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Патент USA US3079239

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States
iiQQ
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3,979,229
points of at least 1100° C. are particularly suitable in
the practice of the present invention and are the pre
PROCES§ FGR PIRGDUCENG TITANIUM
_
3,079,229?
Patented Feb. 26, 1963
ferred temperature-controlling compounds.
DHSULFEDE
Frederick W. Garret, Niagara Falls, Ontario, Canada,
and Samuel McCaun, Niagara Falls, N.Y., assignors to
gmfll Carbide Corporation, a corporation of New
or r
No Drawing. Filed Apr. 15, 1960, Ser. No. 22,415
9 Claims. (Cl. 23-134)
Included
among these are sodium chloride, potassium chloride,
calcium chloride, and magnesium chloride. The salts
may be employed individually or in combination. The
total amount of salt employed may vary over a wide
range, e.g., between about 20 and 60 percent by weight
of the total mixture of titanium, sulfur and temperature
10 controlling salt. However, it has been found that the
This invention relates to a process for the production
of titanium disul?de.
it is well known that the higher sul?des of titanium
possess excellent lubricating qualities which are superior
most desirable results are obtained when the salt is added
to the reaction mixture in amounts equalling aboutv 30
to 50 weight percent of the total reaction mixture.
The use of the temperature-controlling compound and
to such lubricants as graphite and molybdenum disul?de 15 maintenance thereof in a molten state in the process of
for many uses. However, of the higher sul?des of ti
this invention has many advantages. Primary among
these is the fact that this material, physically, partially
binds the titanium and sulfur particles together. This
lar in appearance to graphite, has a high thermal stability,
prevents separation of the reactants before the titanium
adheres better to metal surface than graphite, and is very 20 disul?de-forming reaction is completed and also inhibits
easily ground to a ?ne powder.
vaporization of sulfur during the reaction. Another ad
The reaction between titanium metal and sulfur is ex
vantage derived from the process of this invention is that,
tremely exothermic. In this reaction, it is di?icult to
during the titanium disul?de-forming reaction, the molten
tanium, the optimum lubricating properties are possessed
by ititanium disul?de. Titanium disul?de, although simi
control and limit the temperature obtained, which in a
short time goes from about 650° C., the approximate tem
perature necessary to initiate the reaction to 2000° C. and
higher. Because of this rapid increase of temperature,
salt heaps to prevent contamination and/or a reaction
between the reactants and any gases present in the reac
tor. In addition, the temperature-controlling compound
absorbs a portion of the heat of reaction to prevent ther
vaporization of a substantial portion of tne sulfur occurs.
mal disproportionation of the titanium sul?de formed.
Thus, it is dimcult to consistently produce a stoichiometri
After the reaction mixture is uniformly blended, it is
30 introduced into a suitable reaction vessel. Many different
cally balanced titanium disul?de product.
It is an object of this invention to provide an improved
process for producing titanium disul?de.
v
types ofreaction vessels can’ be employed. A_ reaction
vessel-found particularly suitable for carrying out the
'
Other aims and advantages of this invention will be
process of this invention is one that ‘can be sealed to airi
apparent from the following description and appended
tightness and purged with an inert‘ gas such as, for ex;
claims.
ample, argon or helium. To insure the absence of air
The process that satis?es this invention comprises in
therefrom, a slight positive pressure of inert gas. should
troducing into a mixture of ?nely-divided titanium and‘
the maintained. The reaction mixture is heatedto about
?nely-divided sulfur wherein sulfur is present in at least.
650° C. after which'tirne no further heating is necessary
the stoichiometric amount necessary to produce titanium
because of the exothermicity of the reaction.
. v
disul?de, at least one temperature-controlling compound 40
A suitable manner of initiating the reaction is by pass-,
selected from the group consisting of alkali and alkaline
ing electric current through a titanium coil immersed in
earth metal halides having a boiling point of at least
the reaction mixture. By employing a titanium coil in
1100° C. The mixture is heated to a temperature of
this manner, a relatively short heating‘ period of about
about 656° C. to initiate the titanium disul?de-forming
30 to 90 seconds is su?icient to bring a localized portion
reaction. The temperature-controlling compound be 45 of the reactants to self-reacting temperature. Although
comes molten as the temperature of the mixture rises
other methods of heating are acceptable,‘localized heating
and the temperature of the mixture is controlled by the
is sufficient because of the e'xothermicity of the reaction.
molten salt which absorbs a portion of the heat of reac
tion and which also holds the particles of titanium and
sulfur together in the mixture allowing them su?icient
Upon completion of the reaction, the product is cooled,
50 removed from the reaction vessel, crushed to a suitable
time to react and at the same time preventing vaporiza
particle size, and leached to remove the contaminating
salt. A weak acid is employed during the leaching step,
tion of the mixture. Upon completion of the reaction,
the titanium disulfide is cooled, crushed, and leached with
i.e., an acid inert to titanium disul?de such as 12 percent
acetic acid. Stronger acids, such as hydrochloric, canbej
employed; however, the use of such an acid also requires
the use. of a sequestering agent, such as gluconic acid, .t
an acid inert to titanium disul?de.
In order to insure a uniform blending of the reactants,
all of the reactants are preferably comminuted to a ?ne
ness of approximately 100 mesh (U.S. screen series) or
maintain any dissolved titanium in solution.
smaller. Any suitable means for reducing particle sizes
can be employed.
The amount of titanium and sulfur employed in the
process of this invention is the stoichiometric amount
necessary to produce titanium disul?de. However, it
has been found preferable to employ a slight excess of
sulfur over and above the stoichiometric amount required
to produce titanium disui?de. This excess is preferably
from about 5 percent by weivht to about 20 percent by
weight.
'
The following examples will serve to better illustrate
the present invention.
60
Example I
A dry, blended mixture was prepared containing 2160
grams of titanium (200 mesh by down), 3024 grams of.
sulfur (200 mesh by down), and 2592 grams of mixed,
alkali metal salt (200 mesh by down). The sulfur com
ponent corresponded to about 5 percent excess by weight
above the stoichiometric requirement needed to produce
titanium disul?de, and the salt was equivalent to 33 per
cent by weight of the total reaction'mixture. The salt
To the reaction mixture is added at least one tempera
consisting of equal gravimetric parts of sodium chloride
ture-controlling compound selected from the group con 70 and potassium chloride. The blended mixture was intro
sisting of alkali and alkaline earth metal halides. The
duced into the reactor which ‘was sealed and purged of
alkali and alkaline earth metal halides having boiling
the existing atmosphere for several minutes with argon
3,079,229
3
4
gas. The charge was subsequently heated by means of a
titanium .co-il for 11/2 minutes, after which time the self
propagating exothermic reaction began. After the re
reaction, cooling and crushing the titanium disul?de
formed thereby and subsequently leaching the titanium
disul?de with acetic acid to remove the salt therefrom.
4. A process in accordance with claim 3 wherein the
action abated and the vessel was brought to room tem
nerature, thev product was removed and crushed 'to about
1-00- meshby down particle size. The crushed product
wast-leached with 12 percent acetic acidfor approximately
selected temperature-contro-lling salt is sodium chloride
and potassium chloride in substantially equal gravimetric
parts.
30_,1ninu,tes,v while being agitated. The product obtained
5. In a process for the production of titanium, disultide
analyzed;42.4.4v .percentbyweight of titanium, 53.90 per
by heating to at least about 650° C. a mixture of ?nely
cent by, weightof sulfur, and 0.70 percent by weight of 10 divided titanium and at least the stoichiometric amount
oxygen, this being equivalent to a sul?de of titanium hav
of ?nely-divided sulfur to initiate the titanium disul?de
ing; ‘an empiricalformula TiSM.
forming reaction, the improvement which comprisesradd
ing to the mixture of titanium and sulfur, prior to the
initiation of the titanium-disul?de forming reaction, at
adtnblsndsimixmre was prepared; containing 720 15 least one temperature-controlling salt selected from the
gramsof titanium (200 mesh by down), 1056 grams of
group consisting of alkali and alkaline earth metal halides
sulfur ‘(200 mesh by down), and-I888 grams of a mixed
having‘ a boiling point of at least 1100° C., the propor
alkalirmetal salt (200 mesh by down). The sulfur com
tionrof said salt in said mixture being between about 20
ponent corresponded to about 10 percent excess by weight
and Y60 percent by weight of the total mixture of titanium,
above'fthe stoichiometric‘ requirement needed to produce 20 sulfur and said temperature-controlling salt and being
titanium disul?de, and‘the salt was equivalent to about
such; that at least substantial melting of said salt is
33Ype'rcent by weight oflthe total reaction mixture. The
achieved due to the heat of the titanium disul?de-forming
salt consisted ofequal gravimetric parts of sodium ‘chlo
reaction ,to provide a molten salt binder for the reactant
Example 11
chloride.‘ The blendedmixture was
materials and thereby inhibit vaporization of sulfur.
introduced into the. reactor which was sealed and purged
of a, existing, atmosphere for several minutes with argon
'‘
25
The. charge. wassubsequently- heated by means of a
divided titanium and at least the stoichiometric amount
of ?nely-‘divided sulfur to initiate the titanium disul-?de
U 'u'rnT’cToil for 1%..minutes, after“ which time. the _self<
propagating exothermicreaction began. After the re
actionflabateduandr the vesselwas broughtto room tem
100:
30
‘t'ur'e‘, the] product was removed and crushed ,to about
mesh. b.y_,down particle size. The ‘crushed product.
wasileachedwitli l12.per_cent acetic acid'fo-r approximately
3.0‘n1inutcswhile being ,agitat'ed. The product obtained
forming reaction; the improvement which comprises add
ing ‘to-‘the mixture of titanium and sulfur, prior to-the
initiation-of the titanium~disul?de forming reaction, at
least one temperaturewcontrolling saltselected from the
group consisting of alkaliand alkaline earth metal halides
having a boilingpoint of at least .1 100° C., the proportion.
"z'eiiillb percentlby?weight of titanium,v 53.8percent
- y weight of sulfur, and 0.52 percent by weight of oxygen,
thi's-beingliequivalent to asuliidei'ofti'taniurn having an
35
of_,_said,salt insaidpmixture being between about 30 and
50 percent by weight, of the total mixture of titanium,
sulfur. andjsaid,temperature-controlling salt and being
sinriirilc?llfsimillalists.
whétisclaimsdii'si
’ 6. In a process for the production of titanium disul?de
by1 heating to atileast about 650° C.‘ amixture ofv ?nely
" '
lfiIn .a ,pr6cess-forthe production of titanium disul?dev
40
by'hea git). ,afléast aLbolit?SOf‘YC. 'a mixture of ?nelydiy
titanium and v ?nelyedi'vided? ‘sulfur to initiate. the
titanium‘ disul?de7formin'g' reaction, ‘the improvement
comprises‘providingan excess of sulfur inan
untlof_ between’ about 5 and about 30 weight percent 45
theistoichiometric. amount thereof necessary'to pro~
titanium 'disul?depand adding to the mixture of tita
achieved
thatdueat__toleast
the heat
Substantial
of the titanium
melting.disul?de-forming
of 'said salt
reaction to_p_royide-a- molten salt binder forthe reactant
materials and thereby inhibit‘ vaporization of‘sulfur.
7. In a processfor the productionof titanium disul?de
bygheating teat least about 650° C. a mixture of ‘?nely
divided titanium and at least, the ,stoichiometric amount
of?nely-divided sulfurtoinit-iate the titanium disul?de
forming reaction, the improvement ‘which comprises add-
ing to the mixture of titanium; and sulfur, priorstopthe
initiation of thertitanium-disul?de forming'reaction, at
11.1.. I v‘aiidis'uliur, prior to the initiation of the titanium’
di'sul?, ,e-foririihg' reaction, at least one temperature
controlling,,salt,‘selectedv frornthe group consisting of
least one temperature-controlling salt selected from the
group consisting of alkali and alkalineea-rth metal halides.
aikalifarid alkaline earth metal halides having a boiling
p'o tof iatileast 1100" C.,‘psaid?salt being present in- an
t bstw?sii alPQ‘iI 39 and abQ?UQ Percent by Weight
“total mixture of
sulfurv :saiditemperaé,
havi'nga boiling point of atrleast 1100’ C., the proportion
oflvsaid salt in said mixture being between‘ about 20 and
processiin accordance. withgclaim 1, wherein the;
60v percent by weight of the totalmixturegof titanium,
sulfur. andsaid temperature-controlling.salt and being.
that at‘ leastsubstantial melting, of said salt is
achieved dueto the heat of the titanium disul?de-forming
hurritchloride' insuhstantiallyequal gravimetric
reaction to. provide. an amount of molten salt su?icient
to hold’ the reactant materials together until the titaniumv
"
temperature-controlling salt, is “sodium, chloride
disul?de-forming reaction. is substantially complete.
‘"3. In a processforrthe production. of titanium disul?de,
bgheatingtqf abqut 650° 0.1a mixture or ?nely-divided
60
titanium and ?nely-divided sulfur to initiate the titanium
disul?de-forming reaction, the improvement which com
prises providing an excess of sulfur in an amount of be
tween about 5} and‘ about‘30 weight percent over the
stoichion'i'etric amount thereof necessary to produce tita
niurn disul?d'e andadding to the mixture of titanium and
sulfurfprior to the initiation of the titanium disultide
forming i'ea'ction, at least'one"temperature-controlling salt.
seIectedTfre-m'the‘group: consisting’of alkali
alkaline
earth metal halides having a boiling point of at least
~ 70
1‘1‘00°'=C;, said vsalt being presentllin an‘amount between,
aboutj30 and-about: 50percent'by weight of the total mix
tureofutitanitimpsulfurland said temperature-controlling.
Salaam. estate. at tee-?annel seems-forming;
, 8. In a process for the production of titanium disul?de
by heating to at least about 650° C. a mixture of ?nely
dividedtitanium and at least the stoichiometric amount
of ?nely-divided sulfur to initiate the titanium disul?de
forming reaction, the improvement which comprises addi
ingto. thernixture of titanium and sulfur, prior to the
initiation .of'the titaninm-disul?de forming reaction, at
least one. temperature-controlling salt selected from the
group consisting of alkali and alkaline earth metal halides
having aboiling point of at least ~1100° C., the proportion
of said-salt insaidmixturebeing between about 30 and
50 percent by weight of the total mixture of titanium,
sulfur and said temperature-controlling’ salt and being
such that atv least substantial melting of said salt is
achieved. due to the heat of the titaniumdisuliide-forming
reaction to provide anamount of molten salt 'sufmcient
3,079,229
5
6
to hold the reactant materials together until the titanium
about 60 percent ‘by weight of the total mixture of ti
tanium, sulfur and said temperature-controlling salt.
disul?de-forming reaction is substantially complete.
9. In a process for the production of titanium disul?de
by heating to at least about 650° C. a mixture of ?nely
divided titanium and ?nely-divided sulfur to initiate the
titanium disul?de-forming reaction, the improvement
which comprises providing at least the stoichiometric
amount of sulfur necessary to produce titanium disul?de
and adding to the mixture of titanium and sulfur, prior
to the initiation of the titanium disul?de~forming reaction,
at least one temperature-controlling salt selected from
the group consisting of alkali and alkaline earth metal
halides having a boiling point of at least 1100“ C., said
salt being present in an amount between about 20 and
References Cited in the ?le of this patent
UNITED STATES PATENTS
1,796,265
Freudenberg et al. ____ __ Mar. 10, 193-1
127,245
Switzerland __________ _._ Aug. 16, 1928
FOREIGN PATENTS
OTHER REFERENCES
Treatise on Chemistry, Roscoe and Schorlemmer, page
799, vol. II (The Metals), Macmillan and Co. (London).
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