
6___________ 7________ 8
O-N
On
I
2500
2000
1900
1800
1700
1600
1500
WAVENUMBER
Figure 11.
1400
IN
1300
1200
1100
KAYSERS
Infrared Spectrum of Known a -Pinene Sample
W AVELENGTH
4
IN
M IC R O N S
5
50
40
30
-67~
W AVENUMBER
Figure 12.
IN
KA Y S E R S
Infrared Spectrum of a-Pinene Distilled From
Crude Sulfate Turpentine (Reactor Feedstock)
W AVELENGTH
IN
M IC R O N S
6___________ 7________ 8
k
I
2500
2000
1900
1800
1700
1600
1500
W AVENUMBER
Figure 13.
1400
IN
1300
1200
1100
1000
KAYSERS
Infrared Spectrum of a-Pinene Reactor Product
900
-:
Table XVI.
69-
Effect of Temperature op Sulfur Removal
F e e d s t o c k a - P l n e n e , Springfield, Oregon
Reactor
s : 25 pslg
Hydrogen-Rate: .5000 SCF/bbl .
Sulfur- Content )f Feedstock:: 510 ppm
Reactor- Temp
°F
Trial I
S,V.
Trial 2
^300
-2.5
350
■2,5
50
350
'5.0
250
---
350
.10.0
315
—
400
2.5
70
75
400
5.0
LT\
CO
■ loo
400
.10.0
175
205
450
2.5
. '75
90
450
5.0
-
220
500
2.5
-115
.500
.10.0
140
O
LT\
'155
.82.5
^
90;
.
.Average Conversion
56,8
220
■ 95
10.0
■Trial 3
-51.0
---5-5
38.2
8-6.9
81,8
"- -
.62.8
—
83.8
HO
■
--
79.9
---
----
69.7
130
‘---
76.0
■
■
72.5
a -Plnene, Springfield, Ore.
Sulfur = 510 ppm
Reactor Pressure: 25 psig
H 2 Rate:
5000 SCF/bbl
-oi~
Total Sulfur (ppm)
Feedstock:
Reactor Temperature °F
Figure 14.
Temperature Effect on Sulfur Removal
• 'Table XVII.
Effect of Pressure on SVIfur'Removal
■Feedstock:
a-^Pinene, .Springfield, Oregon
Reactor Temperature: 400°F
:Space Velocity: .2.5 hr -1
■ H 2 R a t e : ' 5000 SCF/bbl
Sulfur Content of Feedstock
510 ppm
Reactor Pressure
(psig)
. Trial I
•Trial 2
Average
■ Average
Conversion
25
70
75
72.5
85.8
■100
105
95
-100.0
80.5
'175
'125
105
II 5.O
77.5
250
.145
135
140.0
72.6
Total Sulfur (ppm)
220
20
-
25
-L_
-J--------- 1--------- 1--------- 1--------- 1_________ i_
50
75
ioo
125
150
175
Reactor Pressure (pslg)
Figure 15.
Pressure Effect on Sulfur Removal
200
225
250
-73Table XVIII. •Effect of .'Space Velocity on Sulfur-Removal
■Feedstock: .-a-Flnene, Springfield, Qregon
Reactor Temperature: 400°F
Reactor•Pressure: :2 5 'pslg
H 2 'Rate: .5000 SCF/bbl
Sulfur Content of Feedstock:
$10 ppm
Space Velocity,
■hr"1
-Trial -.1
Trial 2
- Trial 3
Average
Conversion
■50
.---
--
90.2
2.5
■55
■70
75
86,9
5.0
85
■100
—
81.9
1755
205
--
.62.7
240
LOv
CXI
10.0
'15.0
O
1 .2-5
.52.0
~hL-
Total Sulfur (ppm)
260
Figure 16.
Space Velocity Effect on Sulfur Removal
-75• 'Table XIX. .Effect of Hydrogen Rate on Sulfur-Removal
•Feedstock:
a-Plnene, Springfield,■Oregon
Reactor Temperature: /UOOcF
Reactor Pressure: .250 pslg
Space Velocity:
5' hr-1
Sulfur Content of Feedstock;: 510 ppm
Hydrogen Rate,, SCF/bbl
Sulfur (ppm)
'Conversion
2500
-510
3 9 .2
•5000
■ 180
64.7
.10,000
•150
■70,7
Percent Conversion
100
-76-
20
-
0 —
1000
___I____________ I____________ I____________ I____________ I____________ I____________ I____________ I____________
2000
3000
4000
5000
6000
7000
8000
Hydrogen Rate, SCF/bbl
Figure 17.
Effect of Hydrogen Rate on Sulfur Removal
9000
10,000
-77Table XX; .Composition.of Reaptor Products
•Feedstock:
Temp
SF
Pressure
(psig)
.SV
hr"1
Feedstock
25
25
25
25
25
25
-IOiO
400
400
400
.400
400
25
100
175
■2.5
•2.5
■2.5
400
400
400
400
'400
25
25
25
25
25
)00
350
400
450
500
500
250
500
a-Plnene, SprlngfIeld,•Oregon
9 4 .9
•2.. 5
2.5
2.5
■2.5
2.5 •
2.5
2.5
.■1.25
2.5
■5.0
•10.0
-1 5 , 0
•Camphene
B —
'Plnene
92.6
92.0
81.9
77.5
-3 9 .0
7 8 ,5
81.9
69.0
•71.6
•71.5
. •19.0
41.5
.
81.9
88.8
9 2 .4
9 2 .7
.
3.4
5.1
6.0
'
■11.3
'15.1
3 8 .1
. '12.6
1 1 .3
1 8 .3
.•'■17.9
-18.4
bPinene
Dipentene
Pinane
'1.7
-2.3
-2.0
1.8
2.4
5.0
6.5
1 7 .5
6,5
-1,8
-2.1
■1,5
2.0
10.6
■9 . 0
8.1
0 .9
.
• 1,8
. 1.7
- 1.7
.2,6
■5.4
5.0
3 9 ;0
42.0
3 6 .9
/11.3
6.2
4.8
■4.7
"Mis c
. 21,6
5 .0
3.4
'■1,1
T'
-T
78
O- PtNCNC
H EEDSTOCK
d
Figure 18.
Chromatogram for a-Pinene Feedstock
Is!
79
■REACT OS_BR O DUCJ-
4 0 0 ° F___ 2 5 p s ig _ SV = S-S
Figure 19.
Chromatogram for Reactor Product at 400°F,
25 psig, SV = 2.5.
REACTOR—EROO-UCT-
PSpcij
R V ,194
W|
Figure 20
I
Chromatogram for Reactor Product at 400°F, 25 psig, SV = 1.25
-80-
AnrPF
REACTOR PRODUCT
SOOpsig
Figure 21.
SV= 2 .5
Chromatogram for Reactor Product at 400°F, 500 psig, SV = 2.5
Table XXI.
Sulfur Removal on Different Feedstocks
Reactor Temperature: 400°F
Reactor Pressure: ■25 ‘pslg
.Space Velocity:
2..5. hr -1
H 2 R a t e : 5000 SCF/bbl
Source
Sulfur (ppm)
a-Plnene F e ed,.Springfield,■Oregon
Reactor Product
510
a-Plnene Feed, .Toledo,,Oregon
Reactor Product
720
a-Plnene Feed,.Missoula, .Montana
Reactor Product
a-Plnene Feed,,Everett, Washington
Reactor Product
a-Plnene Feed,.Jessup,-Georgia
Reactor Product
55
Conversion
89.2
— — "
65
■9 1 .0
..150
50
66,7
-..i860
580
.190
55
.68,8
— — —
71.0
'Table X-XII. ,Sulfur Removal on Crude Sulfate Turpentine (CST)
Reactor- Temperature: .400°P
Reactor-Pressure: .25'psig
Space. Velocity: ■2.,5 hr "1
H 2 R ate: 5000 SCP/bbl
Source
CST, Springfield,•Oregon
Reactor Product
GST,,Toledo,,Oregon
Reactor Product
GST,'Missoula, .Montana
Reactor Product
GST,.Everett, Washington
Reactor Product
OST,,Jessup, Georgia
Reactor Product
Sulfur (ppm)
Conversion
2400'
705
■70.7
.5860
1355
3290
700
■ 12,800
2550
365
260
60.2
■ ■ ■■
78.8
_* ■
80.0
■ ■—
28,8
-84Table XXIXI. .Catalyst Life
Feedstock; ■a-rPlnene, Springfield, Oregon
,Sulfur Content of Feed:
$10 ppm
Reactor Temperature: 400°F
Reactor Pressure: 25 psig
Space Velocity,: 2.5 hr -1
H 2 Rate:
5000 SCF/bbl
■Catalyst-Volume: -12 cc
Vol Oil/Vol Catalyst
Sulfur
Conversion
80
.?0
.86.3
186
60
88.3
592
55
8543
-85Table XXIV.. . Properties of Houdry "Series
Cobalt Molybdate Catalyst
I.
Chemical Composition:
C o O
-MoO3
15#
AlgO 3
82#
N a g O
■2.
3.,
Surface Area:
Pellet Size:
0 .05#
:310-540.meters2/gram
Diameter -- 0.115-0.135 inch
-Length
4. .Average Pore Diameter:
5.
.
— .0.094-0.250 ,inch
58 Angstroms
Bulk Density: -O.8O-O. 9O g/cc
6 . Pellet Density:
1.3 g/cc
■LITERATURE CITED
I.
Adams, D .■F ., and R ; .K . .Koppe, "Gas Chromatographic Analysis of
'Hydrogen Sulphide, Sulfur Dioxide,.Mercaptans,.and Alkyl
Sulfides and Disulfides",. TAPPI, V o l ..42,.No. 7,,p p . 601605, (July. 1959) . .
.2.
ASTM Standards on Petroleum Products and Lubricants, American
Society for Testing Materials
(195$) •
.5.
"B. C . Research Council Discovers Method to Reduce Kraft Mill
Odors", Paper Trade Journal, January 194-9, P- 14-.
4-.
Bergstrom, H. 0. V. , "Pollution of Water and Air by Sulfate Mills,"
Pulp and Paper Magazine (Canada), V o l , 54-,.No.. 12,
pp 135-140,
5.
(1953)-
Bialkowsky, .H. W., and G. 0. Dehaas-, "A Catalytic Oxidation Pro­
cedure for-Determining Sulfur Compounds in Kraft Mill
Gases," TAPPI j -Vo I . .36,-No. 7, pp 330-536, (1953),
6 . Bonnholm, G.- G., "Purification of Sulfate Turpentine Oil,"
Finnish Paper-Timber Journal, .22, 339-34-2 (194-0).
7- .Campetti,.J. C., "Purification and Sweetening of Sulfur-Containing
Turpentine," ItalyaPdtent 574-,248 , .March 16, .1958 •
8.
Chermin, H. A.- G., "Thermo Data for Petrochemicals",.Hydrocarbon
Processing -and Petroleum- Refiner,.V o l ..4-0,. Nos. 6 ,, 9,
and 10,.pp 179-182,. 261-263,1145-147.
9.
Collins, R . A., "Refining Sulfate Turpentine", U. S . Patent
2,409,614, ,Oct...22 ,,1946.
10.
Colombo, P., Corbetta, D., Pirotta,- A., and A. Sartori, "Critical
Discussion on the Analytical .Methods for-Mercaptan and
Sulfur Compounds",.TAPPI,.Vol. 40,.No. 6 ,.pp 490-498,
(July. 1957).
11.
12.
.Doss, .M. P ., Physical Constants of the Principal Hydrocarbons,
.The Texas Company,.New,York,,(1943).
Dusenbury,,M. R., and,Reese,,J. E., "Some Observations on Sulfate
Turpentine-Recovery",-TAPPI,-Vol..35,'No; 8 ,,pp 365-367,
.(1952).
13.
Efishev,. I. .I. , et al. , "Industrial.. Purification of Sulfate Tur­
pentine", Bumazh. Prom., 2 9 , -No. 6 ,,pp 23-25, (1954).
-87Literature Cited (Continued)
14.
■Enkvist,.T . , "Experiences Obtained During■Tests for Volatile Sulfur
Compounds.in Sulfate Turpentine1', Finnish Paper Timber
Journal, 2,9,,No..), pp )8-44, (1947).
1) .
16.
Felicetta, V . F . , Penis ton, Q,. P., and J.-L.. McCarthy, "Deter­
mination of Hydrogen Sulphide,.Methyl•Mercaptan,Dimethyl
Sulphide and Disulphide in Kraft Pulp.Mill Process Streams",
TAPPI,-Vol. )6,.No. 9, pp 425-4)2.
•Glasstone, S . , Thermodynamics for Chemists, D. Van Nostrand Company,
■Inc.,.New-TsfIey^ (T947).
17. •Gorlovskii, S."I., et a l ., "Turpentine", Russia Patent 121,98),
August 18, 1959.
18 . .Hashimoto,.M., "Turpentine as a ByPProduct from the Relief of
Sulfate Digesters", Japan TAPPI, No. 4, pp 8-15 (1954).
19•
Hodgeman, C , D . , -and H . - N . H o l m e s , Handbook of Chemistry and
Physics, Chemical Rubber Publishing Company, Cleveland,
Ohio, (1956).
20.
■Jennings, W..H., "Refining of Sulfate Wood Turpentine", U. S .
Patent 2 ,283,067, (1942).
21.
.Kiovsky,..J. R., Ph.D. Thesis, Montana State College,
(1962).
22. .Koester, D. W.,.Houdry Process and Chemical Company, Correspon­
dence with Arthur-Y. .Falk, April 25,-196).
2) .
L a n g e , N. A.,.Handbook of Chemistry,-Handbook Publishers,■Inc.,
Sandusky, Ohio, (195&)•
24.
Lardieri,,N. L., "Present Treatment Practice of Kraft Mills on
Air-Borne Effluents", Paper Trade Journal, April 14,
1958, PP 28-)).
25.
Lorand, E..J., "Odor Refining of Sulfate Turpentine",-U. S . Patent
2,395,055,.Feb..19, 1946.
26.
27.
.McCumber,.H..T.,.M.S. Thesis, Montana State College,
(196)).
McGregor,,G . . H . , Refining'Sulfate Turpentine", U. S . Patent
2,459,570,Jan..18,.1949.
-
88-
LIterature Cited (Continued)
28. .Mirovj-N. T . , "Distribution of Turpentine Components Among Speeies
of the .Genus Pinus", ■The- Physiology of Forest Trees,
The Ronald Press Company,-New 'York, Jl958)•
29. -Orr, L. E .,.M.S . Thesis,.Montana State College,
(1961).
JO.
R e id,-R.-C., and T.-K. Sherwood, The Properties of Gases and .Liquids,
.McGraw-Hill Book Company,.Inc.,.New York, (1958).
31.
Simonsen,. ,J.,L. ,-.The -Terpenes , Cambridge University Press , -Vol..I I ,
2nd Edition, (1957).
32.
Smirnov,.D ,.N .,■a n d .N ..V .-Fetkevich, "Removing Sulfur Compounds-From
Sulfate-Turpentine'-', Russia Patent 46,579 > •April 30,.1936.
33.
"Terpene Process Cools Erratic Menthol Supply", Chemical Engineering,
April 16,.1962, pp 80-8l.
34. -Trimble,.F., "Refining Sulfate Turpentine and Tall Oil",.U. S .
Patent 2,310.046, (1943).
35.
Zubyk, W..J.,-and Connor, A. Z., "Analysis of -Terpene Hydrocarbons
and Related Compounds by Gas Chromatography", Analytical
Chemistry, July i960,,p..912.
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