Note: Descriptions are shown in the official language in which they were submitted.
~13~?d75;
A method is disclosed for the preparation of chalco-
genides o the formula MXy ~herein M is selected from the group
consisting of ruthenium, osmium, rhodium, irldiumî preferably
ruthenlum, rhodium and lridium, most preEerably ruthenium, X
is selected rom the group consisting of sulfur, selenium,
tellurium and mixtures thereof, preferably sulfur and selenium,
most preferably sulfur; and y is a number ranging from about
0.1 to about 3, preferably 0.1 to about 2.5, or M is manganese,
rhenium or technetium, and y is about 1.5 to about 4, prefer-
ably about 2, which method comprises preparing a neat or nonaqueous reactive solution ox slurry wherein is added (i) a
ruthenium, osmium, rhodium, iridium, manganese, rhenium or
technetium salt, the anion of the salt preferably being select- !
ed from the group consisting of halide (preferably chloride),
acetate, carboxylate, nitrate and sulfate, and (ii) a source
of sulfide, hydrosulfide (HS ), selenide, tellurlde ions, and
mixtures thereof, preferably sulfur and selenium, most prefer-
ably sulfur, said source being selected from the group consist~
ing o~ K2X, KHX, Li2X, NaHX`, NH4~X, (NH4)2X, Na2X, (RNH3)2X,
liHX,(R,R~NH2)2X, (R,RIR'~NH)2X wherein R, R7 and Rl' are the
same or different Cl-C20 alkyl, C6 C20 Y
Cl-C8 alkyl, C6-Cl~ aryl and X is a chalcogenide select-
ed from sulfur, selenium, tellurium, and mixtures thereof,
preferably sulfur and selenium, most preferably sulfur. The
reaction may be run neat, ~hat is, in the absence of any added
solvent. Alternatively, a nonaqueous solvent may be utilized,
and, if used at all, is selected from the group consisting of
ethers having 4-8 carbons, acetoni~rile, benzonitrile, pyridine,
propionitrlle, N-methylformamide, dimethyl formamide (DMF),
l,2-dimethoxyethane (DME1r propylene carbonate, ammonia,
aromatics of 6-20 carbons, preerably C6-C12, molten sulfur,
sulfur dioxide, diglyme, ethylacetate, esters of from C4 to C5,
l., ~
~IL;372~5
sulfolane, dimethylsulfite, ~ributylphosphate, Cl-C30 amines,
preferably Cl-C~0, C5-C12 alkanes, preferably C6-C8, anhydrous
acids such a9 formic, and glacial acetic, alkyl halides of
from 1 to 20 carbon atomq, aryl halides of from C6-C20 wherein
the halide is selected from the group consisting of C1, Br and
I and typical hydrocarbon feedstreams. Te~rahydrofuran (THF),
ethylacetate, dimethyl~ormamide (DMF), chlorobenzene, chloro-
form, pyridine, propylene carbonate and acetone may be used as
solvents of choice.
The reaction proceeds spontaneously upon mixing at
low temperatures, temperatures below ~00C, and at atmospheric
pressure. The products may be isolated by filtration and wash-
ing using excess solvent (when a solvent is used) or by pumping
off the coproduced anion salt if it is volatile. Osmium
disulfide produced by the above method possesses a layered
structure having lattice parameters a - 3~52 and c = 6.15 and
a surface area of about 50 m2/gm. The technetium dichalco-
genide and rhenium dichalcogenide also possess a layered
structure, The manganese dichalcogenide possesses a pyrite
structure or an MnS structure depending on conditions of
preparation~
Compounds of the formula MXy wherein M, X and y
are as deflned above, prspared by the low temperature, non-
aqueous precipitation technique herein disclosed are superior
sulfur-tolerant catalysts in catalytlc processes, for example,
hydrodesulfurization (HDS), hydrodenitrogenation (HDN), hydro-
conversion, hydrogenation.
U.S. Patent 3,291,720 to Dobres et al describes a
process for hydrorefining and hydrocracking hydrocarbons with
a supported xhodium sulfide catalyst. The rhodium catalyst
ls prepared by impregnating a base with a rhodium solution
- 3 -
..~
~3~Z7~
such as of rhodium chloride and thenconverting to the sulfide
in situ by generating an H2S atmosphere.
~. M. Jaeger and J, H. deBoer Proc. Acad. Sci.
Amsterdam 23 95-lO~ (1920) disclose that at lower temperatures
(i.e.~vo C) quadxivalent Ru salts and (NH4)2S give a greenish~
black preclpitate which i9 soluble in an excess of the pre-
cipitating agent~ It should be noted that the method of
preparation involved in the article appears to be an aqueous
technique.
Lutz et al, Z. Natur~orsch, Teil B, 1971, 26 (11),
1096~7'describe the preparation of heavy metal sulfides by
precipitation from organic solvents. In2S7, CoS, NiS, CuS,
ZnS, CdS, HgS, PbS, Ag2S and a number of thiospinels were
precipitated from solutions of the metal naphthenate in C6H6,
THF, or naph~halene by H2S.
Numerous examples exist in the art of the use of
metal sulfides as hydrodesulfurization catalysts. Vol-
Epshtein et al, Soviet 323,431, describes the desulfurization ;~
of naphthalene and naphthalene containing fractions by hydro-
gen~tion under a pressure of hydrogen at elevated temperature
using a catalyst consisting of palladium sulfide on a carrier.
The catalyst preerably contains 0.3 to 5% Pd. The process
is carried out at 230-320C.
Dovell in U.S. 3,538,161 describes the preparation
of the selenides and tellurides of Ru, Rh, Pd, Os, Ir and
Pt and their use as catalysts in a number of organic reduc-
tions. The selenides were prepared by passing H2Se gas
through a solution of RuC14 (for example) in 50 ml of concen-
trated HCl diluted to 700 ml by H20. Precipitation of
Ru2Se3 was complete inrv l.S hrs. In like manner were pre-
pared the selenides o~ Rh, Pd, Os, Ir and Pt and the ~ellu-
ride~ of Ru, Rh, Pd, Os and Pt. ~iphenyl disulfide was
~ 4 -
- /'
~372~i
converted to thiophenol by the action of Rh telluride. Thus,
no C-C bonds are broken and the process has not resulted in
hydrodesulfurization. Schwartz in U.S. 2,448,790 describes
stable colloidal solutions of sulur and metal sulfides.
Colloldal solutions of As, Se, Mo, Sb, Sn, Ti, Pt and ~u sul-
~ides may be formed, for example, by dissolving one part of
powdered As in ~ive parts of 30~ NH4HS at room temperature.
To one part of the resulting sulfoarsenate, olle part NH4
reslnoleate and one part H2O are added. The mixture is decom-
posed with formalin or phorone until all the NH3 is combined
with the aldehyde or ketone.
The Group VIIb di- and poly-chalcogenides (MXy
wherein M is manganese, rhenium and technetium, X is sulfur,
selenium and tellurium and y is 2 or greater) have tradition-
ally been prepared, when preparation was possible at all, by
high temperature solid state techniques, or by aqueous prep-
aration methods which result in compounds possessing a high
degree of trapped water and hydrolysis products. The di-
and poly-chalcogenides have attracted great interest because
of their highly anisotropic pxoperties and intercala*ion
properties. Intercalates made using various metal chalco-
genides are useful as lubricants, battery cathodes and super-
conductors. (SPe Gamble et al, U S. 3,766,064).
However, a major drawback in the use of chalcogenides
is the difficulty encountered in their preparation.
ReS~ is normally prepared by the thexmal decom-
position of Re2S7, see J. Less Common Metals 24, 73-81,
1971. Re2S7 is itself prepared by treating acid perrhenate
solutions with gaseous H2S. The brown precipitate which
results is washed and dried over P2O5 or silica gel. The
product obtained contains excPss sulfur and water~ Re2S7
~37Z75
is amorphous to X-ray, This material i9 thermally decomposed.
At 400-450 C the product is still rich in excess sulfur and
has a composition of about ReS2 ,~. Crystalline layered ReS2
which is obtained only at temperatures over 1100C. is no
longèr amorphous to X-ray, possessing well developed crystal-
lite structures and large particle sizes. A similar situation
prevails for TcS2.
The stoichlometric ruthenium, rhodium, irldium,
osmium, rhenium and technetium chalcogenides, prepared by the
nonaqueous precipitation technique of the instant process are
finely divided small composite particles or completely non-
crystalline. They possess crystallite sizes of about 50 A x
100 A or less, and particle sizes of 0.1 micron (1000 A) or
less, preferably less than 0.05 micron (500 A), that is,
particulate material which is amorphous to X-ray diffraction
(see "X-ray Diffraction by Polycrystalline Materials", Ed.
Ho5~ Stokes, H~P~ Rooksby and A.J.C. Wilson, Chapter 17, A.R.
Stokes, pg. 409, 1955, Publ., J. Wright, London).
Figure I is an X-ray comparison of cryskalline tri-
clinic ReS2 with paracrystalline ReS~. The sharp X-ray
pattern is that of ReS2 prepared by prior art technique while
the broad pattern ls that of ReS2 prepared by the nonaqueous
precipitation technique described in the instant specification.
From the figure it can be seen that the two materials are
dramatlcally di~ferent physically. In regions where the
prior art compounds give a sharp pattern, the compound of the
instant invention does not exhibit any variation in signal
intensity at all.
Particles of 0.05 micron (500 ~) or less exhibit
blurred X-ray patterns or no X-ray pattern at all (amorphous).
Crystallite sizes of 50A x lOOA are determined by use of a
scanning electron microscope (SEM). Layered stoichiometric
-- 6 --
~13'727~i
rhenium dichalcogenide ancl technetium dichalcogenide obtained
by prior art high temperature synthesis techniques produce
X ray patterns and therefore cannot be finely divided or of
small particle or cyrstallite size In addition Re sulfides
prepared below 400C by aqueous methods are never stoichio-
metric and are always of the type ReS2~x.
Finely-divlded, high-surface area, small particle
(0.1 mlcron ~1000 ~ or less, preferably less than O.OS
mlcron) small crystaliite tabout 50 A x 100 A or less) pro-
ducts are described The chalcogenide is selected from the
group consisting of sulfur, selenium, tellurium and mixtures
thereof, preferably sulfur and selenium, most preferably,
sulfur. These chalcogenldes are prepared by the low-tempera-
ture nonaqueous precipltatlon of said material from solutions
comprislng mlxtures of the salts of the metals, typical anions
of the salts being halide (preferably chloride), acetate,
carboxylate, perfluorocaxboxylate, amines, acetylacetonate,
hexafluoroacetonate, sulfate and nitrate, the carbonaceous
moiety being a Cl to C8, preferably Cl to C3 hydrocarbon or
~0 fluoxocarbon, with solutions of or slurries of sources of
sulfide, selenide, telluride lons and mixtures thereof. The
products of the low-temperature nonaqueous precipitation
technique are distinguished from materials prepared by high-
temperature (greater than 400C.) methods of the prior art by
exhibiting markedly different surface areas, particle sizes
and crystallinity characteristics.
A method is described for the synthesis of chalco-
genides of the metals specified above which comprises prepar-
ing a nonaqueous reactive solution or slurry wherein is added
(i) a metal salt, the salt anion being selected from the group
consistlng of halide, acetate, carboxylate, perfluorocarboxy-
late, acetylacetonate, hexafluoroacetylacetonate and (ii) a
- 7 -
L3~275
1 source of sulfide, selenide, telluride ions and mixtures
2 thereof, preferably sul~ide and selenide, mos~ preferably sul-
3 fide, said sources conveniently being Li2X, hydrosulide salts
4 [i.e., N~X, ~1411~], (~14)2~, Na2X, 1~2X, (RN~13)2X- (R,i' N~2)2
(R,R',R" NH)2X ~herein ~, R', R" are the same or different
6 and are selec~ed from the group consisting o Cl-C20 ~lkyl,
7 prefexably Cl to Cg, or C6-C20 aryl, preerably C6 to Cl2,
8 and X is the chalcogenide selected rom the group con~isting
9 of sulfur, selenlum, teIlurium and mixtures thereo~, prefer-
ably sulfur and selenium, most preferably sulfur and a non-
11 aqueous solvent selected from the group consisting o ethers
12 o~ from C4 to C~J acetonitrile, benæonitrile, dimethylform-
13 amide (DMF), propylene carbonate, aromatics of C6 C20 carbons,
14 pre~erably C6 to C12, ammonia, molten sul~ur, diglyme, sulfur
lS dioxide, ethylaceta~e, esters o from C4 to Cg, sulfolane,
16 tributylphosphate, anhydrous acids, such as ~ormic acid, gla
17 cial acetic acid, alkylhalides of from Cl ~ ~20. prefera~ly
18 Cl to Cs~ and arylhalides of from C6 to C~o, preferably C6 ~
19 Clo, pyridine, propioni~rile, N-methylformamide, dimethyl-
suli~e, Cl-C30 amines, preerably Cl to C20, Cs - C12 alkanes,
21 pre~erably Cs to Cg. The solven~s o~ choice are te~rahydro~
22 furan (THF~ dimethyl~ormamide (DMF) 3 chl~robenzene, chloro-.
23 form, pyridine, e~hyl ace~ate and acetone. Alternatively,
24 the reaction may be run nea~J that is, in ~he absence of any
solvent. The products may be isolated by filterlng, washing
26 with e~cess solven~ or.by pumping of~ the anion salts i~ they
27 are volatile. In si~uations wherein the sulfide, selenide
28 and/or ~ellur.de ion sources are already solutions, no addi-
2~ tional solven~ is needed during the course of the reaction
~ although a volume of nonaque~us solvPnt (i.e. one which does
31 not offer or accept protons, i.e. aprotic as opposed to protic
32 may be added so as to facilitate product isola~lon. When
- 8 -
,, . , . . , ~ . . . , , . . ~ .
~3~7~;
_ deslred, the material so obtalned
1011
12
13
14
16
17
18
19
21
22
23
24
26
27
28
29
31
32
~ - 8a -
,~ ,
~L3~7~i
can be pretreated for use as a catalyst, for example~ in an
H2S~H2 atmosphere for ~everal hours, temperature of pretreat-
ment being 300-600C, pre~erably 350-500C, the H2S~H2 atmos-
phere being 1~ H2S to 100% H2S, the balance being H2, prefer~
ably 3~ to 20% lI2S, the balance being H2. Alternatively, the
material can be pretreated in situ in the catalytic reactor,
the sulfur-containing hydrocarbon feed stream alone being
sufficient to e~fect the desired change. Typically, the cata-
lytic processes will be run at temperatures ranging from
ambient to 500C, preferably 100~450C, most preferably 200
400 C, at pressures o~ from 1 atm-5000 psig of H2, preferably
100 - 2000 p9ig o H2 and at space velocities o from 0.1 - 10
V/V/hr., preferably .1-5 V/V/hr. When the compound is to be
used as a catalyst, it may be prepared ln the catalytic reac-
tion vessel by introducing the appropriate starting materials
(from those recited above) into the vessel, using the hydro-
carbon feed stream to be catalytically treated as ~he non-
aqueous solvent.
When one uses a Group VIII chalcogenide of the type
descrlbed above in the supported state, the metal chalcogenide
will be present at from 0.01 to 30 wt. % metal based on total
catalyst, preferably 0.1 to lQ wt. ~ metal based on total
catalyst.
Typically, a metal salt such as ReCl~ or RUC14 i5
reacted with a solution of, or a slurry of a convenient sul-
fide, selenide or telluride lon source such as Li2S, Na2S, K2S,
hydrosulfide salt (i.e. NH4H5, NaHS), (NH4j2S, (RNH3)~S,
(~,R'NH2)2S, (R,R~RIlNH)2S, wherein R, R7 and R'l are the same
or different Cl_C20 alkyl or C6-C20 aryl~ preerably Cl to
C8 alkyl or C6-C12 aryl, Li2Se, Li2Te, (NH4)2Se, in a non-
aqueous solvent such as THF, other organoethers, acetonitrile
propylene carbonate, DMF, molten sulfur, etc. The reaction
_ 9 ~
which occurs may be represented by the following equation
(when M is a ~4 metal ion):
nonaqueous
MZ4 ~ 2 A2X ~ MX2~ ~ 4 ~z
solvent or neat
where M - a Group VIII or VIIb metal,
A = alkali metal ~ NH4 ~ R, R' R~' NH ~, R,
R NH2 ~ or other cation as defined above,
Z - convenient anion such as Cl ~, Br ~ I ~
acetate Q carboxylate ~ nitrate ~, sulfate ~ etc. as
recited above,
X = sulfur, selenium or tellurium.
Any convenient souroe of M ~ M ~ , preferably
M ~ 3 and M ~ 4 can be used. Complexes ~ormed in solution
which can be isolated as solids may be used as M ~ sources.
The reaction is normally but not necessarily, con-
ductPd in the absence of an excess of sulfide, selenide or
telluride, although other starting materials may be present
in excess~ Since particle size depends on the rate of mixing
of reagents, the reaction may be allowed to proceed instantly,
upon total admixtuxe o~ one reagent to the reaction solution
yielding fine products or, upon the measured addition of small
increments of one reagent to the reaction solution, the
reaction not achieving totality for several daysO
The temperature of the reaction may range from -78C
to 400C, e.g., 0 to 400C., preferably ambient (25C) to
300 C. It should be noted that any convenient temperatures
below 400C. may be used, the only requirement being that the
low temperature chosen be above the freezing point of the non-
aqeuous solutlon used or slurry f~rmed. These temperatures
are markedly lower than those needed when prepariny dichalco-
genides via solld state or gas phase methods wherein reaction
temperatures up to and exceeding 1000C are commonplace.
-, -- 10 --
1~3~7~
The products obtalned from the low temperature
nonaqueous precipltation technique are di- and polychalco-
genides, particularly dichalcogenldes and more particularly
disulfides, and have unlque properties. The products may be
stolchiometric~ The partlcle size and cr~stallinity of these
materials can be greatl~ varied by practiclng the preparative
methods of the instant lnvention. Surface areas can be ralsed
tothe point where the dichalcogenide will remain suspended in
solutlon and homogeneous dispersions created~ This effect
can be increased by using more polar nonaqueous solvents such
as DMF or basic solvents 5uch as pyrldine or propylene
carbonate whlch have a natural tendency to attach to the sùlfur
layers and cause dlspersions. These same solvents are those
which tend to intercalate in crystalllne transition metal
dichalcogenides. Such dispersions can be gelled by proper
variation o~ conditions or adsorbed on basic substrates such
as CaO.
The above-mentioned preparation allows one to choose
between a wide range of partlcle size, crystalllnity and
3urface area compounds. Sollds may be prepared which have the
~ollowing properties:
A. Hlgh-sur~ace area, small-particle size and
; amorphous structure. Such characteristics are achieved by
use of a solvent which may have the ability to form inter-
calation complexes with the chalcogenide. Alternatively,
chalcogenides formed neat or in the absence of an interca-
lation solvent may be treated with an intercalate to achieve
the same result. Such intercalates may be a strong Lewis
base such as pyridine, ammonia, Cl - C20 amines, aldehydes,
ketones, amides, heterocycllc bases, anilines and ethers
The intercalated chalcogenide i5 then subjected to heat
treating at between 75-200C with pumping under vacuum when
-- 11 -
~37~7~
necessary to drive off the lntercalating solvent leaving a
high-surface area, small~particle size amorphous chalco-
genide. Example: ReS2 or RuS2 prepared from ethylacetate
and treated at 400C in H2~ gave a poorly defined X-ray
pattern which lndicates a crystallite size of at least le~s
than 0.1 micron and a Brunauer, Emmett and Teller (BET)
surface area of 50 m /gm. Treatment temperatures less than
400C yield hlgh-surface areas or completely amorphous
solids,.
B. Low surface area, small particle size and
amorphous solids. Example. The same ReS2 or RuS2 as men-
tioned ln tA) if not heat treated gave an amorphous X-ray
pattern and a BET surface area of 10 m /gmO
C. Homogeneous disper~ions: conditions can be
arranged a~ above so that all or part of the chalcogenides
remain in suspension as a homogeneous dispersion in solution.
Appropriate solvents which are used for the generation of
dispersions include propylene carbonate, dimethylformamide
(D~ pyridine, acetonitrile, benzonitrlle, propionitrile,
l,2 di-methoxyethane, dlgylme and N-methylformamide. Such
materials can be removed ~rom solution by the addition of
a basic solid such as MgO. For example, ReS2 or RuS2 prepared
in propylene carbonate will result in a black opaque disper-
sion. The ReS2 or RuS2 may be adsorbed by shaking the dis-
persion with MgO which results in a dark gray material when
dried. Correspondingly, the original solution is clear after
such treatment with the excess MgO.
D. High-surface area composite - Group VIII or
VIIb dichalcogenide~metal oxlde ~olids. Composite material
may be prepared with the chalcogenide being adsorbed on a
metal oxide due to the Lewls acid nature of the chalcogenide.
Exc~mple: ReS2 or RuS2~MgO material described in (C~ above.
- 12 -
The metal oxides which may be used in this embodiment are any
metal oxide9 which exhibit Lewis acidity, for example, MgO,
CaO, ~12O3, the oxides of Groups IV, V and VI of the Periodic
Table of the Elements, preferably TiO2, ZrO2; alternatively,
acti~iated carbon ox charcoal may be used.
E. Gels and Glasses - Gels containing the Group
VIII ox VIIb dichalcogenides may be produced by preparation
in certain amines, such as ~rihexylamine, or by carefully
removing solvent from ethylacetate solutions of ReC15 or
RuC14~2Li2S. The gels produced yield glasses when the sol-
vents are removed.
All of the preparative work described below was
carried out either in a dry box or under a blanket o~ nitro-
gen, Both the starting metal ~4 and ~5 compounds and the
sul~ides and selenides thus produced are sensitive to moisture
and oxygen, especially in ~inely powdered form as results
from the heterogeneous precipitation methods described. All
solvents were dried by standard techniques prior to use and
anhydrous reagents were always employed.
Chalcogenides
1. Ruthenium
RuS2 was generally prepared from the tetrachloride
but preparation from the trichlorida is also possible~ There
were significant differences in the activity and selectivity
between the two preparations:
RuC14 ~ 2 Li2S ~ RUS2 ~ 4 LiCl
7.40 gm of RuC14 (30.47 mm) was dissolved in 100 ml of ethyl
acetate and 2.80 gm Li2S (60.94 mm) was added in the dry
state. Thls was stirred for 4 hours and filtered, yielding
a black powder which was still wet with ethylacetate. The
filtrate was partially green indicatiny suspended particles
~ 13 -
~L~372~5
of RuS2. The sample was then heat treated in pure H2S at400 C for 1.5 hours, cooled to room temperature, washed with
12~ acetic acid, ~.tltered and heated again in pure H2S for
1.5 hours~ This treatment yielded a black powder wetghing
6~683 gms ~theoretical yleld of RuS2 = 5.11 gms) which showed
only RuS2 in the X-ray pattern. Chemical analysis showed 3.89
moles of sulfur ~or each ruthenium atom with less than ~%
chlorine. Infrared analysis also indicated the presence of
an extra phase. This extra phase appears to be atomic sulfur
caused by the catalytic decomposition of H2S = H2 ~ 5
This was further confirmed by treatment of the
RuS2 as produced above with mixtures of H2/H2S providing
lower partial pressures of sulfur. For example, RuS2 after
being run in the flow reactor for more than 1000 hours showed
only RuS2 in the X ray pattern and gave the following chemical
analysis:
Theoretical
7be~etiral xuS~ Measured 1- ?5 o. 25
Ru61.2 % 62.4 % 63.1 %
S 38.8 ~ 34.6 % 35.0 %
C 0.0 % 2.1 ~ 1 9 %
~ O
Total100.0 % 99~1 ~ 100.0 %
All results indicate that RuS2 itself has a range of possible
non-stoichiometry and the above example corresponds to the
formula RuSl 75. It may be noted that if one su~st~tutes the
carbon found in the analysis ~or the missing sulfur, this
give~ a compound of formula RuS1 75Co 25. This suggests that
the carbon is replacing the sul~ur on the surface of the
catalytically active particles, The infrared spectrum of
RuS2 which has been treated to remove excess sulfur is very
similar to that of FeS~. These compounds freshly prepared
had BErr surface areas ln the neighborhood of 70 m /gm.
'~;,
3L~ 3~727~i
2RuCl3 ~ 3Li2S et1lyl acet ~ Ru2S3 ~ 61,iCl
~u2S3 -~ H2S 400 C~ 2RuS2 ~ H2
The preparation erom the trichloride is exactly analogous to
the above preparation from the tetrachlorlde yielding RuS2.
The catalytic activity i5 slightly different for the two
preparations. This is undoubtedly due to a difference in the
physical state o~ the RuS2.
2 osmium
OsS2 was prepared from the tetrachloride:
OsCl4 ~ 2Li2S--~OsS2 -~ 4LiCl
4 grams of OsCl4 was added to lO0 ml of ethyl acetate yield-
ing a greenish solution. l.12 gm of Li2S was added as the
solid and the solution turned black with stirring. The
solution was filtered and a black powder was obtained which
was treated at 400C in a stream o H2/l5% H2S for 2 hours.
The solid was then washed with 12~ acetic acid and treated
again for 2 hours at 400C in H2/l5~ H2S. The resulting
black powder weighed 2.80 gms (theoretical = 3.10 gms) with
a BET surface area of 20 m2/gm. X-ray analysis as discussed
below indicated that the OsS2 was a previously unknown layered
compound which could be converted to the known pyrite type
by heatlng in vacuum at 600C. The osmium sulfide prepared
by this method was con~erted to Os metal under reactor
conditions. However, the chemical analysis indicated that
the stoichlometry was OsS. In H~/l5~ H2S the OsS2 had been
partially converted to the metal after several hours.
3. Iridium
__
IrS2 was prepared from the tetrachloride:
IrCl4 ~ 2Li2S --~t IrS2 ~ 4I,lCl
2.00 gms of IrCl~ was dissolved in 175 ml of ethyl acetate.
-- 15 --
~ . I .
~37~
The solution became dark brown. To this 0.55 gms of Li2S
was added neat with the color changing from a dark brown to
golden. After stirring ~or 3.5 hours a golden powder was
recovered, 1.8 gms of the product wa~ heat treated in 15~
H2S/N2 ~or 2 hour9, washed in 12% acetic acld then reheated
in 15~ H2S/N2 ~or 2 hours yielding a black powder with a BET
surface area o 60 M2/gm, The acetic acid wash caused
bubbling and fizzing whlch indicates lncomplete reaction of
Li2S. As in the case of RuS2 prepared in H2S the product
contained excess sulfur. X~ray powder diffraction yielded
a very diffuse pattern probably of pyrite type IrS3. However,
this compound reverted in the reactor to Ir metal ~ S .
4. Rhodium
Rh2S3 was prepared in the same manner as in the
previous examples from the trichloride: -
2RhC13 + 3Li2S -,~Rh2S3 ~ 6LiCl
X-ray analysis before and a~ter reaction indicated the pre
sence o~ Rh2S3 which had a BET sur~ace area of 15 M2/gm.
5. Rhenium ~,
ReS2 from ReC15 by the reac.tion.ReC15 ~ 2.5 Li2S > ~
~ . .
ReS2 ~ LiCl ~ .1/2 S
3,64 grams of ReC15 were reacted at room temperature
with 2.30 gram~ of Li2S in 100 ml ethylacetate and stirred.
The black product was filtered and dried in H~S at 400 C.
The product analysis was ReS2 0:~
Theore tical Measured
% Re 74~39 74.40
~ S 25.61 25.49
X-rays indicated that the product corresponded to ReS2 and
line broadenlng indicated a crystallite size of about 40 x
80A. The BET surface area was 50.2 m2~gm. Product before
heat treatment was completeIy amorphous to X-rays, indicating
- 16 -
~ ~o~
crystalline oxder of le9s than 5~, thus an amorphous solid.
ReS2 from Re.C.14.by:thë r.e.a.cti.on Re.Cl.~. ~ .2 Li2S -
~ReS2. ~ 4 LiCl
In an exactly analogous manner, ReS2 was prepared
from ReC14 at room temperature with the same results except
that excess sulfur did not have to be removed by washing or
heating. However, this product is considerably more active
than that prepared from the pentachloride, in the hydro-
sulfurization of dibenzothiophene (DBT).
6, ReS2 Dispersion
2.33 gram~ (8 mm) of ReC15 was added to 80 ml of
propylene carbonate. To this was added 0.89 grams of Li2S
(19 mm) and the solution ~as stirred for 4 hours yielding
a black liquid whlch was 0.lM in ReS2 and could be continuously
diluted to any concentration. This black liquid passed
through normal filter discs and was stable.
7. ReS2Gel
,
Theabove-described ReS2 dispersiorl gelled if the
concentration was greater than ,033 M, upon standing for
several days.
8. ReS2 Glass
The above~described gel yielded a ~eS2 glass if the
olvent was pumped off and the LiCl removed by washing with
a suitable solvent (methanol).
9. ReS2/MgO Composi.tion
_ _ , . . .
A 0.lM dispersion of ReS2 in propylene carbonate
was prepared as described above. 25 ml of this dispersion
was contacted with 4 grams of MgO and stirred for 4 hours.
The initially white solid was filtered and dried in H2S at
400C for 1 hour yielding a dark gray solid, The solid
ReS2/MgO composite contained 2~33% Re. The amount of ReS2
- 17 -
- 1~3~
adsorbed on the MgO can be controlled by varying stirring
time and concentration as shown in Figure II.
10. ReS~,/Al203 Composl,tion
In a similar manner, ~4 grams of A12O3 was contact-
ed with 114 ml of the 0.lM dispersion and stirred for 6 hours.
The dark gray ReS2/A12O3 contained 1.64% (wt) Re.
Platinum and Palla'di'um
Both platinum and palladium were fairly inactive in
hydrodesulfurization and thus their activities were not great-
ly affected by method of preparation. Pd5 was prepared from
the dichloride in a similar manner to the compounds previously
described:
d 12 Li2 PdS -~ 2 LiCl
PtS was prepared in this manner but was also prepared from
the tetrachlorlde. This reaction led to chemical results
differing from previous examples:
PtC14 + 2 Li2S aceYate ) PtS2 ~ 4 LiCl
PtS2 ~ PtS
1.0 gm of PtC14 was dissolved in 200 ml of ethyl acetate
and then divided into two samples. 100 ml was allowed to
stand. Upon standing the solution began to darken and pre-
cipitation began to occur. A golden film began to form as
well as crystals. The crystals when examlned under polarized
light were highly pleochroic transmitting light perpendicu-
lar but not parallel to their long axis indicating the fox-
mation of a Pt chain complex~ Preliminary chemical analysis
indicates a-PtC14:LiCl:ethyl acetate complex.
Treatment of the remaining portion of the solution
with Li25 as in previous examples yielded PtS after heat
t~eating.
- 18 -
\~
~37~7S
TABLE I
PARTICLE SIZE ANALY5IS OF CATALYSTS
_._ ___
Particle BET
t _ ucture hkl B Size A M2/gm~
OsS2 (Fresh) Layered 002 3.3 29 20
110 2.1 51
Os ~ S Metal 101 2.9 35 15
RuS2 Pyrite 200 1.2 90 52
h~S3 Rh2S3 200 0.6 162 15
lQ Irs2~x(Fresh) Pyrite 200? 7.0 14 73
Ir ~ S Metal 111 1.2 82 15
PdS Pds 200 0.3 324
PtS Cooperite 110 0.5 202 11
Ruthenlum, rhodium, iridium and osmium transition
metal chalcogenides, preferably sulfides, prepared with high
surface area as described herein, are excellent hydrodesulfur-
ization, sulfur tolerant, hydrogenation and hydrodenitrogena-
tion catalysts under typical conditions found in hydrofining
processes of petroleum and coal based feedstocks. The Ru, :~
~h, Ir and Os sulfides are also effective as hydrogen-donor
catalysts, i.e. they will abstract hydrogen from hydrogen- ~ -
donor solvents like decalin, tetralin, etc. and use the
abstracted hydrogen in the hydrosulfurization process.
The Ru, Rh, ~r and Os binary chalcogenides,
preferably the sulfides, ef~ectively desulfurize DBT at
elevated temperatures, e.g., 200-500C, and pressures accord-
ing to the following reaction:
- 19 -
- ~13~2~5
1)~ + excess H2
Dibenzothiophene Biphenyl
5 wt. %
DBT BP
~3~`+ CrO
Cyclohexylbenzene Bicyclohexyl
CHB BCH
The amount of CHB and BCH formed serves as a measure of the
hydrogenation capabilities of these materials in sulfur
environments. Tables I~ and III summarize the hydrodesulfur-
ization and hydrogenation activity of the Group VIII metal
sulfides.
.
,
'':
- 20 -
~3'~275
TABLP II
HYDRODESULFURIZATION ACTIVIT~ OF GROUP VIII
TRANSITION METAL SULFIDES
... ., ..,., . .. ... . . _ _
Conditions: Carberry Reactor, 400C, 450 psi,
10~20 mesh catalyst particles
Activity
molecules DBT-~x
Catalyst 1ol6- - -S -
x ~ BP CHB
lG eS2_x 0~9
COgS8 1.6
NiS 1.6
RuS2 ~RUs2-x 210 20
RhSl 5 RhSl 5 x 70
PdS 9
OsS2--~SS2_~ 85
IrS2--~IrS2_x67
PtS -~ 7
TABLE III
HYDRODESULFURIZATION AND HYDROGENATION ACTIVITY
Conditions: Carberry Reactor, 350C, 450 psi,
20/40 mesh par~icles
Activity
molecules DBT-~x
~ ~:=
x ~ BP CHB
RUs2--~Rus2-x 113 24
RhSl 5t RhSl.5-x 10
OsS2-~ OsS2 x 40 17
I~S2-~IrS~ x 21 17
PtS -~ 4 0~4
- 21 ~
~372~5
These bulk sulfides will maintain their hydrode-
sulfurization activity and hydrogenation activity for ex-
tended periods of time in a flow reactor configuration under
wide ranges of temperatures, pressures and liquid hourly
space velocities. In act, when compared to a commercial
Nalco cobalt molybdate on ~-A1203 (JCM-468) catalyst (CMA),
several of the subject materials display comparable to super-
ior activity per gram.
Table IV summarizes the flow reactor data obtained
on RuS2 ~bulk) and where possible compares it to the commer-
cial CMA catalyst described above. This binary sulfide
maintained its activity over an extended period of 1053
hours (44 days).
372~75
r l 0
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rY H o ~ ~) Ln ~D Ln ~ ~I
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- 23 -
.~
~7275
The Group VIII transition metal chalcogenides,
preferably sulfides, prepared via nonaqueous dispersions on
supports described herein are active hydrodesulfurization,
hydrogenation and hydrodenitrogenation catalysts and are
often ~uperlor to prior art materials. For comparative
purpo~es the materials were prepared by the following
techniques:
5upport
) 4 i2 ~ MS2/Support
Slurry
Propylene Carbonate
3) Support Aqueous Dry 80~100C Presulfide
Impregnation
Incipient wt- Vacuum Oven 15~ H2S/H2
ness of water 12 hrs.25-400C
soluble salt 2 hrs.
4) Support Aqueous Dry 80- Reduce Presulfide
Impregnation 100C in H2
Incipient wet- Vacuum 500C 15% H2S/H2
ness of water Oven - 1-4 ~rs 25~40~C
soluble salt 12 Hrs 2 hrs.
The hydrodesulfurization of supported ruthenium catalysts
i~ c~mpared on a per gram and per millimole Ru basis in
Tables V and VI. Table V indicates that RuS2 supported on
MgO, Material 1, prepared with the nonaqueous dispersion,
displays superior activity compared to prior art Materials
2 and 3.
- 24 -
,;'
~ .
:
37~275
m o
m
a ~:
~ a)
~1
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~ a) _l
u, ,, ~ ~1 ,~
O ,1 ~ a~ ,~
~ ~ ~ ~ .
.,1 ~ ~D
i~ h o
H ~ ~C
C~ U~ :
~ .
1~
H ~ ~ C~
P ~ ~ ~q U~
U~
H O U ~ t
P ~ ~ ~ `
00 ~ ~
E~ ~ ~ ~ ~C
5~ ~ '
~ ~ O
o ~ a~ ,,
H
~ ~ i~ ~ O
1~ P r4 h h 8
5~ P~ q~ o ~ o~
E4 0 t,) ~ N ~) ec rl
o .- ~:5 ~ Q~
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. æ
E~ C~ ~
co c~
. o o o
I o
x o o
c~
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v
~ ,~ ~
~1
-- 25 --
~L137~75
Table VI provides additional data indicating that
supported Group VIII chalcogenides prepared via nonaqueous
dispersion techniques, are superior HDS catalysts compared
to prior art materials, i.eO Material 2 is superior to prior
art Materials 3 and 4; Material 5 is superior to prior art
Material 6. In addition, Table VI demonstrates that Group
VIII chalcogenides supported on a basic support such as MgO
via dispersion techniques are superior to other dispersion
supported materials: Material 1, RuS2/MgO is a much better
HDS catalyst per gram and per millimole of Ru than Materials
2, 5, or 7.
~ 26 -
;
`- 1~37~75
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P; ~ C) ~1
P~ H O
Ecl P ~
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. ~ ~ ~ ~0
~; ~ ~ ^~
O E~ O ~
E-l O P; ~1 ,,
E~ O ~30 ~30
~ ~D ~ O t~ O ~I O ~
P. U~ ~ P. S~ ~ h t~7 :
S~ q~ ~ ~ q~
P~ O O ~`I N ~7 r) ~ ~ t`3 ~)
1~ ~1 ~ 1~ U C~
O t~ O, X ~ X X ~ X
H ~ K 0
h V .0 :~
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_ 27 -
.
- ~37~7~
ReS2 supported on a basic oxide such as MgO pre-
pared according to the following procedure, i5 an active
and selective HDS catalyst for resid-like organosulfur mole-
cules, i.e. DBT.
Slurried in Li S
ReC5 ~ ~g ~---~~~~~~`~ ) ~ ReS~/MgO
Propylene Stir ~ LiCl
Carbonate 4 hrs. @ (Solvent)
room temp.
ReS2~MgO ~ ReS2 (1-10% Re)/MgO
1 hr.
Table VIl presents the data obtained at 400C and 450 psig.,
H2 flow AV 100 cc/min.
2~ -
~3
~:~L3~5
,_
~,
a
~1 ~ ~
.. ..
~n oo oo
U~
a~
~O cn cr~
E~ ~ I~a~
Q) ~n
~1 :~ r~ I
U ,~
o~
~ ~ .,. ,, ~
m
H
O El "~ ~ O N
u~ a~u) ~
h~I N~I N
.
_
~ t`N .--1
. . I ,.
~, ~1 o t~
~ ~ O
_
~1 ~ Iq
a)
_~
C) ~ ~ +
C) ~ U~ ~ .
_ f~ 1 l 4 P
~_ m m
6P o'P
o _,
~ ~ ~ ~o
r~
U~
"~ ~: ~ U~
C~ C~ ~;
., -- 23
~,
1~37~75
Table VI~ indicates that under comparable conditions but with
lower metal loading and less catalyst, ReS2 (2.1~ Re)/MgO
is approximately as active as CMA at a space velocity equal
to 1 V/V/H. ~Iowever, Re52/MgO is much more selective toward
desulfurizati.on as evidenced by the selectivity factors.
Consequently, under conditions necessary to desulfurize
resid., i.e. T = 400C, P~ 450 psig, 9V = 0.5-l ~/V~H,
ReS2/MgO is as active (on mole % conversion basis) as CMA
but is far more selective.
TABLE V}I}
HYDRODESULFURIZATION ACTIVITY OF GROUP VIII
BINARY_SULFIDES VIA HYDROGEN DONOR REACTIONS
Conditions: Carberry Reactor, 450 psi, He at-
mosphere. ~ecalin serves as
hydrogen source.
16 Activity
Temp. Par~icle rxlO Molecules DBT-~BP
y~ __ CSize, Mesh _ gm-sec
RuS2-~RuS2_x 35010/20 14
OsS2~ OsS2 x 40020/40 23
A ~
The bulk and supported ~roup VIII transition
metal chalcogenides, preferably sulfides, described herein
are active HDN catalysts for the removal of organic nitrogen
from petroleum, shale and coal based feedstocks.
Table IX summari~es some typical results which
reflect the HD~ activity of th0se materials using a model
organonitrogen compound, quinoline. The degree of nitrogen
removal was followed analytically by determining the nitrogen
content of the feed (ppm) before and after contact with the
catalyst in a high pressure and temperature flow reactor.
These materials will be effective denitrogenation catalysts
over a range of temperatures~ e.g., 250-500C, hydrogen
pressures and space velocities.
- 30 -
1~3~Z7~ii
TABLE IX
H~DRODENITROGENATION ACTIVIT~ OF GROUP VIII
CH~LCO~EN~DES
Condltions: High Pressure Flow Reactor;
Feed: .8% S, .099~ N in decalin
(S as DBT,
N as quinoline)
T-280C, P=450 psi, LHSV= 1.3
~ % N i~ Feed % N in Product ~ HDN
RuS2 0.099 0.013 87
- 31 ~
