CA1142471A - Method of use of group ivb to group viii chalcogenides as catalysts - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE

A process for the treatment of hydrocarbon feed streams wherein said hydrocarbon feed streams are contacted with a catalyst at a tempera-ture and pressure and under conditions sufficient to effect the desired change in the hydrocarbon feed stream, which comprises using as a catalyst a material of the formula MXy, M being defined as a transition metal.
selected from the group consisting of Group IVb, Vb, VIb, VIIb, ruthenium, rhodium, iridium, osmium and uranium, X being sulfur, selenium, tellurium or mixtures thereof and y a number ranging from about 1.5 to about 4, which material is prepared by reacting neat a salt of metal M with a source of sulfide, selenide, or telluride ions, said source being selected from the group consisting of Li2X, Na2X, K2X, NaHX, LiHX, KHX, NH4HX, (NH4)2X, (RNH3)2X, (RR'NH2)2S, (RR'R"NH)2X wherein R, R' and R" are the same or different C1-C20 alkyl or C6-C20 aryl at a temperature of from 0° to 400°C.

Description

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l . An improved process i5 described for the catalytic

2 treatment of hydrocarbon feedstreams containing organic sul^

3 fur such as coal liquefaction products and heavy resid oils

4 which compr~ses contacting said feedstream and hydro~en with s a catalyst at a temperature and hydrogen pressure and for a 6 time suficient to effect the desired change in the feed, 7 the improvement comprising using as the catalyst a composi-8 tion of the formula MXy wherein M is a transition metal se-9 lected from the group consisting of Group IVb, Vb, VIb, VIIb, ruthenium, rhodium, osmium, iridium, and uranium, X is 11 a chalcogenide selected from the gr~up consisting o~ sulfur, 12 selenium, tellurium and mixtures thereof, preferably sulfur l3 and selenium, most preferably sul~ur, y is a number ranging 14 from about 1.5 to about 4~ particularly 1.5 to about 3 The 1$ : ca~alytic materials have a crystallite size of about 50 A x 16 10~ A or less and a part~cle si~e of 0~1 micron or less, 17 preferably O.05 micron or less. The catalyst is prepared by 18 reac~ing neat or in the presence of an added nonaqueous sol-19 ~ent, the desired metal salt or salts, the anion of the salt preferably bèing selected from the group consisting o ha-21 lide (preferably chloridej, acetatq, carboxylate, per1uoro-22 earboxylate, acetylacetonateg hexafIuoroacetonate, nitrate 23 and sulfate and a source of sulfidq, selenide or telluride 24 ions, said source being selected from the group consisting Of Li2X, Na2X, K~Xy NaHX, LiHX, NH4HX, KHX7 (NH~)~X, 26 (RN~3)2X, (RR'NH2)2X, (RR'R"NH)2X wherein R5 R' and R" are 2~ ~he same or different Cl~C20 alkyl, C6-C20 aryl, preferably 28 Cl-Cg alkyl, C6-C12 aryl and X is a chalcogenide selected frQm the group consisting of sulfur, selenium, tellurium and ~ mixtures thereof, preferably sulfur and selenium, most pref-31 erably sulfur. The nonaqueous solvent (if one is used~ i~
32 selected from the group consisting of ethers having 4-8 2 - ~ .

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1 carbons1 such as tetrahydroEuran (THF)~ acetonitrile, ben-2 zonitrile, pyridine, propionitrile, N-methylformamide, di-3 methylEoYmamide (DMF), l,2-di-methoxyethane (DME), acetone, 4 propylene carbonate, ammonia, C6-C20 aromatics, molten sul-fur, qulfur dioxide, diglyme, ethylacetate, esters of from 6 C4 to ~5, sulolane, dimethylsulfite, tributylphosphate, Cl 7 C30 amines~ Cl Cl2 alkarIes, anhydrous acids, al~ylhalides of 8 from l 20 carbons such as chloroform and aryl halides of 9 from 6-20 carbons, such as chlorobenzene, wherein the halide 10~ is sel~cted from t~e group consisting of Cl, Br and I, and 11 the hydrocarbon feed to be catalytically treated. The ca~a-12 .lyst orms spontaneously when the reac~ants are mixed at 13 temperatures below 400C. and at atmospheric pressure. The 14 catalyst may be isolated.by filtration and washing with ex-cess solvent (when o~e is used) or by vacuu~ pumping any 16 volatile coproduced anion sal~ Pre~erably the chalcogçnide 17: is sul~ur and y is about 1~5 to about 2, most preferably 2~
18 The catalytic material can be prepared outside the 19 catalytic rea~tor or it can be prepared in the ~e~ctor it-sel by the introduction of the appropriate, desired start-21 ing materials (as outlined above) into the reactor with the 22 hydrocarbon eed as the nonaqueous solvent.
23 The ca~alytic processes which are benefited by the 24 use ~herein o~ the above described compositions are hydrode~
2s sulfurizat~ (HDS), hydrodenitrogena~ion (HNN), hydroconver-26 sion and hydrogenation 27 Typically, the ca~alytic processe~ are run at t~m~
28 peratures ranging from ambient to 500~C, preferably lO0-~ 450C, mos~ preferably 200-400C at pressures o from l atm.
to 5000 psig H2, preferably lO0 ~o 2000 psig H2 and at space 31 velocities of .l to lO V/V/Hr., preferably .l to 5 V/V/hr.
32 Petroleum crude oils and especially the heavy ,.

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1 residuals and shale oil and tar sand oils derived therefrom ~on~ain sulfurous compounds in large quantitiçs. The lique-3 faction products obtained from coal also contain consider-4 a~ble quantitie$ o organic sulfur compounds. Typically, S 9ul~ur content for the various hydrocarbon feedst$eams is in 6 the range of from about l to about 6 percent. Because of 7 the d~l~terious ef~ects sulfur compounds have on ~he env~-8 ronment, it is necessary to remove most, if not all, of the 9 organic sulfur from the hydrocarbons before these hydrocar-bons are useable as uels. Consequently, new and improved 1, prQcesses and catalysts ~or effecting this removal are con-12 s~antly being sought.
13 In the past, transition metals of from Group IVb to 14 VII have been used to effect this hydrodesulfurization. Such metals, however, quic~ly become deactivated. To overcome 16 this, metal sulfides have been utilized as HDS catalys~s.
7 The literature is replete with descriptions of ~ hydro~enation and hydrodesulfurizstion processes utilizin~
19 sulfided IVb to VIIb metals in supported and unsupported con-dition. See for instance, U.S. 1,932,369; U.S. 3,694,3$0.
21 U. S. Patent 3,840,473 describes a hydrodesulfurizatlon pro-22 cess using phosphate-free catalysts of Group VI and/or Group 23 VIII metals, their oxides or sulfides, on a nonzeolite car-24 rier, wi~h addition of l-lO wt. % Group IVb metal as promoter.
U.S. Patent 2,835,349 to Hans~ord describes a pro-26 ~ess for hydrocracking and desulfurizing a mineral oil feed-27 stock containing at least about 0.1% S which comprises con-28 tacting the ~eedstock with a catalyst in the absence of H2O
and 02 but wi~h about lO00 to lO,000 SCF of H2/barrel of feed wherein the catalyst comprises a major portion of an 31 adsorbent acidic oxide carrier having cracking activity and 32 ~ minor portion of chromium sulfide at tempera~ures, pres-~l~Z9~1 sures and space velocities sufficient to effect the conversion.The chromium sulfide is prepared by the reduction of chromium sulfate which has been deposited in the carrier from aqueous solution.
U.S. Patent 2,531,767 to Chenicek teaches the use of Mo sulfide as HDS catalyst.
~ ritish Patent 362,354 describes a desulfurization process using rhenium or compounds thereof brought in colloidal form onto suitable carriers together with other metals or com-pounds. In an example a catalytic mass consisting of molybdenumoxide in carbon and rhenium sulfide (ReS2) in carbon was used to desulfurize a light Venezuelan motor cylinder oil containing .41% S. The end product obtained contained 0.16% S.
It has been discovered, and forms the basis of this disclosure, that catalytic processes and hydrodesulfurization processes in particular, can be improved in terms of activity and selectivity by using a catalyst as described in the foregoing.
It is to be noted~that o~ the catalysts described in this dis-closure, NbS2 is not included among those catalysts useful in the hydrodesulfurization process.
Typically, a metal salt of the transition metal-such as TiC14 is reacted with a nonaqueous solution of, or a slurry of a convenient sulfide, selenide or telluride ion source such as Li2S, hydrosulfide salt (i.e. LiHS, NH4HS, KHS, NaHS), (NH4)2S, Na2St X2S (RNH3)2S, (RR'NH2~25, (RR'R'INH~2S wherein R, R' and R'l are the same or different C~-C20 alkyl o~ C6-C2~ aryl, preferably 1 8 Y 6 C12 ~ryl~ Li2Se, Li2Tel (NH~)2Se, in a non-aqueous solvent such as THF, ethers, acetonitrile, propylene carbonate, DMF, molten sulfur, etc. The reaction which takes place is. nonaqueous MZg + 2A2X s or neat MX2 ~ 4AZ
M= all Group IVb, Vb, VIb or VIIb transition metals or ruthenium, rhodium, iridium, osmium or uranium; A = alkali 1 metal, NH4~, RR'R"NH~, or other cation as defined above;
2 Z = convenient anion such as Cl, Br, I, acetate, carboxylate, 3 nitrate, etc., as recited above, X = sulfur! selenium or 4 tellurium.
Any convenient source of M~2 ~ 5, preferably 6 M-~5, moSt preferably ~4, can be used. Comple~es formed in 7 solution which can be isolated as solids may be used as M~4 source. In some cases (such as Nb and Ta) a pentavalent 9 salt may be used directly because reduction of M~5 to M+4 occurs, for example:
11 NbCls ~ 2.5 Li2S ~~~ NbS2 ~ ~5LiCl + 0.5 S
12 The reaction is normally but not necessarily con-13 ducted in the absence of an excess o sulfide, selenide or 4 telluride ion sources although other starting materials may ~5 be present in excess. Since particle size depends on the 1~ rate of mixing ~f reagents, the reaction may be allowed ,~o 7 proceed instantly, upon total admixture of one reagent to 18 the reaction solution yielding fine products, or upon the 1~ measured addition of small increments of one reagent to the ~ rea~tiQn solution, the reaction not achieving totality ~or 2~1 several days.
~2 The temperature of the reaction may range from 23 -78 to 400C, e.g , 0 to 400C., preferably ambient 1~5C) 24 to 300C but the temperature chosen should be above the freezing point of the nonaqueous solution used or slurry ~26 ~ormed. These temperatures are markedly lower than those 27 needed when preparin~ dichalcogenides vla solid state or g~s 28 ph~se mçthods wherein reaction temperatures up ,to and exceed-ln~ 1000C are commonplace.
The catalysts prepared by the recited procedure ~1 may be used in a supported or unsupported form. The mate-32 rials may be de~osited on the support by adsorption thereon ~ 1 ~2 ~

1 of the metal sulfide from a homogeneous dispersion produced 2 by reacting the reagents in certain solvents such as propy-3 lene carbonate. The supports are any typical inert or re-4 fractory oxide material, such as silica, the oxides of Groups IV-VI, especially TiO~, ZrO2, ZrTiO4, etc., preerably 6 MgO, CaO, alumina, silica-alumina and high surace area 7 carbon.
8 EX~MPLE 1 - Preparation of TiS2(ZrS2, HfS2 and VS2~
9 The following example employs TiC14 as a starting lo material. It was found that the procedure worked equally 11 well fo~ ~rC14, HfC14, MoC14 or VC14. A solution of 10 12 millimoles Qf TiC14 (1.9 g) in tetrahydrofuran (75 ml) was 13 made up in a dry box (TiCl~ is not stable in air or moisture).
14 To this s~irred solution at room temperature was added 0.96 lS g ~20 millimoles) of lithium sulfide. The yellowish ~Qlu- -6 tion immediately began to darken. The reaction wàs allowed 17 to proceed several hours although it was essentially complete 18 within one hour. The resulting dark brown solid was fil 1~ ter~d and washed with 10 ml THF . From the combined filtrates 83% o calculated ideal yield of lithium chloride was iso 21 lated after evaporation of the solvent. An elemental analy-22 sis of the dark brown powder remaining after drying revealçd 23 it to be TiS2 containing one-half mole of sol~ent tetrahydro-24 furan and Less than 5% by weight LiCl. Be$0r2 catalytic evaluation, the powder was heated at 400C in a stream of 26 H21H2S for 1 hour, cooled, then washed with 12% acetic acid;
27 then reheated in a H2/H2S stream for one hour after whieh the 28 chemical analysi~ showed only metal and sulfur with approxi- -29 mately 2:1 sulfur to metal ratio. The sulfidin~ step, how-ever, is not essential to the successful practice o~ the in~
31 vention, it merely be~ng an optional preerred step.
EXAMPLE 2 - Preparation of NbS2 (Tas2) . - ~

1 This procedure is applicable to those transition 2 metals of Group Vb and VIIb which form pentahalides (Nb-a~d 3` Ta and Re) and the example is given for niobium pentachlor-4 ide:
To a solution of 10 millimoles of NbC15 (2.68 g) 6 in 50 ml r~F was added l.lS g lithium sulfide (25 millimoles~
7 ~and the mixture was stirred in the dry box overnight. The 8 dark product obtained on ~iltration was ~ound to cont~in 9 60a/~ by weight NbSl,g7. This sample was then treated as in Example 1 upon which the analysis was close to 100% NbSl,g7.
11 EXAMæLE 3 - Pre~aration of Molybdenum Disulfide l2 Addition of lO millimoles of molybdenum tetra-l3 chloride and 20 millimoles of lithium sulfide to 30 ml THF
14 witb stirring results in a fine ~lack solid which on filtra-l$ tion and drying contains 70% by weight MoS2~ Most of the l~ additional weight can be attributed to solvent which can be 17 removed by heating to about 150C and pumping (1 torr). A
18 H2/H2$, 12% acetic acid, then H2/H2S treatment yielded a ~19 black powder.
- :
EXAMPLE 4 - Li2Se ~ ZrC14, ZrSe2 21 Into 50 ml acetonitrile, 10 millimoles~zirconium 22 tetrachloride is ~dded and then, with stirring, 20 milli~oles 23 of lithium selenide is added~portionwiSe. After several 24 hours'stirring, the solid product is collected on a filter and washed with acetonitrile and dried. Thus, 10 millimoles 26 Of zirconium diselenlde is afforded.
2~ EXAMPLE 5 - Neat Preparation of Crystalline TiS2 from 28 NH3, H2S and TiC14 In a three-necked fla~k, approximately $ grams of (NH4)HS or (NH~2S was prepared by flowing in NH3 gas and 3l H2S gas. To the res-tlting white solid, 3.8 gms of TiC14 3~ (20 mmol) was added dropwise. A reaction immediately l occurred yielding a black brown solid, which was TiS2 +
2 (NH4)Cl. This black-brown solid was removed from the flask 3 and sealed in vacuum in a 20 mm diameter quar~z tube 25 4 inches in length. The tube was placed in a temperature gradient wi~h one end at 380C and the other at 100C for 6 one day. (NH4)Cl sublimed and condensed at the colder end 7 thus e~fecting se~aration~ At the hot end, the TiS2 anneal-8 edl yielding a perfect crystalline X~ray powder pattern.
9 EXAMPLE 6 - ReS2 From ReCls by the Reaction ReCls +
2 . 5 Li2S ~ 5LiC1 ~ %S ~ ReS2 ll 3.64 gm$ of ReCls were reacted at room temperature 2 with 2.30 gms of Li2S in 100 ml ethylacetate and stirred.
13 The black product was filtered and dried in H2S at 400C.
l4 The product analysis was ReS2Oo l$ Theoretlcal Measured __ 16 % Re 74-39 74~40 17 % S ~5.61 25.~9 18 X-rays indicated that the product corr~sponded to ReS2 and 19 line broadening indicated a crystallite size of about 40x80 A. The BET surface area was 50.2 m2/gm. Product before 21 heat trea~ment was completely amorp~ous to X-r~ys, indicat-22 ing a erystalline order of less than 5 A, thus an a~orphous 23 solid.
24 EXAMPLE 7 - ReS2 From ReCl~ by the Reaction ReC14 +
2Li2S - ~ ReS2 ~ LiCl 26 In a manner exactly analogous to Example 6, ReS2 27 was prepared from ReC14 at room temperature with the same 28 results except that excess sulfur did not have to be removed 29 by washing or heating.
30 EXAMPLE 8 - ReS2 Dispers i ons 31 2.83 grams (8 mm) of ReCls was added to 80 ml of 32 propylene carbonate. To this was added 0.89 gms of Li2S

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1 (l9 m~) and the solution was stirred for 4 hours yielding a 2 black liguid which was O.l M in ReS2 and could be continuou~-3 ly diluted to any concentration. This black liquid passed 4 through normal filter discs and was stable.
EXA~PLE 9 - ReS2/MgO Composition A O.l M dispersion of ReS2 in propylene carbonate 7 ~as prepared as in Example 8. 25 ml of this dispersion was ~ contacte~ with 4 gms of MgO and stirred for ~ hours. The 9 i~itially white solid was filtered and dried in H2S at ~00C
for l hour yielding a dark gray solid. The solid ReS2/MgO
1I composite contained 2.33% Re> The amount of ReS2 adsorbed 12 Qn the MgO can be controlled by varying s~irring time and 13 concentration.
14 If the reactions herein described are carried out in appropriate media, stable hamogeneous dispersions of the 16 chalcogenides in the liquid result (either accompanied by 17 or in the absence of the precipitated solid). Appropriate 18 solvents include propylene carbonate, dimethyl0rmamid2 ~DMF~, 19 pyridine, acetonitrlle, benzonitrile, propionitrile, l,2 di-me~hoxyethane, diglyme and N-methylformamideO Alternatlvely, ~1 if in addition to a nondispersing solvent (such as THF) a 2~ dispersing agent such as pyridine (or alkylamines~ is 23 initially present, a similar dispersion will result. Murphy 24 and Hull (J. Chem. Phys, 62, 973 (1975)) have described dis-persions of TaS2 in aqueous media which are considerably less 26 stable due to eventual decomposition of the sulfide by wate~
27 (hydroly~is). In nonaqueous solutions such as those describ-2~ ed in the instant invention decomposition does not occur 29 and stability lasts for mon~hs.
As Hydrodesulfurization Catalysts ~1 A, Materials of the formula MXy wherein M, X and 32 y are as prPviou~ly defined and which materials are prepared - ~0 2 ~ ~

1 in acco~dance with the procedures outlined hereln are su~e-2 ~lor hydrodes~lf-lri.~.a~i.oll cfltalys~s. The c1esulfur;.z~ti.on of 3 dibenzothior)hene (DRT) i.s an in(:1ust:ry-wi.de, acce~ted tes~ o:E
4 the HDS activlty of v~rious materi.als. 'rhese mat~r;.al.s de-sulfuri~e DBT at temperatures ~ 300C flnc1 hydrogen Dressure 6 ~ 250 psi according to reaction (l) yielding biphenyl (BP) 7 and cyclohexylbenzene (CHB):
8 (l) 2 ~ ~ excess H2 catalyst;
9 ~ S'~'J Decalin DBT 5 wt. ~/O BP
11 ~ + 2 H2S

~ The amount of CHB formed in 2.0 hrs. at 25C - 400C is 14 used as a measUre of the hydro~enation activity of the sulfide 1$ in a sulfur or H2$ environment.
16 The catalyst pretreatment entails exposure to 15~/o 17 H2S/H2 (55 cc/min.) for 2 hours at 25 - 40QC. When appro-18 priate, the novel materials are compared to prior art binary 14 sulfides and to commercial cobalt molybdate on ~-alumina.
The rate constants for the desuluxization of DBT
21 for the unsupported materials were calculated a3 per gr~m o 22 material; b) per millimole of metal and are reported in 23 Table I.

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1 The rate constant per gram of catalyst for com-2 me~cial cobalt-molybdate (Nalco-~CM 468) ono~ -alumina 3 under identical conditions is 67 x lOi6 molecules of DBT
4 converted/gm-sec.
The literature teaches tha~ layered sulfide~ pre-pared according to prior art reactions (2~ and (3):
7 (2) M + 2S -~ MS~
8 M = Group IV VIIB
4 (3) NH4MS4 H~2 ~ MS2 ~ H2S + NH3 M = Mo, W
11 are catalytically active for desulfurization reactions.
12 HQwever, the materials prepared by reactions described in 13 the fore~qing are more active per unit gram of ~aterial 14 under the same conditions of temperature, pressure, catalyst mesh and quantity. The comparative data i9 summarized in 16 Ta~le II. Materials 2 and 5 are prepared via the nonaqueous 17 precipi~ation technique described herein whilQ mate~lals l, 18 3 and 4 are prepared by typical prior art techniques:
19 clearly, the nonaqueous precipitation technique yields ~ superior catalys~s.

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1 . B. ReSy (wherein y is about 1.$ to about 4) ~ ma~erials prepared by the nonaqueous precipitation tech-3 nique described in detail above, are superior HDS type 4 catalysts compared to ReSy materials prepared by p~ior art $ tech~ques. In Table III, materials 1 and 2 are prepared

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8 nique. Clearly, the nonaqueous precipitation materials ~ are superior.

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- 16 _ t7~3l In Table IV, the ReSy type materials are compared ~ for their activity/gm or the desulfurization of DBT tp BP
3 and t~eir hydrogenati~n ac~ivi~y as re~lected by convers~on 4 to CHB. Materials 1, 2 and 3 are prepared by no~aqueous pre~ipitation while material 4 is prepared by a typical 6 prior art technique. The nonaqueous precipitation materials 7 are a~ain clearly superior HDS and hydrogenation ca~alys~s, 8 ~deed their activity per g~am is superi~r to ~ co~mercial

9 cobalt maly~a~e on ~-alumina catalyst (CMA) ~aterial.
lQ Data arç given in Tables V and VI for other 11 materlals prepared by the nonaqueous precipitation method.

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~ HYDRODESU~FURIZATION ACTIVITY OF G~OUP VIII
3 TR~NSITION METAL SVLFIDES
4 Conditions: Carberry Reactor, 400C, 450 psi,

10/20 mesh catalyst parti~les 6 ~ctivity 7 1~olecules DBT-~ x 8 Catal~t r x 10 9 x ~BP CHB
10RuS2~ RUS2-x 210 20

11 RhSl 5 -~RhSl.5-x

12 OsS2-~ OsS2_~ 85

13 IrS2--~IrS2-x 67 ~4 TABLE VI
Hy~Ro~EsuLFuRIzATIoN AND HYDRO~NATI~N ACTIVITY
~6 OF GROUP V~II TRANSITION METAL SULFIDES
,~ r , ,~
1~ Condi:~ions: Garberry Reactor, 350~C, 450 p9i~
18 20/40 mesh particles 19 Activity 2b 16molecules DBT ~ x 21 ~ r ~c 10 gm - sec _ _ 22 x - BP CHB
23 RuS2 _~RU$2-x 113 24 24 RhSl,5 -~hSl.5-x 4 10 OsS2 ~~fi$2-~ 4~ 17 ~6 IrS2 -~IrS20x 21 17 27 ~. ReS2 supported on refrac~ory oxides and hi~h ~8 su~face area ~asic or açidic solids such as MgO, ÇaO, 29 ~-A1203, prepared ac~ording to the follqwir~g procedure?
reac~ion ($), is an active HDS catalyst for resid-like ~1 organosu~ur molecules, i.eO, DBT:
32 (5) ReGlx ~ Support . ~ Li2 ~ ~
33 Propylene Stir 4 hrs 34 CarbQna~e at rloom temperature 1 ReS2/Support ~ ReS2(0.1%-10% Re)/
a 400 C Suppo~t ~ 1 hr.
4 I~ Table VII, the ReS2 supported catalysts pre-pared by the nonaqueous dispersion technique on various 6 ~idic and basic supports described herein are ~ompared 7 wi~h supported rhenium catalysts prepared by typical prior 8 art te~hniques.
9 In general, the metal chalcogenide will be p~esent at rom 0.~1 to 30 wt. %, preferably 0.1 to 10 w~. % metal 11 bas~d on total catalyst.
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1 An activity comparison of the ~ -Al203 supported ~ rhenium catalysts indicates that the nonaqueous dispersion 3 material, compound 3, displays comparable activity to prior 4 art material 5. Material 4 however, displays the best acti-vi~y of the alumina supported catalysts. The ac~ivity of 6 this material was increased considarably by the elimina~lon 7 o~ ~he calcin~tion step. Consequently, prio~ art ~chniques 8 in which calcination at elevated temperaturesin air are 9 routine yield inferior catalytic ~aterials for hydrodesul-furiz~tion-11 The activity advanta~e of the nonaqueous disper-12 sion prepa~ation over aqueous methods is more dramàtic ~hen 13 the support is MgO. In this case, the activity is two to ~4 fo~r times higher than prior art materials; material l~ i8 1$ ~.2 ~ 4.5 ti~es more active per gram and per milllmole of 16 rheniu~ than materials 6 and 7 respectively.
7 In Table VIII, the HDS activity of ReS2 (2.1% Re) ~8 l~go is ~resen~e~ and com~ared to CM~ at 400C and 4$0 psig, 19 H~flow ~lOO cc/min.
Table VIII indicates that under comparable con 21 ~itlops bu~ wi~h lower metal lQading and less ca~alyst, R~S2 22 ~2.1 ~f~ Re~lMgO is approximately as ac~ive aæ CMA at a ~pace ~3 velocity equ~l to l V/V/H. However, ReS2/MgO is much more 24 selective toward dèsulfurization as evldenced by the selec-2~ tivity actors. Consequently, under conditions necess~ry to 26 desulfurize resid, i.e. T - 400~C, P ~ 450 psig, SV ~ 0.5-l 27 V/Y/H, Rqs2/Mgo is as active (on mole % conversion basis) as 28 CMA but is far more selective; thus the pre~erred ca~alys~.

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Claims (11)

1. THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
   PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
   l, A process for the treatment of hydrocarbon feedstreams wherein said hydrocarbon feedstreams are contacted with a catalyst at a temperature and pressure and under condi-tions sufficient to effect the desired change in the hydro-carbon feedstream, which comprises using as a catalyst a material of the formula MXy, M being defined as a transition metal selected from the group consisting of Group IVb, Vb, VIb, VIIb, ruthenium, rhodium, iridium, osmium and uranium, X being sulfur, selenium, tellurium or mixtures thereof and y a number ranging from about 1.5 to about 4, which material is prepared by reacting neat a salt of metal M, with a source of sulfide, selenide, or telluride ions, said source being selected from the group consisting of Li2X, Na2X, K2X, NaHX, LiHX, KHX, NH4HX, (NH4)2X, (RNH3)2X, (RR'NH2)2X, (RR'R"NH)2X
   wherein R, R' and R" are the same or different C1-C20 alkyl or C6-C20 aryl at a temperature of from 0° to 400°C with the proviso that when the treatment is a hydrodesulfurization process the catalyst is not NbS2.
2. 2. The process of claim 1 wherein the catalytic reactions in which the materials are used are selected from the group consisting of hydrodesulfurization, hydrodenitro-genation, and hydrogenation run in the presence of hydrogen.
3. 3. The process of claim 2 wherein the catalytic reaction is hydrosulfurization.
4. 4. The process of claims 1-3 wherein the transition metal is selected from the group consisting of Group VIb and Group VIIb transition metals.
5. 5. The process of claims 1-3 wherein X is sulfur.
6. 6. The process of claim 1 further characterized by the use of a non-aqueous solvent in the preparation of the catalyst.
7. 7. The process of claim 6 wherein the non-aqueous solvent is selected from the group consisting of acetonitrile, benzonitrile, propionitrile, acetone, C1-C20 alkyl halides, C6-C20 aryl halides 1,2-dimethoxyethane, diglyme, N-methyl-formamide, dimethylformamide, C6-C20 aromatics, pydridine, C1-C12 alkanes, C4-C8 ethers, anhydrous acids, propylene carbonate and the hydrocarbon feedstream to be catalytically treated.
8. 8. The process of claim 6 wherein the catalyst is prepared in a catalytic reactor chamber by the addition of the appropriate starting materials, the hydrocarbon feed stream to be catalytically treated being the non-aqueous solvent.
9. 9. The process of claim 1 further characterized by the catalyst being deposited on high surface area supports selected from the group consisting of high surface area carbon and high surface area refractory oxides.
10. 10. A process for the treatment of hydrocarbon feedstreams wherein said hydrocarbon feedstreams are con-tacted with a catalyst at a temperature and pressure and under conditions sufficient to effect the desired change in the hydrocarbon feedstream, which comprises using as a catalyst a material of the formula MXy wherein M is a transi-tion metal selected from the group consisting of Group IVb, Vb, VIb, VIIb, ruthenium, rhodium, iridium, osmium and uranium, X is a chalcogenide selected from the group consisting of sulfur, selenium and tellurium and mixtures thereof, and y is a number ranging from about 1.5 to about 4, which material has a particle size of 0.1 micron or less and a crystallite size of about 50 .ANG. x 100 .ANG. or less with the proviso that when the treatment is a hydrodesulfurization process the catalyst is not NbS2.
11. 11. The process of claim 10 wherein the catalyst is ReS2.