Патент USA US3079239код для вставки
5 see States iiQQ 1 2 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).