[1]IV Ir 32167y497 United States Patent Office s.@tented Jan. 26, 1965 s,,ilfides. The improve d activity of the catalysts cf this inventio n is realized by preparat ion of the catalysts in a particula r manner to provide catalysts in which the concent @ration of the molybde num compou nd ranges between alou,t 12 md about 35 w,-,iaht percent (calculat ed as molybde num trioxide) , based on the total weight of the catalyst and such that the catalytic iagent comprisi ng nickel is present in an amount to pioiide a finished catalyst in which the alitomic ratio of molybde num to nickel is be10 tiveen about I and 4. Superio r hydroge nation activity is obtained with the catalysts in whir-h the atornic ratio of nlolybde num to nickel is between abotit 2 a@d 3 ' To obtain this preferre d atomic ratio within the aforesai d concent ration of the molybde num compou nd, the catalytic 15 a.@ent comprisi ng nickel is present in an amount between abolt 2.3 and about 9.1 wei,- ht percent (calcL,.I ated as 14,iO), based oi, the total weight of the catalyst. As indicat ed above, silica is used as the stippor t of the catalys ts of the prese nt inve@ition . 'ne silica emplo yed 20 may be prepare d by me+,hod s well know@l to tiaose skilled in the art. For exami)le , siliceous hydroge ls may be prepare d by hydroly sis of an allcyl orthosili cate such as ethyl orthosili cate. Another met'-lod compris es commin gling - @Ln acid siich as a hydroch loi-ic acid or stilfuric acid with 25 commer cial water soluble sodium silicate under conditio, @is to precipita le silica, followed by washin. @ with acidulat ed water or otlier@v ise to remove sodium ions. Pr;or to use in the preparat ion of the catalysts of this inventioi i, the silica gel is prefera bly calcined at an ele@,at ed tempe rature st,.ch as between aboiit 600' F. and about 1200' F. The catalysts of this inventio n may be prepate d by a variety of methods without departin g from the scope of this inventio n. The preferre d method compris es impre.- n-,ttion of sil-ica, prefera bly a high purity sil-ica, either 35 @.n the form of a hydrotis gel or calciiied gel, with the precurs or of the molybde ntim catalytic agent prior to imprenation with the precurs or of the nickel catalytic a.-ent. This method leads to the producti on of catalysts of enhance d activity as compare d with catalysts prepare d by 40 the reverse order of impregn ation of the silica. In a mo.-.- specific embodi ment of this inventio n the silica is impregn a@ted with -a solution of the molybde num preculrs or compou nd, typical example s of which aie silicomol ybdic acid, phospho molybdi c acid and ammoni um 45 molybda te. The composit e is then dried, if desired, and is pre'Ler ably calcined at an elevated temperat ure prior to incorpor ation of the n-' ckel precurs or compou nd. Typical example s of the latter type compou nd are nickel acetate, nicl-,el chloride , nickel sulfate !and nickel nitrate. The - 10 com posite is then dried, if des.red, arid/or calcined at an elevated temperat ure. Iinprov ed catalysts also@ are produred by passing hydroge n sulfide into the silica impregn ated with the molybde num and nickel pre@ur sor compou nds. Another suitabl6 method of prepa@ ration 55 compris es dry mixing of the silica and molybde num piecurso r co@npo und follovie d by calcinati 6n of the mixture. NVhen employe d, the drying steps may be efferted at a temperat ure of between -,tbout 100' F. iand about 400' F. Cal cin eLi on is eff ect ed at an ele val ed te mp era tur e suc h 60 as betwe en about 600' F. and about 1200' F. in the prese nce of air, nitro,- en, oxyge n or inert gases. li acco rdan ce with a pref erre d emb odim ent of this invei -tion, the calci ned com posit e com prisi ng the oxid es is prec ondit ione d with a gas,- ous strea m @co - nipri sing hy65 dro--- n suifide, or the metal sulfide s may be forme d in situ such as, ' Or ex,- ..mple, wlien the feed stock to be treate d contair s a high sLIfLr conten t. When the catalys ts are precondi lioned by contqcti ng with hydro.- en sulfide, hydroge n is preferab ly em@ ployed as the carrier gas althougli 70 other carrier gas-,s such as nitrogen and argon may be employe d. The concentr ation of hydroge n sulfide iq the carrier gas may vary between about 0.1 and about 5 mole 3,167,497 HYD'@IOG7-NATION CATALYQJT AND PROCES-S Erne-ct Solomon, Montcl,.iir, N.J., assignor, by mesle ,issignments, to P-aliman Incorporated, a cerperation of Dela-tvare No Dravving. Filed Aug' 11, 1959, ger. No. 832,892 14 Claims. (Cl. 208-143) This inveition relates to a process for the hydrogeilaLion of unsaturated hydrocarbons. In one ast)ect this iTivention relates to aniniproved type of catalyst particularly usef,dl forthe hydrogen-ation of unsaturated hydrocarLoPs and,to a method of preparation of such catalyst. in a-@iother aspect this irvention - relates to a process for altering the hydrogen-carbon ratio of a single unse@turated hydrocarbon or of,a mix-ture of unsatlrated h@,dro@-ar'oons by hydrogenation in the presence of a particl!ar catalyst. The treatinent of unsaturated hydrocarbons with hydroaen in the presence of a hydrogeiiatioli catalyst is ;,7,-@ 1 1 k,own,in the ar@t. With some exceptio@ns the desirability of liquid fuels @and lubricants is rol,,ahly propoFtio-ii,-,l to the combined hydrogen that each contai.-is. With the exception of cracked products, however, ma-@iy petroleum frac',ions contain little or none of the easily hydro.-enated olefinic -groups so that deepseated chemical cha@i.-es arc necessary to promotethe entrance of hydrogen atoms :Into the molecules. High grade kero--cnes are made up of saturated hydrocarbons, paraffins;and naphther@es and are low -iii sil-Ifur, ni,rogen and oxygen conipou-@ids. Fowever, kerosense distillates f@rom many crudes usually possess few or none of these characterislics. By hydro.-enation, aromatics of such kerosene distillates C,,in be converted to naphthanes, any of the:olefins pr6sent are saturated while sulfu@r, nitrogen and othe:.- extraneous elements are substantially,removed as hydrogen sulfide, ammonia, etc., by the cracking and reduction of correspondiig compouiids. The hydro.-en of aromatir, hydrocarbons whether they are substantillly the only components of the charge stock or jare present as components of a hydrocarbon fraction is relatively difficult to effect. With t-he presently us,-d catalysts a relatively severe corabination of conditions must be applied even with catalysts of high activity. Under such severe conditions the selectivity of catalvsls decreases due to concomitant reaciions such as hydrocracl,ing. This latter reaction is especially undesircole when it is desired to produce high yields of relatively piire petror,hemicals since it leads to loss of yield of the desired product and makes the process more difficult to control to,obtain the desired results. It is an obj--ct of this invention to provide an improved hydra,@enation process. 1-t is a further object of this invention to provide an improved process for the hydrogenation of arom-@Ltic hydrocarbons -in good yield and selectivity. It is a further object of this invention to provide a process of hydrogenatin- a hydrocarbon fraction containing unsaturated hydrocarbons by cont-,Lcting said fraction m,@ith an imi)roved catalysts comprisin.- a compotind of molybdenum. It is a further object to provide a new ind improved particular hydrogenation catalyst and -a method for the manufacture thereof. Various other objerts and advantages of this invention will become apparen@t to those skilled in the art from th-. accompanying desrription and disclosur@-. The above objects are accomplished by providiii.- a particular catalyst composition co@-Dprisin,a molybdenli-.ii and nirk-el in a part.icular atomic - ratio stipported o-@i silica. The catalytic agent may be in clementql form although it is preferred that the molybdent,.rii and nickel be i-i combine,d fonn such as in the 'Lorm of their oxides aid/or
[2]3,167,497 p.-reent, preferably between about I and about 3 mole percent. The preconditioning with hydrogen sulfide may be effected at a temperature between about 400' F. and about 1000' F. and at a pressure between about 50 and about 2000 pounds per square inch gauge. This treatment is 5 preferably.continued until sulfiding reaches a steady state, i.e., until the inlet and outlet gas compositions are identical. As a result of sulfiding, the oxide of - molybdenum is prob-,tbly converted tO MOS2 or MoS3 or mixtures thereof, andthe oxide of nickel is probably converted to 10 NiS or Ni2S3 o,r mixtures thereof. The above-described catalysts find particular utility in the hydrogenat;on of unsaturated hydrocarbons including olefhiically and aromatically unsaturated compounds. The feed stdck may consist of a single unse@- 15 urated compound such as when a high pur,'ty product is desited or it may comprise a mixture of such - hydroca@r@ bons. Thus, for example, aromatically unsaturated compounds stich as benzene, styrene, toluene, naphthalene, ard darivatives thereff, are @.uitable a-@id typical reactants 20 as well as aliphatically unsaturated compounds inoludin.- acyclic and alicyclic compounds such as, L'or exainple, cyclohexene, cyclohexadiene, butenes, pente.-ies, he,xenes, heptenes, cyclopentadiene, meth yleyclopentene, trimethylethylene, octenes, nonenes, acetylenes, indene 25 and derivatives thereof. Also included witbin the scope of this invention is the hydrogenation of gasoline p,roduced by a catalytic erE-.cking process s7ach gasoac usually being high in olei'ins, par-ticularly .nonoolefins. Othe.- feed stocl@s which maY 30 be hydrogenated by the catalysts of this invention are those in which the carbon to hydrogen ratio is high, such as reduced crude oil and vacuum tower bottoms, i.e., hydrocarbon stock from which the lighter distillable fractions have been removed. Hydro.-enation of such residual 35 oils increases the gravity thereof and tends to prevent excessive coke lay down during subsequent treatment thereof such ias during a subsequent hydrocracking process. In addition, the feed stock may be a hydrocarbon fraction boilin.- withi-@i the range of about 325' F. to 40 about 600' F. such as in particular a kerosene fraction containing unsaturated components. By hydrogenation, the aromatics contained in the petroleum fraction are converted to naphthenes, a-@ly of the olefins which may be present are saturated to form a hydrogenated product 45 substantially free of unsaturated compone-@its and of improved smoke point. At the same time, sul.'Lur, vitrogen and other extraneous elements which are usually present in the kerosene fraction or vacuum bottor@is feed stocks, for example, are substantially removed probably in the 50 form of hydrogen sulfide, ammorilia, etc. In accordance with the process of this invention, a hydrocarbon or hydrocarbon fraction such as those described above, is contacted with the catalysts of this invention in the presence of added hydrogen under hydro55 genation conditioris with net consumptioii of hydrogen to cause selective hydro.-enation of the feed components witli minimum hydrocracking, to produce product having a lower degree of unsaturation which, in the case of a hydrocarbon fraction boilin.- within the kerosene range, is 60 evidenced by improvement in smoke point. The process of this invention may be conducted over a wide range of temperatures without departing from the scope of this invention. The operating condilions include a temperature within the range of from about 200' F. and about C5 850' F., a pressure between about 0 pound per square inch gage (p.s.i.g.) and about 2000 p.s.i.,a. and a space velocity (defined :as the feed p--r hour per pound of catalyst) between about 0.1 and about 15. Generally speaking, the conditions within wbich optimum results 70 are achieved, i.e., hi@-h activity and good selectivity, include ft, temperdture of between about 400' F. and about 800' F., a pressure between about 200 and about 1000 p.s.i.g. and a weight space velocity of between about 1 and about 10. Wh,-n a kerosene fraction is to be hy- 75 4 dro.-enated in accordance wiht this invention, it has been found that particularly good results are obtained at a temperature between about 400' F. and about 700' F. within the aforesaid preferred pressure range. Hydrogen should b-. introduced into the reaction zone at a rate ol from about 300 to about 20,000 standard cubic feet per barrel (s.c.f.b.) or the hydrogen to hydrocarl--on mole ratio may fall within the range of from about 0.35 to about 50, preferably ftom - ,tbout I to about 25 moles of hydrogen per mole of hydrocarbon with the total reaction pressure maintained between about 0 and about 2000 pounds per sq-uare inch gage (p.s.i.g.'), preferably betw-,en about 200 and about 1000 p.s.i.g. It is desirable that the hydrogen partial pressure be carefully controlled withir. the pre.Lerred range of from about 15 to about 1500 pounds per scluare inch absolute(p.s.i.a.), preferably from aboct 100 to about 900 p.s.i.a. to effect the desired conversion while maintaining the activity of the calalyst at @a high level. The catalysts of this invention are also useful for desulfurizing hydrocarbon oils, e.g., nadhthas, kerosene, gasolin.-, gas oils, total crldes, etc. The desulfurization is eftected at a temperature of about 600' F. to @about 900' F., preferably about 650' F. to about 850' F. The desulfuriz,,ition reactions can bc, effected at either exceptionally high pressurp-s in the order of up to about 2000 p.s.i.g. or at pressures as low as 100 p.s.i.g. More usually, desulfurization by means of the catalysts of this invention is accomplished at a pressure of about 500 to about 1000 p.s.i.g. TI@e desulfurization is effected in the presence of hydrogen and the conditions of operation are such that hydro.-en is consumed in the operation. Generally, the hydrogen is supplied to the process at the rate of between about 3000 and about 10,000 s.c' f.b. Generally, the weight space velocity ranges between about 0.1 a-iid about 15 pounds per hour of hydrocarbon feed charged to the desulfurization zone per pound of catalyst present therein, and more uslially from about 1 to about 8. The catalysts of this invention may be employed effectively as pellets, pills, spheres, rings, extrlsions, lumps, granules, extrusions or iii a Dowdered state and these forrps may be used in both duidized systems and those employing moving beds of contact material in either concurrent or countereiirrent flow relative to the reactants. The catalysts of this inven@:on may also be employed in a slurry type system without departing from the scope of thl:s invention. The following examples are offered as a better understapding of the preseit invention and are not to be construed as unnecessarily limiting thereto. CATALYST I A solution of ammonium molybdate prepared by dissolving 2.951 grams of (NH4)6MO7014-4H20 (Mallinekrodt Analytical Reagent) in 10 ml. of distilled water, was added to 17.102 grams of powdered silica, prepared by calcining desiccant grade silica gel (99.9 weight percent SiO2) for 2 hours a' 1000' F. After mixing thoroughly, tle mixture was dried at 250' F. for about 18 hours. The dried solid was then impregnated with 1.877 grams of ammonium molybdate telrahydrate in 10 ml ' of water and redried at 250- F. for about 23 hours. The dried powder was calcined for 2 hours at 1000' F. and the resultant calcined composite (20.93 grams) was then impregnated with a nickel acetate solution containing 2.690 grams of nickel acetate tetrahydrate, Ni(CH,COO),-4HO in abolit 10 ml. water, and mixed thoroughly. The wet paste was dried at 250' F. for 116 hours and the dried powder was then calcined for 2 h6urs at 1000' F. Th6 calculated composition, based upon ingredients added, was 18.1 we;,-ht percent M003, 3.7 weight perce-.it NiO and the remainder SiO2, the atom ratio of Mo/Ni b-.ing 2.5.
[3]A 0,167,,197 6 CAT ALYSTII A,i ammonium molybdat,- solution prepared by dissolvin g 28.85 -rams of (NH,,)6MO7024-4H20 in 50 ml. ol- hot dist'lled water, was qdded to 50.0 grams of powdered silica gel prcpared by calcining desiccant grade 5 silica gel (9.@.9 weight percent SiO2) for 2 ho-,rs at 1000' F. The resultant paste was mixed th6roughly and then partially dried at 250' F. for 4 hours and then remixed 'co a pas'Le and redried at 250' F. for 18 hours. The dried product was 'Lhe-@i calcir@ed for 2 hours at 1000' F. 10 The calciied product (70.0 grams) was theii impreg,.iated with an aqueous soltition of nickel acetate tetrahydrate prepa red by dissolving a to@'al of 16.33 grams of nickel acetat e tetrahyd,-ate in sufficient water to forn-i a paste of th@. combined iraterials. The paste was then placed in 1,5 an oven at 250' F. and re,-nixed for 1 hour and then dried overni ght. The product was mixed, dried an ad,,Ii'Lional 2 hours, r-@mixed and dried -,tpother hour at 250' F. to ,ive a fairly homogencoasly colored product. The yi@-ld of dried gro-cnd product was 76.1 grams. A portio-@i o'L 20 t'his material was caic;ned for 2 hours at 1000' F. TIie c,,ilcul ated co-mposition, based upon in.-redients added was @,10. 0 weight PerCC-@lt M003, 6.5 weight perceiit Ni,3 a-iid ti-,e re-@nainder S-iO2, the atom ratio of Mo/Ni being 2.4. 25 CAIALYST !II 1 A sbILiLion o-f arniiioniu-iii mo lybdate prepared by dissolviiig 1.476 grams of (NH4)0@klOF7024-4H20 in 10 ml. distille d water, was added to 18.551 gra.-iis of powdered silica -orepared by cale:@n;n,@ desiccart grade silica gel 0 (99.9 weight percent silica) for 2 horrs at 1000' F. After thorou .-h mixing, the mixt,,lre was d@ied at 250' F. for 18 ho,,irs ' The dried powder was reimtregrza'ted w@th ad,,iL-lon,al ammonidm riiolybdate soiution, i.e., 0.824 gram of (NT--14)6MO7024-4H20 in wa',cr, to wet th-. so'lid thor- 35 ou,-hly, and redried 18 liou@-s at 250' F. 'Elie dried solid was ca'.-.inp-d 'Lwo ho-Lirs at 1000' F. The calciried product (20.166 grams) was i,-ripre.-nated with an aqueous solu'@ioii containin- 1.277 grar@is of nickel acetate t,@trahydrat@ to give a homo.- encous pas'@e. The paste was dried to a 4( solid at 250' F. iii ai oven. After 93 hours at 250' 11., the solid was then calcined 2 hours at 1000' F. The calcialated composition, based rpon ingredients added, wlis 9.01 weight perce-it M003, I.o7 weight percent NiO an d the remainder SiO2, thC Mo/Ni atom ratio being 2.5. 45 CAT,A-LYST !V Powdered si'lica prepared by calcining desiccant grade s:iica -el (99.9 weigl@it percent SiO I _,) for. 2 hotirs at 000' F. and weighing 23.946 grams was added to a solu- 50 t-lo-,l of 6.630 grams ammon@'@U-m molybdate (NH4) 6MO7024 - 4I-120 dissolved in 30 ml. o@' hot d@stl'll-@d water. The well-mixed paste was dried to a solid in an oven at 250' F. for 19 55 hoi:.rs. Tl-.e solid was mixed thoroughly and then calcined 2 hours at 1000' F. The calcir@ed product, weighiii@- 29.058 -rams was impregna@ed with an aqueous solution containing 1.543 graiiis nick,-l acetate tetrahydrate. The sliirry was mixed thoroL,,,-hly a-,id dr,'.ed to a solid at 60 250' F. for 22 hours. The dried product was calcined 2 hours at 1000 'F. Th,- calculated compositioii, based upon ingredients added, was 18.1 wei.-ht percent M003, 1.58 weight p-,rcent iNiO, aiid fac remainder S:@02, the l@,lo/Ni atom rat;o being 6. 65 CATAL YST V to 40 grams o'L si'iica (99.9 percent pul-ity) and 8.07 grams of aldm;r@um sulfate A12(SO4)3'18H20 was added 200 cc. of distilled water. The mixture was the-@i - stirred 70 and warmed for 2 hours at 100' C. The mixture was then '@iltered and washed with 300 cc. of distilled water andt'ii,'.s wasrepeatedfivetimes. Thefiltereakewasdried in an oven at 250' F. for about 16 hours, and was then calcined for 2 hours at 1000' F. To 33.2 grams of the 75 silica/alumina (1.94 vieight percen@, alumina) so prepared was added a solutio-@i of 18.51 grams of ammonium molybdale in 150 cc. of hot distilled water. The mixture was then dried at 250' F. for about 26 hours, and was then caleir@ed for 2 hours at 1000' F. ilollovied by the addition thereto of 7.49 grams of nickel acetate tetrahydrate t d',ssolved in 30 grams of water. The mixture ivas mix--d -horoaghly and then dried in an oven at 250-' F. for about 27 hours followed by calcination for 2 hours at 1000' F. The calculated composition, based iipon -.n,-redients added, was 30.2 we-'@gI.-t percent MoO @ 3, 6.3 weight percent nickel ox;Clo, 1.2 wei.-ht perce-@it A12,03 alid 62.3 weight percent sio,. CATALYST VI A solution of 0.602 gram of nickel acetate tetrahydrate iii 19 -rams of hot d,stilled water was added to 19.75 grams of powdered silica gel prepared by calcin-"ng desicca-@it grade silica -el (99.9 weight percent SiO2) for 2 hours at 100kl' 1-7. The paste was mi ixed thorotighly, dried to a solid iii an oven at 250' F. for about 19 hours, aid then calci.ied for 2 hours at TOOO' F. The calcula'Led composition, based upoii irgredi@ents add-.d, was 0.91 we:l,-ht percerit NiO or. silica. CATALYST VII To 47 granis of silca powder (99.9 perceit purily) ther@- was ao@ded 200 cc. of concentrated nitric acid and 13.26 grams of arqmonium molybdate tetrahydrate. The re8ultant mixture was warmed and the white vol,,iininous material was filtered, and ti'ien bven dried for about 22 hours at 250' F. In order to re'ease and decompose th-, rit,-ic acid gr-.dLally, the dried composile was heated at 400' F. for 2 hours, at 600' F. for 9 hours a-id t!aen calci@@,ed for 2 hours at 1000' F. The calc - uiated cor@lt)osition, based upoii ingredients added, was 17.16 weighcpercelit MoO3 -ind 82.84 weight percent SiO2, CATALYST VIU A solution conlaining 3.46 grams of phosphomolybdic acid hydrate, H3PM01204c" H20 (72.69% D/iOO3), and 1.72 grams of nickel acetate tetrahydrate dissolved in 30 cc. of distilled water, was added to 21.96 grams of adsorptive alumina of the gamma crystahine form and analyzing 99 percent A1203, 0.02 PerCe@lt SiO2, 0.06 percent Na.,O and 0.03 percent Fe2O3. After the inixture -was stirred thoroiighly, ihe excess water was removed by evaporation. The mixture was then dried at 210' F. for 22 hours, follovied by caleination for 2 hotirs at 1000' F. The calculated co-@nposition, based upon ingredients added, was 10.07 wei,@ht p,-rcent M003, 2.07 weight percent NiO, 0.53 weight percent H3PO4 on gamma-a'@umina. CATALYST IX A solutio-ii of 6.92 grams of phospliomolybdic acid hydrate, H3PMOl2O4O-H20 (72.69% MoO3), and 3.45 grams of nickel acetate dissolved in 30 cc. of distilled water, was added to 18.93 grams of adsorptive gammaalumina analyzing 99 per,.ent A1203, 0.02 percent SiO2, 0.06 perceiit Na2O and 0.03 percent Fe2O3. The mixture was mixed thoroughly, dried in an oven at 210' F. for 22 hours followed by calcination at 1000' F. for 2 hours. The cale-ulated con-iposition, based upon ingredients added, was 20.14 weight percent M003, 4.14 weight percent NiO, 1. I weight percent H3PO4 and 74.55 weight percent A1203, CATALYST X A solution of 7.430 grams of ammonium molybdate, (N H@)6MO7024.4H20, in 15 ml. of distilled water was added to 12.706 grams of adsorptive alumina analyzing 86 weight percent A1203, 6 weight percent SiO2 and I weight percent Na2O which had been previously calcined at 1000' F. A sniall aniourit of excess water was evaporated d,'@rectly until a well-i-nixed paste resulted. The paste was then dried to a solid in an ioven at 250- F. for 22 hours and the solid then calcined for 2 hours at 1000' F.
[4]3,167,497 7 The 18.564 grams of calcined product was impregnated with a solution of 4.16 grams of nickel acetate tetrthydrate dissolved in sufficient water to give a homogeneous paste. The paste was dried at 250' F. for 92 hours and the resultant sobd was calcined 2 hours at 1000' F. 5 The calculated composition, based upon ingredie-@its added, was 30.2 weight pereent M003, 6.3 weight percent NiO, 1.6 weight percent SiO2, 58.7 weight percent A1203 and 3.2 weight percent loss on ignition, the Mo/Ni atom ratio bc,ing 2.5. 10 The relative effectiveness of the above-described catalysts was determined by using the same in a laboratory hydrogenation test unit using benzene as the typical test feed, the test operation being carried out at conversions well below equilibrium conditions in order to obtain aii 15 accurate coniparison of the catalyst activities. In these tests, the reactor (8" lo-@ig with 1/2" inner diameter) was charged with 1 or 5 grams of catalyst powder using glass wool as packing, and alundum as the preheat zone. The reactor was connected into the unit and a hydro,-en-hy20 drogen sulfide gas naixture containin.- 2 inole percent hydrogen sulfide was passed through the reactor at a pressure of about 325 p.s.i.g., the tei-nperattire was then raised to aboiit 750' F., and was held under these conditions for about I hour while passing the H2/H2S gas streani there25 through. At the start of each run, the H2/H2S stream was then allowed to pick -up benzene the mole percent of benzene in the H2/H2S stream bei-@g constant at 0.55. In testin.- ca@-li catalyst the flonv rate of the H2/H2S/benzene mixture throligh the reactor was changed in order to obtain at least two different conversions for each catalyst for calci-ilation of the hydrogenation rate constant at a definite temperature, i.e., at 750' F. expressed as k75o. p. The value of "k" represerits the efficiency of the catalyst to hydrogenate benzene to saturited liquid product at standard conditions of 325 p.s.i.g. and 750' F. in the above-described system, and it relates to space velocity and conversion. The value of "k" was tllen conve.@ted to the space velocity reqtiired to obtain a 90 percent conv--rsion of benz-,ne under these test conditions. It should be borne in mind that in this test operation the contart tinic in each instance was very low due to the fact that only 1 or 5 grams of catalyst were employed. This was done in order to operate well below equiebriurn conditions and thus obtain accurate comparisons. In each instance, ho@vever, at higher contact times, i.e., in the presence of more catalyst, the conversion of benzene is proportionately hi.-her, but the activity of the catalyst rema-ins the same. The test conditions and results of these runs are set forth in the following Table 1. Table I Run No ------------------------------------ 1 2 3 4 5 Catalyst No -------------------------------- 11 III IV v Composition: Percent MoO3 -------------------------- 18.1 30.0 9. 0 is. 1 30. 2 Percent NiO ---------------------------- 3. 7 6.5 1.9 I' 6 6.3 Mo/Ni ---------------------------------- 2.5 2.4 2.5 6.0 2.5 Support -------------------------------- (1) (1) (1) (1) (2) Pretreatment of cat,,ilyst: Charge, grams -------------------------- 5. 0 5.0 5. 0 5.0 5.0 Temperature, ' F---------------------- 750 750 750 750 750 Pressure, p.s.i.g ------------------------ 328 328 330 300 326 Gas composition ----------------------- (1) (1) (1) (1) (3) Time, hours ---------------------------- 1.0 1.0 1.0 1.0 1.0 Test conditions, Catalyst temperature, ' F -------------- 750 750 750 750 750 750 750 750 750 752 757 707 707 750 750 750 Reaction p'cessure, p.s.i.g --------------- 329 329 329 329 329 329 322 322 322 330 330 330 330 327 327 327 Flow rate, standard cc./min ------------ 103 66 115 124 ------ 176 298 ------ 131 95 170 160 124 226 272 168 Feed ----------------------------------- (4) (1) (1) (1) (1) (1) (1) (1) (1) (1) (1) (1) (1) (1) (1) (4) Carrier gas ----------------------------- (1) (1) (3) (1) (1) (1) (3) (3) (1) (1) (1) (1) (1) (1) (1) (1) Results: Conversion, percent -------------------- 47 65 44 63. 4 ------ 41.2 11 ------ 13 32 22 17 18 36. 6 28. 2 42.4 Hydrogenation activity constant, k760-r13.6 22.6 4.6 7.9 19.2 Space velocity required to obtain 90% conversion of belizene ------------------ 0. 0032 0. 0054 0.0011 0.0019 0.0046 Run No ------------------------------ 6 7 8 9 10 Catalyst No ------------------------- VI vii viii ix x Composition: PerCeRt M003 ------------------- 0 17.1 10.1 20.1 30 2 Percent NiO --------------------- 0.9 0 2.1 4.1 6 3 MO/Ni --------------------------- ------ ------ ------------ 2.5 2.5 2:5 Support -------------------------- (1) (1) (1) (1) (1) Pretreatment of catalyst: Charge, grams ------------------- 5.0 5.0 1 1 4.8 Temperature, I F---------------- 752 750 750 750 750 Pressure, p.s.l.g ------------------ 320 320 325 3 25 319 Gas composition ----------------- (1) (1) (1) (1 ) (3) Tiine, hours ---------------------- 1.0 1.0 1.0 1.0 1.0 Test Conditioias: Catalyst temperature, ' F -------- 752 750 750 7 50 750 Reaction presslire, p.s.i.9 --------- 330 320 325 3 25 319 Flow rate, standard ce./m in ----- 63 42 70 52 113 81 43 121 94 45 100 47 159 Feed ---- ------------------------ (4) (4) (4) (4) (1@ (4) (4) (4) (4) Carrier gas ----------------------- Restilts: Conversion, percent -------------- 0 0 8. 7 13.2 6.0 7.8 9.0 8.3 9.3 16.0 52 68 25 Hydrogeiiation activity coiastant, k750-F --------------------------- 0 1.4 6.5 8.5 12 Space velocity required to obtai]l 907, conversion of benzene - ------------ 0. 0003 0. 0015 0. 0020 0. 0028 ISiliCa. 2Silicaplusl.2%alumina. 32molepereentH2SinII2. 4Beiizene. 5AIuminia.
[5]Inspection of the @esults of Table I above shows that the catalysts of tljis i--veDtion, such as, for example, Catalysts I and 11 possess @@,,i;-,@erior hydrogenation activity as compared with the alumiia supported Catalysts Viii, IX and X. For example, the catalysts of this invention possess a bydrogenation activity which is at least 50 petcent hig-aer than the activity of the allmina slipported catalysts containing substantially the same content of the catalytic a.-ents of molybde-@ium and nickel. This is apparent by com_paring the restlts obtained with Catalyst 1, wh'ch possessed a hydro.-eiiation actiiity of 13.6, w-'@th that of alumina supported Catalyst IX, which possessed a hydrogenalion activity of 8.5, ard by comparing the results obtained with Catalyst II which had a hydrogenation activity cons,ant of 22.6, with that of alumina suppo.@ted Catalyst X Nihich possessed an activity o' 12. ..ispection of -@h, results obtai-@i--d with Cat'alyst VI (employed in rt,.n No. 6) a-@id CeLalyst VII (en-linloyed in run No. 7), wh-@ch cotisisted of r@ickel oxide and mol@7bd-@-,ium oxid-,, respectively, or silica, sho,,T,,s that 'Lbe -,"@iivity of th-,@e catalysts was at best very low. From the data of Table 1, it also is appqrent that the addition of a low cor@eentra@lion of alumina slch as 1.2 weight Percent as in Catalyst V (ernoloyed in r,,in No. 5) lowered the activity of Lhe catalyst. For e--,ampl,-, cOmrare th-- results obtained in run number 2 which em@loyed Catalyst II having a hydro@.en-@ition activity of 22.6, with the results obta,'@ned in run niimber 5 which employed Catalyst V which ex'@iibited a hydro.-ena@Lion activity c@f 19.2. It also is to be noted that the activity oi- Catalvst 1, con'laining about 18.1 wei.-fit i3orcent molybdenum trioxide and in wliici-i the atom ratio of MO/Ni was 2.5, possessed about thre-. times thehydrogenation acllivity as compared with the activity of @-atalyst 1-'T, in which the atom ratio vias the same but vihich contained aoout 9 weignt percent molybdenum trioxi de, On the o'cher hand, at the same concentration of molybdenut-n 'Irloxide such as abotit 18 weight percent it was found that increasing the atom ratio of Mo/Ni from 2.5 to 6.0, d,-creascd the activity of the catalyst si,-nificantly. In this coinectio-i, compare the results obtained ii, rtin r@umber I with those obtained in run number 4. In another exaritjle, a catalyst (Catalyst XI) containin- 13.8 percent molybdenum oxide and 3..l percent cobalt oxide supported on gamma-alumina, was tested employing the same procedure and -substantially the same conditions as employed in runs 1-10 of the above Table 1. The op-@rating conditions and results of this test are given in the following Table 11. Table 11 Run No ------------------------------------------- 11 C,ttalyst No ----------------------- ---------------- XI Co.mposition: Pe,-c-,nt MoO3 --------------------------------- 13 8. Percent CoO ----------------------------------- 3.i. Stipport ------------------ --------------------- Alumina. Pretreatment of catalyst: Charge, grams --------------------------------- 5.0. Tempe@-at,-,re, '-F ------------------------------ 750. Press@ire, P.S.i.9 -------------------------------- 318. Gas compositioia ------------------------------- 2% TT2S in 112Time, hours --------------------------- -------- I.O. Test conditions: catalyst temperature, "r ---------------------- 750. Reaction pressi-,re, p.s.i.g--@ -------------------- 318. Flow rate, standard cc./min -------------------- 77; 42. Feed ------------------------------------------- Benzene. Carrier gas ----------------------------------- -- 2% 1-12S in H2- Results: conversion, percent ------- 22; 42. --------------------- Hydrogenation activity, IC76o- p ------------------ 4.4. sp@ce velocity required to 6btaill 9o% conver- 0.00io. sion of benzene. From the above data, it is apparent that tiie activity of Catalyst XI was sianificantly less than that of any of the binary catalyst systems employed in the runs of Table 1 with the exceptionof Catalyst III vihich is not within the scope of this invention. 3)167,497 Further irq@ibvement in the hy&ogenation activity o4L the catalysts of this invention is realized by co-precipitation of the molybdenum and nickel compounds in the for@n of their sulfides in accordance Nvith the procedure typically represented by that employed for the preparation of Catalyst XII. CATALYST XII 69.6 grams of ethyl orthosilicate, (C2H50)4Si, was dispersed in 100 cc. of methanol and 163 grams of de10 mineral;zed water. The pH of the mixture was adjusted to 8 by th-. addition of ammonium hydroxide solution. The mixture was then saturated with hydrogen sulfide followed by the add,"tion thereto of a solutioncontaining 4.63 grams of ammonium molybdate, 1 5 (NH4)6MO7024-4H.,O dissolved in 25 cc. -of demineralized water followed immediately by the addition bf a solution containing 3.02 grams of nickel nitrate, Ni(NO3)2-6H20, dissolved iq 10 20 cc. of demineralized water. About 20 drops of a 50 p,-rcent aqueous solution of ar@imonium hydroxide was then added. After the mixture was stirred for about 1.3 hours, a gel formed. The gel was then placed in an oven maintaiiied at a temp,- ratur-- of 250' F. and dried over a 25 period of about 19 hours. The dried composite was then calciiied for 1 hour in a stream of nitro.acn, raising the temperature gradually froni 600' F. to 750' F. The calr,-alated composition of ttic catalyst con-iposite, ba@-ed upon in-redients added, was 15.1 weight percent MoO3, 30 3.1 weig'ht percent NiO and 81.8 weight percent siiica, the atom ratio of Mo/Ni being 2.5. The hydrogenation activity of Catalysl- XII was th.-n tested under substantially the same conditions empl in carryiiig out the oyed above-described runs. The operating cono.; ions and test 35 @t results are tabulated in the followin- Table III from which it may be seen that coprecipitation of the molybdenur@l and -nickel conipounds in the form of th.-ir sulfides leads to a more active hydro,-enation catalyst than produced by the method employ-,d to produce Catalyst 1 40 above. Table III Run No ------------------------------------------- 12 45 Catalyst No --------------------------------------- xii C oniposition: Percent 1VToO@ ---------------------------------- 15.1. Percerit NiO ----------------------------------- 3.1. Support ---------------------------------------- silica. r)o Pretreatment of catalyst: Charge, grams --------------------------------- I.O. Cat@@lyst temperature, I r@ ---------------------- 750. Pressure, p.s.i.g -------------------------------- 316. Gas coraposition ------------------------------- 2 mole perccnt H2S Tr-.atment time, hours ------------------------- 1. iii H2- .55 Test Conditions: Catalyst tomperatlre, F ---------------------- 750. React'@on pressure, p.s.l.g --- -- ---------------- 318. Flow rate, standard cc./mill ----------- -------- 66; 88. Feed ------------------------------------------- Benzene. Carrier gas ----------------------------------- 2 mole percer@t H2S in H2. Results: 60 Conversion, percent ------------- --------------- 23.7; 10.0. Hydrogenation activity, k7LO' F ----------------- 16.4. The catalysts of this i-@ivention also are particularly suited as catalysts for the hydrogenation of kerosene. 65 TWs is demonstrated by the results shown in the following table IV. In fnese rilns, a kerosene fraction boiling between about 350' F. and about 550' F. and havin- a smolce point of 20 mm. and a gasoline content of 11 weight percent, was employed as the feed. The opera70 tion was conducted employing a 0.5 inch I.D. downflow reactor char,@ed wi+h 10.0 granis of the above-describ-@d Catalysts 11 and XII containing 30.0 weight percent and 15.1 molybdenum oxide, respectively, the Mo/Ni atom ratios being 2.4 and 2.5, respectively. The catalyst tein75 perature was adjusted to the desired bperating tempera-
[6]ture and pressure by :ffowin.- an inert gas therethrough prior to introducing the kerosene feed and hydrogen gas conta;ning 2 mole percent hydrogen sulfide to the reactor. The operating conditions empioyed and results of these tests are presented in the following Table IV. Table IV HYDROGENATION OF KEROSENrl, Run No ------------------------------------------ 13 14 - Catalyst No --------------------------------------- xii 11 Composition: Percent M003 ------------------ --------------- 15. 1 30. 0 Percent NiO ------------------ ---------------- 3.1 6.5 Preconditioniiig of catalyst: Catalyst ellarge, grams ------------------------ 10 lo Temperature, 'F ------------------ ------------ 650 750 Pressure, p.s.i.g ------------------ ------------- 800 800 Tim , liours ------------------------------------ 1.0 1.0 Carrier gas ------------------------------------ (,) (1) Gas rate, cu. ft./hr., 70' F --------------------- 0. 683 0. 547 Operating conditions: Tomper,,iture, ' F----------------------------- 650 "'O Pressure, p.s.i.g -------------- 800 800 Tiule, holirs ----------------------------------- 2. 0 4. 0 Space velocity, We./hr./Wo -------------------- 1.96 0. 57 H2 gas/oil, ivl./M ------------------------------- 9.91 24. 4 Yields, Wc,,ight pereetit: Gas (CI-04) ----------------------------------- 0. 4 0.9 Gasoliiie, 400' F. (end point) ------------------ 14.0 27. 0 Kerosene, 400' F-- ---------------------- ----- 84.8 71.5 Carbon ---------------------------------------- 0. 4 0. 6 liaspections on total liquid productAPI gravity ----------------------------------- 42.9 44.4 Aniline point, ' F ----------------------------- 159.0 163.0 Smoke point, ium ----------------------------- 26.0 30.5 1 2 mole percent H2S in H2. Inspection of the results of Table IV shows that the catalysts of this invention are partictilarly useful for upgrading kerosene fractions by hydrogenation, the degree of hydrogenation being evidenced by the improvement in smoke point of the feed. The catalysts also possess good selectivity as observed by the low yields of carbon and normally gaseous hydrocarbons. It is apparent that various modifications and variations in the catalysts and process of this invention may become apparent to those skilled in the art without departin,@ from the scope of this invention. Having described my invention, I
