CA1077917A - Hydroconversion of heavy hydrocarbons - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE
A catalytic hydroconversion process for hydrocarbonaceous oil is effected by dissolving an oil-soluble metal compound in the oil, converting the compound to form a solid, non-colloidal catalyst within the oil and reacting the oil containing the catalyst with hydrogen.
Preferred oil-soluble compounds are molybdenum compounds. Optionally, a solid iron component is also added to the hydrocarbonaceous oil.

Description

1 ~ 7 791 7 BACKGROUNI) OF T~tE IN~ENTION

2 1. Field of the Invention

3 This invention relates to a process for the hydro-

4 conversion of a heavy hydrocarbonaceous oil in the pr~sence of a catalyst prepared in situ from trace amounts of metals 6 added to the oil as oil-soluble metal compounds.
7 2. Descrip~ion of the Pr~or Art 8 Hydrorefining processes utilizing dispersed cat-9 alysts in admixture with a hydrocarbonaceous oil are well known. The term "hydrorefining" is intended herein to des-11 ignate a ca~alytic treatment, in the presence of hydrogen, 12 of a hydrocarbonaceous oil to upgrade the oil by eliminat-13 ing or reducing the concentration of contaminants in the 14 oil such as sulfur compounds, nitrogenous compounds, metal contaminants and/or to convert at least a portion of the 16 heavy constituents of the oil such as pentane-insoluble 17 asphaltenPs or coke precursors to lower boiling hydrocarbon 18 products, and to reduce the Conradson carbon residue of the 19 oil.
A hydrorefining process is known in which a 21 petroleum oil chargestock containing a colloidally dispersed 22 catalyst selected from the group consisting of a metal of 23 Group VB and VIB, an oxide of said metal and a sul~ide of 24 said metal is reacted with hydrogen at hydrorefining con-ditions. This patent teaches that the concentration of the 26 dispersed catalyst, calculated as the elemental metal, in 27 the oil chargestock is from about 0.1 weight percent to abaut 28 10 weight percent of the initiaI chargestock.
29 A hydrorefining process is kn~wn ~n which a metal component (Group VB, Group VIB, iron group metal) colloidally `' - 2 ~

1 dispersed in a hydrocarbonaceous oil is reacted ln contact 2 with a fixed bed of a conventional supported hydrodesulfuri-3 ~ation cataLyst in the hydrorefining zone. The concentra-4 tion of the dispersed metal component which is used in the hydrorefining stage in combination with the supported cata-6 lyst ranges from 250 to 2,500 weight parts per million (wppm).
7 A process is known for hydrorefining an asphaltene-8 containing hydrocarbon chargestock which comprises dissolv-- - 9 ing in the chargestock a hydrocarbon-soluble oxovanadate salt and forming a colloidally dispersed catalytic vanadium 11 sulfide ln situ within the chargestock by reacting the re-12 sulting solution, at hydrorefining conditions, with hydrogen 13 and hydrogen sul~ide.
14 It has now been found that the addition of a minor amount (i.e. less than 1000 weight parts per million (wppm), 16 calculated as the metal) of an oil-soluble compound of metals 17 of Groups VB, VIB, VIIB and VIII of the Periodic Table of 18 Elements and their conversion products in the oil yield cata-19 lysts which are effective in a minor amount for the hydro-conversion of hydrocarbonaceous oils without the necessity ,., 21 sf utilizing a conventional supported catalyst in combination 22 with the minor amount of dispersed catalyst ~n the hydro-23 conversion zone.
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24 The term "hydroconversion" is used herein to des-ignate a catalytic process conducted in the presence of 26 hydrogen in which at least a portion of the heavy constitu-27 ents and coke precursors (as measured by Conradson carbon 28 residue) of the hydrocarbonaceous oil is converted to lower 29 boiling hydrocarbon products while simultaneously reducing the concentration of nitrogenous compounds, sulfur compounds ., ~` .

i~77917 -1 and metaLlic contamlnants.

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3 In accordance with one em~odiment of the inverltion, 4 there is provided a process for hydroconverting a heavy hydro-c~rbon oil chargestock~ which comprises: (a) adding to said 1 6 chargestock an oil-soluble metal compound in an amount rang-; 7 ing from about 25 to about 950 wppm, caLculated as the elemen-8 tal metal, said metal being selected from the group conslsting 1 9 of Groups.VB, VIB, VIIB and VIII of the Periodic Table of Ele-ments and mixtures thereof; (b) conver~ing said oil-soluble 11 compound within said chargestock in the presence of a hydro~
12 gen-containing gas to produce a solid, noncolloidal catalyst 13 within said chargestock; (c~ reacting the chargestock contain-14 ing said catalyst with hydrogen under hydroconversion condi-, 15 tions and (d) recovering a hydroconverted hydrocarbon oil.
. 16 In accordance with another embodiment o~ the ~l 17 invention, there is provided a process for hydroconverting ~ 18 a heavy hydrocarbon oil chargestock, which comprises: re~
! 19 acting a heavy hydrocarbon oil chargestock containing a catalyst with hydrogen at hydroconversion conditions in a ` 21 hydroconversion zone, said catalyst comprising an effective , , .
:-~ 22 amount of an iron component and a catalytically active metal ` 23 component selected from the group consisting of Group VB, X 24 Group VIB, Group VIIB, Group VIII metals other than iron, of ; 25 the Periodic Table of Elements, and mixtures thereof, said i~ 26 iron component being added to said oil chargestock as solid 1 27 particles, and said catalytically active metal component 28 having been prepared by the steps of:
29 (a) adding to said heavy hydrQcarbon oil charge-~ ~0 6tock an effective amount of an oil-soluble metal compound, 1 _ 4 - .
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1C~77917 1 said metal being selected from the group consisting of 2 ~roup V~, Group VIB, Group VIIB and Group VIII me~als 3 other than iron, of the Periodic Table of ~lements, and 4 mixtures thereof, and (b) converting said oil-soluble metal compound 6 to a catalytically active metal component within said charge-7 stock in the presence of a hydrogen-contalning gas.

9 Figure 1 is a schematic flow plan of one embodimPnt of the invention.
11 Figure 2 is a plot showing the hyd~ocon~ersion 12 response of a Athabasca bitumen eed, containing 350 wppm 13 molybdenum, to the concentration of H2S in the hydrogen fed 14 to the hydroconversion reactor.
! 15 Figure 3 is a plot showing the concentration 16 effectiveness curve for trace molybdenum in the hydrocon-17 version of Cold Lake Crude.
18 Figure 4 is a graphical representation of a photo-19 graph of molybdenum-containing catalytic solids.
Figure 5 is a graphlcal representation of another 21 photograph showing molybdenum-containing catalytic solids.

23 The process o~ the invention is generally applicable 24 to heavy hydrocarbonaceous oils. Suitable heavy hydrocarbon-aceous oil chargestocks include heavy mineral oils; whole 26 or topped petroleum crude oils, including heavy crude oils, 27 polynuclear aromatics such as asphaltenes; residual oils 28 such as petroleum atmospheric distillation tower residua 29 ~oiling above about 650F., i.e. 537.78C.) and petroleum vacuum distillation tower ~esidua ~vacuum residua, boiling

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, ~ 9 ~7 l above about 1,050F., l.e. 565.50C.); tarsS bl~umen; t~r 2 sand oils; shale oils. The process is p~rticular1y well 3 suited to heavy crude oils and residual oils which generally 4 contain a high content of metallic contaminants (nickel, iron, vanad-ium) usually present in the form of organometallic

6 compounds, e.g. metalloporphyrins, a high content o sulfur

7 compounds, a high content of nitrogenous compounds and a ~8 high Conradson carbon residue. The metal conten~ o such 9 oils may range up to 2,000 wppm or more and the SU1LUr con-tent may range up to 8 weigh~ percent or more. The API
11 gr~vity at ~0F. of such feeds may range from about -5~API
12 to about ~35API and the Conradson carbon res;due of the - 13 heavy feeds will general1y range from about 5 to about 50 l4 weight percent (as to Conradson carbon residue, see ~SI~I
test D-189 65). Preferably, the feed stock is a heavny 16 hydrocarbon oil having at least lO weight percent of material 17 boiling above 1,050F. (565.56C.) at atomospheric ~ressure, 18 more preferably having at least about 25 weigh~ percent of l9 material boiling above 1,050F. (S65~56C.) at atomospheric pressure.
- 21 Optionally, a so.id particulate iron component 22 may be added to the heavy hydrocarbon oil chargestock.
23 Suitable i.ron components include elemental iron, lron oxidesS
24 iron sulfides, naturally occurrlng iron-containing ores, mineral mixtures, iron-containing ash materials derived from 26 coal, bitumen and the like, fly ash, iron-containing by-27 products from metal refining operations, e.g., red mud, etc.
- 28 Desirably, the particle sizes of the iron component may 29 range broadly rom about 0.5 micron to about 200 microns, preferably from about 0.5 to 20 microns in diameter. The .
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~7 ~ ~7 l iron componen~, calculated as i it exlsted as elemental 2 iron, based on the weight of the initial oil charges~ock 3 i~ suitably added to the oil feed in amounts ranging from 4 about 0.01 to about 30 weight percent, preferably from about 0.01 to 10 weight percent, and more preferably from about 6 0.01 to about 1 weigh~ percent. It should be unclerstood 7 that the given amounts of iron component re~er to amounts

8 which are added to the oil feed in excess of any iron that

9 ~ay be present as metallic contaminant in the oil feed.
To the heavy hydrocarbon oil chargestock is added 11 ~rom about ~5 to about 950 wppm, preferably from about 50 12 to about 300 wppm, more preferably from about 50 to about 13 200 wppm of an oil soluble metal compound, wherein the metal 14 is selected from the group consisting of Groups VB~ VIB, VIIB, VIII and mixtures thereo of the Periodic Ta~le of 16 Elements, said weight being calculated as if the compound 17 existed as the elemental metal, based on the initial oil 18 chargestock.
19 Suitable oil soluble metal compounds convertible (under process conditions) to solid, non-colloidal catalysts 21 Lnclude (1) inorganic metal compounds such as halides, oxy-22 halides, hydrated oxides~ heteropoly acids (e.g. phospho-23 molybdic acid, molybdosilicic acid); (2) metal salts of 24 organic acids such as acyclic and alicyclic aliphatic carboxylic acids containing two or more carbon atoms (e.g.
26 naphthenlc acids); aromatic carboxylic acids (e.g. toluic 27 acid) sulfonic acids (e.g. tolunenesulfonic acid); sulfinic 28 acids; mercaptans; xanthic acid, phenols, di and polyhydroxy 29 aromatic compounds (3) organometallic c~mpounds such as metal chelates, e.g. with 1,3-diketones, ethylene diamine, 1~77917 1 ethylen~ diamine tet~aacetic acid, phthalocyanlnes, e~c.;
2 (4) metal salts o organic amines such as aliphatic 2mines, 3 aromatic amines, and quaternary ammonium com~ounds.
4 The metal constituent of the oil solubl~ metal compound, that is convertible to a solid, non-coLlo;dal 6 catalyst, is selected from the group consisting o~ Groups 7 VB, VIB, VIIB and VIII and mixtures thereof o~ the Periodic 8 Table of Elements, in accordance wi~h the table published 9 by E. H. Sargent and Company, copyright 1962, Dyna Slide Company, that is, vanadium, niobium, tantalum, chrom-ium, 11 molybdenum, tungsten, manganese, rhenium, iron, cobalt, 12 nickel and the noble metals including platinum, iridium, 13 palladium, osmium, ruthenium and rhodium. The preferred 14 meLal constituent of the oil soluble metal compound is selected from the group consisting of molybdenum, vanadium 16 and chromium. More preferably, the metal constituent of 17 the vil-soluble metal compound is selected from the group 18 consisting of molybdenum and chxomium. Most preferably, 19 the metal constituent of the oil soluble compound is molyb-denum. Preferred compounds of the given metals include the 21 salts of acyclic (straight or branched chain) aLiphatic 22 carboxylic acids, salts of alicyclic aliphatic carboxylic 23 acids, heteropolyacids, hydrated oxides, carbonyls, pheno-24 lates and organo amine salts. The more preferred metal compound is a salt of an alicyclic aliphatic carboxylic acid 26 such as a metal naphthenate. The most praferred compounds 27 are molybdenum naphthenate, vanadium naphthenate and chromiu~
28 naphthena~e. In the embodiment in which a solid iron com-29 ponent is also added to the oil chargestock, then an oil soluble metal compound of a metal other than iron is used.

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~77917 l When the oil soluble compound is added to the 2 hydrocarbonaceous chargestock, it flrst dissolves in the 3 oil and subsequently, under pretreatm2nt or under hydro~
4 conversion conditions herein described, is conv~rted to a S solid, non-colloidal catalyst.
6 Various methods can be used to convert the dis-7 solved compound in the oil. One method (pre-treatment 8 method) o forming a catalyst from the oil soluble compound - 9 of the present inven~ion is to heat the solution o~ ~he metal compound in the hydrocarbon chargestock to a tempera-11 ture ranging from about 325C. to about 415C. and at a 12 pressure ranging from about 500 to about 5,000 psig in the 13 presence of a hydrogen-containing gas. Preferably the hydro-14 gen-containing gas also comprises hydxogen sulfide. The hydrogen sulfide may comprise from about 1 to about 90 mole 16 percent, preferably from about 2 to about 50 moLe percent, 17 moLe preferably from about 3 to about 30 mole percent, of 18 the hydrogen-containing gas mixture. The thermal treatment 19 in the presence of hydrogen or in the presence of hydrogen and hydrogen sulfide is believed to convert the metal com-21 pound to the corresponding metal-containing solid, non-22 colloidal products which axe catalytically active and act 23 as coking inhib-Ltors. The resulting catalyst contained 24 within the oil charge is then introduced into a hydroconver-sion zone which will be subsequently described.
; 26 A preferred method of converting the oil-soluble 27 metal compound of the present invention is to react the 28 solution of the compound in oil with a hydrogen-containing 29 gas at hydroconversion conditions to produce the catalyst Ln the chargestock in sLtu in the hydroconversion zon .

''.'' ' 1~77917 1 Preferably, the hydro~en-containing gas comprises rom 2 about 1 to about 10 mole percent, more preferably from 3 about 2 to 7 mole percent, hydrogen sulfide. The con~eLsion 4 of the metal compound in the presence of the hydrogen-con-taining gas or in the presence of the hydrogen and hydrogen 6 sulfide is believed to produce the corresponding metal-7 contairling solid, non-colloidal cataLyst. ~hatever the 8 exact nature of the resulting metal containing catalyst, 9 the resulting metal component is a catalytic agent and a coking inhil~itor.
11 When an oil soluble molybdenum compourld is used 12 as the catalyst precursor, the pxeerred method o convert-13 ing the oil soluble metal compound is in situ in the hydro-14 conversion zoneS without any pre~reatment.
The hydroconversion zone ls maintained at a tempera-16 ture ranging from about 343 to 538C. (65G to lOC0F), prer-17 erably from about 426 to 48?C. (799 to 900F.), more pref-18 erably from about 440 to ~8C. (824 to 875F.), and at a 19 hydrogen partial pressure ranging from about 500 to about 5,000 psig, preferably from about 1,000 to about 3,000 psig.
21 Contact of the solution under the hydroconversion conditions 22 in the reaction zone with the hydrogen-containing gas con-23 verts the metal compound to the corresponding metal catalyst 24 in situ while simultaneously producing a hydroconverted oil.
The hydroconverted oil containing solids is rem~ved from the 26 hydroconversion reaction zone. The solids may be from the 27 hydroconversion reaction zone. The solids may be separated 28 from the hydroconverted oil by conventional means, for 29 example, by settling or centrifuging or f-lltra~ion of the slurry. At least a portion of the separated solids or solids

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1~77g~7 1 concentrate may be recycled directly to the hydroconversion 2 zone or recycled to the hydrocarbonaceous oil chargestock.
3 The space velocity defined as volumes o oil eed per hour 4 per volume of reaction (V/hr./V) may vary widely depending on the desired hydroco~version level. Suitable space 6 velocities may range broadly from about 0.1 to 10 volumes . 7 of oil feed per hour per volume of reactor, preferably rom - ~ 8 about 0.25 to 6 V/hr./V9 more preferabl.y rom about 0.5 to 9 2 V/hr./V. ~le process o the inventlon may be conducted either as batch or as continuous type operatîon.

11 DESCRIPTION OF T~E P~EFERRED E~ODIM~NT

12 The preferred embodiment will be described with

13 reerence to accompanying Figure 1.

14 Referxing to Figure 1, a petroleum atmospheric residuum eed, that is, a fraction having an atmospheric 16 pressure boiling point of 650F.~ (343.3C~) containing less 17 than 500 wppm o~ added oil soluble metal compound, prefer-: 18 ably molybdenum naphthenate, calculated as the elemental 19 metal based on the initial residuum feed, is introduced by line 10 into a hydroconversion reactor 12 at a space velocity 21 of 0.5 to 2 volumes of feed per hour per volume of reactor.
22 A gaseous mixture comprising hydrogen and from about 2 to 23 7 mole percent hydrogen sulfide is introduced into reactor 24 12 by line 14. The hydroconversion reaction zone in reactor 12 is maintained at a temperature ranging from about 824 to 26 875F. (440 to 468C.) and under a hydrogen partial pressure 27 ranging from about 1000 to 3000 psi.g. The hydroconversion : 28 reactor ef~luent is removed by line 16. The effluent com-29 prise a hydroconverted oil product, gases, and a solid resi-due.

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1{~77917 1 The effluent is introduced into a gas-liquid 2 separator 18 where hydrogen and li~ht hyd~ocarbons are re-3 moved overhead through line 20. Three prefexred process 4 options are available for the liquid stream containin~ dis-persed catalyst solids which emerges from separator vessel 6 18 vi.a line 22. In process option to be designat2d "A"9 7 the liquid-solids stream is fed by line 24 to concentration 8 zone 26 where by mPans~ for example, of distillation~ solvert 9 precipitation or cen-rifugation, the stream is sepa.rated into a clean liquid product9 which is withdrawn through line 28, 11 and a concentrated slurry (i.e. 20 to b~o% by wei~ht) in oil.
12 ~t least a portion of the concentra~ed s~urry can be removed .13 as a purge stream through line 30, to control the buildup 14 of solid materials in the hydrocon~e.si.on reac~or, and ~he baLance o the slurry is returned by line 3~ and line 22 to 1 16 hydroconversion reactor 12. The purge stream may be filter-1 17 ed subsequently to recover catalystan~ liquid product or it 18 can be burned or gasified to pro~ide, respectively, heat and 19 hydrogen for the process.
In the process option to be designated "B", the 1 21 purge stream from concentration zone 26 is omitted and the i 22 entire slurry concentrate withdrawn through line 32 is fed l 23 to separation zone 36 via li.nes 22 and 34. In thls æone, a .1 24 ma~or portion of the remaining liquid phase is separated ;~ 25 from the solids by means of centrifugation, iltration or a 26 combination of settling and drawoff, etc. Liquid is removed ~7 from the zone through line 38 and solids through line 40.
28 At least a portion o~ the solids and associated remaining 1 29 liquid are purged from the process via line 42 to control :¦ 30 the build-up of solids in the process and the balance of the :1 - 12 ~

. ~77917' 1 solids are recycled to hydroconversion reactor 12 vla lirle 2 44 which connects to recycle line 22. The solids can be 3 recycled either as recovered or after su~table clean~lp (no~
4 shown) to remove heavy adhering oil deposit~s and coke.
In option designated "C", the slurry of solids in 6 oil exiting rom separato~A 18 via line 22 ;s red dlrectly to 7 separation æone 36 by way of line 34 whereupon sol:ids and 8 liquid product are separated by means of centrifugation or 9 fil~ration. All or part o~ the solids exi~ing from vessel 36 via line 40 can be purged from the process through line 11 42 and ~he remainder recycled to the hydroconversion reactor.
12 Liquid product i9 recovered through line 38. If desired, 13 at least a portion of the heavy fraction of the hydroconvert-14 ed oil produc~ may be recycled to the hydroconversion zone.

15. The following examples are presented to illustrate the in-

16 vention.

17 EXAMPLE 1

18 Several sets of comparative hydroconversion exper-

19 iments were made. The experimental apparatus and procedure~
used are summarized in Table 1. Detailed inspections on 21 various feeds used in these experiments are listed in Table 22 ~. Table 3 identifies the catalysts and catalyst precursors 23 used in these experiments.
24` Table 4 shows the effectiveness of catalysts pre-pared in situ from oil soluble compounds of various metals 26 relative to catalyst-free control runs. All of the metals 27 tabulated were effective but vanadium, chrom~um and moLyb-28 denum are preferred based on overall ability to suppress coke 29 and gas formation while ~iving attracti~e levels of desulfuri-zation, demetallization and Conradson carbon conversion.
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077~i7 Molyhdenum is most preferred. It should be noted that in view of prior art teachings, e.g. in U.S. patent 3,825,488, regarding the ineffectiveness of chromium, it was found un-expectedly that within the metal concentration range of the present invention and under the conditions of the present invention, chromium was effective and very nearly equivalent to molybdenum.
The experimental runs shown in Table 5 show that catalysts derived from nickel, cobalt and vanadium are im-proved by a brief pretreat in situ with a hydrogen and hydro-gen sulfide-containing gas for optimum activity. Similar results (not shown) were obtained with iron and tungsten catalysts. As will be noted in Tables 6 and 7, molybdenum does not require in situ pretreatment for optimum activity.
A set of runs utilizing Athabasca bitumen feed is summarized in Table 6. The set of runs shown in Table 6 shows that molybdenum catalysts of the present invention do not require pretreatment with a hydrogen sulfide-containing gas to attain optimum activity (compare run lR-12 with lR-ll).
Furthermore, run lR-14 shows that pretreatment of any sort is not necessary for the soluble molybdenum compounds. This result was unexpected in view of the pre~reatment improvement ~ shown in Table 5 when other metal compounds were used as ; catalyst precursors. Run lR-17 shows that pretreating with - H2S in the absence of hydrogen gives a catalyst that is infer-ior to those obtained when the pretreatment gas contains hydro-. ' ~

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~0779~7 gen. Specifically, relative to runs lR-12 and lR-ll, it is seen that the catalyst of run lR-17 is inferior in suppressing coke formation and in promoting Conradson carbon conversion.
For comparison, run 8R-52 is a molybdenum-free ~, ~, :, ,., . . - 14a -.
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1(~77~1~
~ control run.
2 In Table 7 are summariæed results of experiments 3 made with Cold Lake Crude. These runs show that molybd~num 4 does not require pretreatment with hydrogen sulfide-contain-ing gas to attain optimum activity. Compare run lR-73 (H2 6 only pretxeat3 with lR-45 (H2 ~ H2S). It is sho~n further 7 that pretreatment in the absence o. hydrogen, either with 8 pure H2S (run lR-67) or under nitxogen pressure (run lR~75) 9 gave less effecti~e catalysts than obtained with hydrogen in the pretreatment gas (run lR-73). This result, as well 11 as the comparable da~a of Table 6, showing that hydrogen is 12 a beneficial com~onent in the pretreatment step was unexpected 13 in view of prior art teachings (see ~.S. patent 3,165,463, 14 column 5 and ~ and U.S. patent 3,196,104, column 4) which teach that a reducing atmosphere, and in particular, free 16 hydrogen, wi.ll lead to inferior catalyst performance if 17 present in the catalyst act~vation or pretreat step, al~eit 18 at diferent pretreatment conditions than those used in the 19 present invention.
Figure 2 is a plot which shows the hydroconversion 21 response of anAthabasca bitumen eed containing 350 wppm 22 molybdenum added to the feed as molybdenum-naphthenate, to 23 the concentration of H2S in the hydrogen-containlng gas in 24 troduced into the hydroconversion reactor. Pretreatment was not employed in this run series. The hydroconversion runs , .
: 26 were conducted in a continuous autoclave unit at a tempera-27 ture of 830F. (443.33C.) at an oil space velocity of about ~ 28 0.94 to 1.0 V/Hr./V and at a hydrogen-containing gas treat -~ 29 rate of about 4000 standard cubic feed of gas per barrel bf - 30 oil. The treat gas was used once through. The resulting ~077917 1 continuous unit data ~how that there i.s an optinnlm H2S con-2 cenlration between about 2 and 5 mole percent H2S in the 3 hydrogen trQat gas (this does not include H2S generated 4 from the hydxoconversion reacti.on).
The optimum exists for demetallization activity.
6 However, it is al50 seen that gas ~Cl-C4~ yield increases 7 with incre~sing H2S concen.tratio. which will set an upper 8 practical limit on H2S concentrations in reini~g situations 9 where a ~rer.lium is placed on liquid yield.
In Table 8 are summarized results of a set o ex-Ll periments which sho~ that oil solubility is needed for cata~
12 lyst precursors used in forming the efec~ive~ solid, non- ~ :
13 colloidal catalysts of the present in~ention. On an equiva-14 lent molybdenum concentration in feed basis, it is seen that oil insoluble MoO3 powder (run lR-22) showed little improve~
16 ment over a molykdenum-ree control run (6R-34).
17 . .. In contrast, soli~ mol.ybdenum con~aining catalys~
18 formed in situ from a variety of oil soluble molybdenum com-19 pound catalyst precursors (phosphomolybdic acid~ molybdenum hexacarbonyl, molybdenum pentachloride, molybdenum resinate) 21 gave good results.
22 In Table 9 are summarized results of experiments 23 which showed that naturally occurring oil soluble metals 24 contained in the eed were not effecti~e for controLling the hydroconversion reaction, either on an "as is" basis, or 26 after pretxeat with a hydrogen and hydro~en sulfide-contain-27 ing gas. No~e the excessive yields of coke ~nd light gas.
. 28. In Flgure 3 is shown a concentration effectiveness 29 curve or the molybdenum catalyst of the present invention ; 30 in the hydroconversion of Cold Lake Crude. Molybdenum ;
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1~779~7 1 resinate was used as the molybdemlm catalyst precursor. l~e 2 catalyst precursors were pretreated in situ with H~S (10%) 3 plus H2 at 385C. (725F.) for 30 minutes. ~e hydrocon-4 version runs were conducted ~or 1 hour contact at ~20F.
(437.7C.) ~t ~ pressure of 2000~ psig. The molybde~um con-6 centration in the runs was as follows:
7 wppm Moly Run No.
8 40 6~-73 9 100 lR-55 171 6~-70 12 820 6~-68 14 As can be seen -from the pLo~ coke formation begins to in-c~ease as the m~tal concentration rises above about 900 wppm.
lS Demetallization is quantitative well below 1000 wppm and gains 17 in Conradson carbon convers;on bxought by increasing metal 18 concentration were small. For example, doubling the molyb-19 denum concentration (500 to 1000 wppm) had no significant effect on useful Conradson carbon conversion level (55% ver-21 sus 56%).
22 Figure 4 is a graphical representation of a photo-23 graph of the molybdenum-containlng solids recovered ~rom 24 hydroconversion runs of the present invention. The photo-graph ~rom which this graphical representation was made was 26 an optical microscope view of the catalytically active parti-27 cles as they exist in the reactor liquid product (diluted 28 with toluene). This sample was obtained in the hydroconver-29 sion of Cold Lake Crude with 350 wppm molybdenum (added as molybdenum naphthenate). Xt should be noted that the indiv~

iO77917 1 particles had a diameter of approximately 2 microns and 2 ~ere present in larger clusters (10 to 20 microns). ~e 3 2 micron particle size is significantly greater than colloi-4 dal size, i.e.~ from one to 200 millimicrons as defined in Glasstone's Textbook of Physical Chemistry, 2nd Edition, 6 p. 1231, published by D. Van Nostrar,d, 1946.
7 Figure S is a graphical representation o another 8 photograph which shows the non-colloidal character o the 9 molybdenum-containing so]ids (catalysts) of the present in-vention. This sample was obtained in a continuous unit run 11 with Athabasca bitumen eed containiilg 180 wppm molybdenum 12 (added as naphth~nate). It should be noted that the individ-13 ual particle size is of the order of 1 micron.
14 Table 10 summarizes the results of filtrztion runs carried out at hydroconversîon reaction conditions. These 16 runs show that (1) depending on feed, some 65 to 80% of the 17 molybdenum contain-ing solids obtained in the hydroconversion 18 ~un are retained by a 10 micron filter, thereby supporting 19 the par~icle siæe shown in Figures 4 and 5 and (2) that the molybdenum is associated with the solids at process condi-21 tions, i.e. about 80% of the avallable molybenum was found 22 with the 10 + micron solids at 438C. and about 2500 psig 23 reactor pressure.
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24 Table 11 summarizes data of runs comparing the activity of recycle solids obtained rom runs in which the 26 catalyst precursor was molybdenum naphthenate and fresh 27 catalyst prepared from molybdenum naphthenate for Athabasc~
28 bitumen hydroconversion. The runs were conducted at 830F.
29 (443.33C.~ and 2000-~ psig hydrogen pressure for 60 minutes.
In runs 153, 142 and 143, the solids filtered (therefore non-.' `` 1~77917 colloidal in size) from a molybdenum naphthenate run were -utilized as catalyst. In run 145, a conventional supported molybdenum on high surface area carbon hydrotreating catalyst was utilized. It can be seen from the data that the non-colloidal recycle catalyst particles typical of those de-scribed in Table 10 and in Figures 4 and 5 have activity equivalent to fresh catalyst up to a concentration providing about 350 wppm molybdenum (compare run 2R-14 and 143) and are superior to fresh catalyst at concentrations above 350 wppm for suppressing coke formation (compare run 142 and 160). Also, it can be seen that the recycle solid catalyst (run 143) is superior to a fresh powdered conventional molybdenum-on-charcoal catalyst (run 145).
In Table 12 are summarized results of runs utilizing a mixture of fresh and recycle solids to provide maximum coke suppression while maintaining highly active, selective reactions for demetallization and Conradson carbon conversion.
The efficacy of using recycle catalyst in combination with fresh catalyst for hydroconversion of Athabasca bitumen can be seen from the data in Table 12. The combination catalyst (run A) provided a more selective (i.e. less contribution to conversion by coking) Conradson carbon conversion and de-metallization reaction than was obtained in runs using the comparable concentration of molybdenum as fresh catalyst ; (run E) or as recycle catalyst (run C). Furthermore, it can be seen that the low molybdenum concentration equivalent to the ' , 19 , ,: : -, .

10779~:7 fresh molybdenum concentration of the combination catalyst (93 wppm) is relatively ineffective when tested alone as . fresh catalyst (run B) or as recycle catalyst (run D).

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1(~779~7 APPARATUS, GENERAL PROCEDURE AND CALCULATIONS
REACTOR
A standard design 300 ml autoclave furnished by Autoclave Engineers, Inc. was used. Construction is entirely of Hastelloy-C. Gas-liquid contacting and mixing in general is provided by internal stirring. Reactor temperature is measured internally.
~eatup time from ambient to run temperature is on the order of 25 minutes. Heat is provided by a self contained, re-movable, electric furnace.
Cool down from reaction temperature to a thermally non-reactive temperature is accomplished within 1 minute by using both internal (water) and external cooling.
RUN PROCEDURE
Feed and catalyst were loaded into the reactor, which was then flushed with hydrogen and given a 60 min. pressure test atr~2400 psig with hydrogen.
With the reactor pressure tight and equilibrated ot start of run conditions, i.e. about 2000 psig and 24-27 C., the reactor was vented down through a wet test meter to deter-mine the hydrogen charge. The reactor was then repressured to the exact pre-vent conditions and the run begun.
A run was seldom repressured on conditions. Normally, an excess of hydrogen was added initially.
Reaction time or contact time was the actual time on conditions. No adjustments were made to compensate for heatup time.
-, 20 Pretreatment conditions (if used) are described in the data tables. If H S plus H2 were employed in the pretreat then the reactor was cooled to room temperature after pretreat, flushed with hydrogen and recharged with pure hydrogen for the run. When hydrogen alone was used in the pretreat there was no cool down after the pretreat, rather, temper-ature was raised directly to the run temperature.
PRODUCT RECOVERY
The reactor was depressured at room temperature. Gas was scrub-bed to remove H2S and the volume measured using a wet test :
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meter. Composition was determined by mass spectrometry gas analysis.
- Solids were recovered by filtering the liquid product and by scouring reactor surfaces. The solids were washed free of adhering oil with toluene and then dried under vacuum.
Carbon content of the solids was determined as burned carbon.
~DROCONVER~ION CALCULATIONS `
- The percent desulfurization and percent demetallization values cited compare C + liquid product with feed. No attempt has been made ~o adjust for the contribution that coking has made to the desulfurization and demetal-lization results. It is known that coking is a signifi-cant contributor to the results in runs where coke form-ation is not inhibited, e.g. in control runs.
- Coke formation has been taken into account in the Conradson Carbon Conversion numbers. Since coke formation is a mechanism for Conradson Carbon conversion, but not useful for the present purposes, in the Conradson Carbon conver-slon calculated, the conversion to coke has been excluded.
Wt.Con.Carbon Converted-Wt.Coke Formed x 100=% Converted Wt.Con.Carbon in Feed - The liquid sample on which analyses were run was obtained in the filtration step. In addition, liquid product ad-hering to the filtered solids and to reactor surfaces was picked up in toluene and subsequently recovered by strip- -ping away the toluene. This material was periodically checked to make sure that its inspections agreed with those of the main liquid sample. Generally about 10-15% of the total liquid was recovered in the toluene wash. Material balances, overall, have ranged from 97 to 101%.

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. , ~C~77917 TABI,E 2 .

Cold Jobo LakeAthabasca Feed DesignationCrudeCrudeBitumen*
Feedstock No. 1 2 3 API Gravity 8.5 10.4 10.3 Sulfur, Wt. % 4.Q 4.3 4.7 Nitrogen, Wt. ~0.7 0.44 0.43 Carbon, Wt. %83.92 -- 83.63 Hydrogen, Wt. %10.49 -- 10.47 Oxygen, Wt. ~0.57 -- 0.75 Conradson Carbon, Wt. %13.8 12.9 12.3 Metals, ppm 97 74 74 Fe 12 56 248 Viscosity @ 210F. 247 73 --Distillation IBP, ~F. 518 471 478 5% 629 564 564 10% 682 616 631

20% 798 727 728 30% 895 835 823 40% 978 925 ~34 50% 1037 1019 1009 60% -- -- 1024 70% -_ __ __ 80~ ~~ ~~ ~~
90% ---- __ __ 20 95% -- __ __ % Rec 51.8 55.0 58.0 % Res 48.2 45.0 42.0 * Contains 0.6-0.7 Wt. % inorganic particulate matter ''' ' ; - 23 -,: .

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1~77917 . CATALYSTS AND CATALYST PRECURSORS
Oil-soluble compounds used in forming the trace metal catalysts of this invention are listed below along with the name of the commercial supplier and any special conditions used in their application. Generally, the com-pounds were added to the residua feeds as received. Also listed are two solid catalysts that were tested:
1. Metal Resinates - These materials are supplied by Engel-hard Industries and are described by Engelhard as metal-organic compounds that are soluble in hydrocarbons. The metal resinates that were tested along with their Engel-hard identification number are as follows:
Molybdenum Resinate (~ 13.3% Mo), No. 8605 Vanadium Resinate (3.9% V), No. 51-F
Chromium Resinate (9.6~ Cr), No. 52-D
Cobalt Resinate (12% Co), No. A-1100 2. Molybdenum Napthenate - A naphthenic acid sal~ containing 6 wt.% molybdenum supplied by Shepherd Chemical Co.
3. Molybdenum Pentachloride - Resublimed 99+% pure MoC15 obtained from Ventron Corporation.
4. Molybdenum Hexacarbonyl - Mo(CO)6 powder obtained from Ventron Corporatlon.
5. Phosphomolybdic Acid - Crystalline material, 20 MoO3.
2H PO .48H2O, obtained from J.T. Baker Chemical Company.
Disso~ved ln water prior to adding to resid feeds. Solu-tion prepared using two parts by weight of water per part of the crystalline acid.
6. Nickel Octoate - purchased from Research Organic/Inorganic Chemical Corporation. Formula Ni[CoO(C2H5)CHC4H912.
Furnished solvent free.
7. Iron Naphthenate - purchased from MC/B Manufacturing Chemists.
8. Molybdenum Trioxide - Sublimed powder, 99.5% MoO3 from MC/B Manufacturing Chemists.
9. Recycle Molybdenum-Solids Catalyst - Solid material re-covered at end of hydroconversion runs, utilizing moly-naphthenate, by filtration. Washed free of adhering oil with toluene. Toluene displaced with hexane and solids dried under vacuum.
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~077917 lO. Molybdenum Sulfide on Charcoal - a commercial catalyst containing about lO wt.~ MoS2. The eatalyst has a sur-face area of about 970 m2/g and a pore volume of 0.41 cm3/g. Prior to use, the eatalyst was ground to a powder which exhibited a particle size ranging from one to two microns.

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AT REACTION CONDITIONS
- Molybdenum added as naphthenate, 350 wppm on feed - 30 min~ pretreat with H2 @ 385 C., 2400 psig - Hydroconversion @ 435 C., 1 Hr. 2500 psig avg. pressure - Liquid filtered from reactor, on condi-tions, using in-ternal metal frit filter. Retains 10-15 micron particles.
Run No. 2R-43 2R-44 Feed Cold Lake Bitumen Grams solids* produced per 100 g. of feed 0.83 0.91 % retained by 10-15 micron filter 66 80 % passed by 10-15 micron filter** 34 20 Grams moly present per 100 g. of feed 0.0336 0.0348 % recovered with solids ~10 microns 80 79 , % recovered with solids C10 microns 18 --* composite of coke, naturally occurring particulate matter, demetallization products, catalyst metal.
;~ **recovered by filtration at room temperature using a No. 2 ' Whatman* filter paper.

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10~79:17 TABLE l_ Athabasca Bitumen, 830 F., 2000+ psig Hydrogen Pressure, 60 min.
Run A B _ D E
Mo Naphthenate ppm Mo 93 93 -- -- 800 Recycle Solids ppm Mo 800 -- 800 93 --Con. Carbon Conversion % 58 58 58 54 64 Coke, % on Feed 0.14 2.20 0.16 1.85 0.37 Coke Producing Factor 0.018 0.29 0.020 0.27 0.05 a. coke Made , g. Con. Carbon Converted Ni + V Removal, % 86.5 63 84.5 52 93 Metal Removal Factor % Metals Removal 618 29 528 28 251 ~, ~ of Coke Made ; .
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i~77917 EX.~MPLE 2 ComparatiYe hydroconversion experiments were made utilizing a Cold Lake crude oil feed. The catalysts and conditions used as well as the results are summarized in Table 13.

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-~(~1779~7 As can be seen from Table 13, a catalyst prepared from an oil soluble metal compound in the presence of a particulate solid iron component retained, on recycle and reuse, its activity for coke suppression to a greater degree than such a catalyst prepared in the absence of an iron-containing particulate material.
The effectiveness of metals removal from the feed in these multi-cycle experiments is tabulated in Table 14. It can be seen that the effectiveness of the catalyst for metals removal with repeated catalyst use was greater when an iron-containing particulate material was added along with the soluble metal catalyst precursor.

Nickel Vanadium Removal, Wt.% Removal, Wt.%
Run SeriesI II III I II III
1st Cycle 85 84 88 91 86 93 2nd Cycle 66 74 79 77 87 92 3rd Cycle 68 76 79 78 88 93 EXP~IPLE 3 Catalyst recycle experiments were made wherein an iron-containing coal ash was added to the first cycle run along with the oil soluble molybdenum naphthenate catalyst precursor. The solid catalyst recovered from the first cycle was then tested in two subsequent runs to determine activity maintenance in recycle use. As shown by the data in Table 15, ,,, ` .

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10779'17 the catalyst comprised of molybdenum and the iron-containing , coal ash showed good activity retention in recycle runs not only for coke and light gas suppression but also for metals removal and Conradson Carbon conversion.

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Claims (26)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A process for hydroconvertng a heavy hydrocarbon oil chargestock, which comprises:
(a) adding to said chargestock an oil-soluble metal compound in an amount ranging from about 25 to about 950 weight parts per million, calculated as the elemental metal, based on said oil chargestock, said metal being selected from the group consisting of Group VB, VIB, VIIB and VIII of the Periodic Table of Elements and mixtures thereof;
(b) converting said oil-soluble compound within said chargestock in the presence of a hydrogen-containing gas to produce a solid, non-colloidal catalyst within said charge-stock;
(c) reacting the chargestock containing said catalyst with hydrogen under hydroconversion conditions, in a hydro-conversion zone, and (d) recovering a hydroconverted hydrocarbon oil.

2. The process of claim 1 wherein said oil soluble metal compound is selected from the group consisting of inorganic metal compounds, salts of organic acids, organometallic compounds and salts of organic amines.

3. The process of claim 1 wherein said oil soluble metal compound is selected from the group consisting of salts of acyclic aliphatic carboxylic acids and salts of alicyclic aliphatic carboxylic acids.

4. The process of claim 1 wherein said oil soluble metal compound is a salt of naphthenic acid.

5. The process of claim 1 wherein the metal constituent of said oil soluble metal compound is selected from the group consisting of molybdenum, chromium and vanadium.

6. The process of claim 1 wherein said oil soluble metal compound is molybdenum naphthenate.

7. The process of claim 1 wherein said hydrogen-containing gas of step (b) comprises from about 1 to 90 mole percent hydrogen sulfide.

8. The process of claim 1 wherein said hydrogen-containing gas of step (b) comprises from about 1 to 10 mole percent hydrogen sulfide.

9. The process of claim 1 wherein said oil soluble metal compound is converted to said solid, non-colloidal catalyst by subjecting said mixture to a temperature ranging from about 325°C. to about 538°C.

10. The process of claim 1 wherein said oil soluble metal compound is converted to said solid non-colloidal catalyst by first heating the oil chargestock containing the added oil soluble compound to a temperature ranging from about 325°C.
to about 415°C. in the presence of said hydrogen-containing gas to form a catalyst within said oil chargestock and subsequently reacting the oil containing said catalyst with hydrogen under hydroconversion conditions.

11. The process of claim 10 wherein said oil soluble metal compound is converted to said solid, non-colloidal catalyst in the presence of a gas containing hydrogen and hydrogen sulfide.

12. The process of claim 1 wherein said oil soluble metal compound is converted to said solid, non-colloidal catalyst in the presence of a hydrogen-containing gas under hydroconver-sion conditions thereby forming said catalyst in situ in said oil in a hydroconversion zone and producing a hydroconverted oil.

13. The process of claim 1 wherein said hydroconversion conditions include a temperature ranging from about 343°C. to about 538°C. (650 to 1000°F.) and a hydrogen partial pressure ranging from about 500 to about 5000 psig.

14. The process of claim 1 wherein the space velocity of said oil chargestock in said hydroconversion zone ranges from about 0.1 to 10 volumes of oil chargestock per hour per volume of hydroconversion zone.

15. The process of claim 1 wherein the reaction product resulting from step (c) comprises a hydroconverted oil con-taining solids, the additional steps which comprise separating at least a portion of said solids from said hydroconverted oil and recycling at least a portion of said solids to step (a) or to step (c).

16. The process of claim 1 wherein said catalyst is the sole catalyst in said hydroconversion zone.

17. The process of claim 1 wherein an iron component is added to said oil chargestock as solid particles and wherein said oil soluble metal compound added to said oil chargestock is selected from the Group consisting of Group VB, Group VIB, Group VIIB and Group VIII metals other than iron, of the Periodic Table of Elements, and mixtures thereof.

18. The process of claim 17 wherein said iron component is selected from the group consisting of elemental iron, iron oxides, iron sulfides, naturally occurring iron-containing ores, mineral mixtures, iron-containing ash derived from coal, bitumen and the like, fly ash, iron-containing by-products from metal refining processes and mixtures thereof.

19. The process of claim 17 wherein said iron component comprises a member selected from the group consisting of elemental iron, iron oxides, iron sulfides and mixtures thereof.

20. The process of claim 17 wherein said iron component is present in said hydroconversion zone in an amount ranging from about 0.01 to about 30 weight percent, calculated as the elemental metal based on said heavy oil.

21. The process of claim 17 wherein said added iron com-ponent is present in said hydroconversion zone in an amount ranging from about 0.01 to about 10 weight percent, calculated as the elemental metal based on said heavy oil.

22. The process of claim 17 wherein said iron component ranges in size from about 0.05 micron to about 200 microns in diameter.

23. A hydroconversion catalyst prepared by the steps which comprise:
(a) adding to a heavy hydrocarbon oil chargestock an oil-soluble metal compound in an amount ranging from about 25 to about 950 weight parts per million, calculated as the elemental metal, based on said oil chargestock, said metal being selected from the group consisting of Groups VB, VIB, VIIB and VIII of the Periodic Table of Elements and mixtures thereof;

(b) converting said oil-soluble metal compound within said chargestock in the presence of a hydrogen-containing gas to produce a first solid, non-colloidal catalyst within said chargestock;
(c) reacting the chargestock containing said catalyst with hydrogen under hydroconversion conditions in a hydro-conversion zone to produce a hydroconversion zone effluent comprising a hydroconverted oil and a second solid, non-colloidal catalyst;
(d) separating said second catalyst from said hydro-conversion zone effluent, and (e) recovering the separate second catalyst.

24. The catalyst prepared in accordance with claim 23 wherein said second catalyst recovered in step (e) comprises solid particles having a size greater than 0.5 micron in diameter.

25. The hydroconversion catalyst of claim 23 wherein said oil soluble metal compound of step (a) is selected from the group consisting of chromium compounds, molybdenum compounds and vanadium compounds.

26. A process for hydroconverting a heavy hydro-carbon oil chargestock, which comprises:
(a) reacting said oil with a hydrogen-containing gas under hydroconversion conditions in the presence of the catalyst recovered from step (e) of claim 23.