CA1334840C - Hydroconversion of heavy feeds by use of both supported and unsupported catalysts - Google Patents
Hydroconversion of heavy feeds by use of both supported and unsupported catalystsInfo
- Publication number
- CA1334840C CA1334840C CA 609476 CA609476A CA1334840C CA 1334840 C CA1334840 C CA 1334840C CA 609476 CA609476 CA 609476 CA 609476 A CA609476 A CA 609476A CA 1334840 C CA1334840 C CA 1334840C
- Authority
- CA
- Canada
- Prior art keywords
- oil
- metal
- catalyst
- concentrate
- dispersible
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Abstract
Disclosed is a catalytic process for hydroconvert-ing heavy hydrocarbonaceous feedstocks to lower boiling products wherein a catalyst precursor concentrate or cata-lyst concentrate is first prepared in a heavy oil medium then fed to a hydroconversion zone which may also contain a supported hydrotreating catalyst. The hydroconversion zone may be operated in either slurry or ebullating bed mode
Description
33 13~O
BACXGROUND OF THE l~v~N~lON
Field of the Invention This invention relates to an improvement in a catalytic hydroconversion process utilizing both an un~upported metal-containing catalyQt prepared from a catalyst precursor disper~ed in a hydrocarbonaceous oil and a supported catalyst co~po~ition.
Description of Infor~ation Di~closures There is ~ubstantial intere~t in the petro-leum industry for converting heavy hydrocarbonaceous feedstocks to lower boiling liquid~ and ga~e~. One type of proce~s is a ~lurry proce~s utilizing a cata-ly~t prepared in a hydrocarbon oil fro~ a thermally decomposable or oil ~oluble metal compound catalyst precursor. See, for exa~ple, U.S. Patents 4,226,742 and 4,244,839.
It i8 also known to u~e such catalysts in h~dLoco..~ersion p~_e ~r (i.e., coal liquefaction) in which coal particles are slurried in a hydrocarbo-naf E;"~ material. See, for example, U.S. Patents 4,077,867 and 4,111,787.
Another type of process used for converting heavy feedstocks is a process wherein the feedstock is sub~ected to hydroconversion conditions in an ex-panded, or ebullating, b-d of hydrotreating catalyst, 133~IO
such as Ni/Mo or Co/Mo on alumina See, for example, U S Patent Nos 4,549,957 and 4,657,665 The term ~hydroconversion" as used herein refers to a catalytic process conducted in the pres-ence of hydrogen in which at least a portion of the heavy constituents of a hydrocarbonaceous oil is con-verted to lower boiling products It may also simul-taneously reduce the c~ entration of nitrogenous compounds, and metallic constituents All boiling point~ referred to herein are at~ospheric pressure equivalent boiling points unles~
otherwi~- specified It has been found that introducing a cata-lyst precursor mixed in r-latively larg- amount~ in a hydrocarbonaceou~ oil (i , cataly~t pr-cursor con-centrate) into a hydroconversion zone containing a heavy hydrocarbonaceou~ chargestock ha~ certain advantages when compared with a process wherein the cataly~t pr-cur~or i~ introduced into th- hydrocon-version zon- without fir-t forming a concqntrate;
that is, by introducing th- cataly~t precur~or di-rectly into the feed in th- reactor The advantages includ- (i) ease of nixing the precursor with a ~all ~trean in~tead of the whole feed; (ii) the ability to store the precursor concentrate for future u~- and/or activity certification; and (iii) the abllity to u~e a hydrocarbonaceous oil, other than the feedstock, as di~persing m-diu~ for th- catalyst precur~or, which hydrocarbonaceou~ oil other than the feedstock can be more optimu~ for developing catalyst activity _ 3 _ 133~
Further, it has now been found that pre-treating a catalyst precursor mixed in relatively large amounts with a hydrocarbonaceous oil (i.e., cataly~t precursor concentrate) to convert the cata-lyst precursor to a ~olid catalyst in the oil, and subsequently introducing at least a portion of the resulting catalyst concentrate into the hydrocarbo-naceous chargestock to be hydroconverted will provide certain advantages. Such advantages include greater flexibility of conditions, for example, use of higher concentrations of sulfiding agent than the concentra-tions that would be used to treat the total charge-stock, flexibility of heat balance, and economy of energy. Treatment of only the catalyst precursor concentrate al o peroits reduction of ~ize of equip-ment needed compared to treatment of the catalyst precursor in the total chargestock. Furthermore, preparing a catalyst concentrate permits storing the catalyst concentrate to use as needed on-site or to send to another 6ite.
SUMMARY OF TU~ l~.v~r.~-~ON
In accordance with the present invention ther- is provided a process for converting heavy hydLG~arbonaceou~ feed~tocks to lower boiling pro-duct~. Th- prc~ comprise~:
(a) forning a ~ixture of a heavy hydrocarbonace-OU8 oil and a dispersible, or decomposable, metal compound, said metal being selected from the group consisting of Groups II, III, ~V, V, VIB, V$IB, and VIII and mixture~ thereof of the Periodic Table of th- Elements;
- 4 - 1 3 3~ 0 (b) introducing at least a portion of said mix-ture into a hydroconversion zone containing a heavy hydrocarbonaceOUS chargestoc~ and a supported cata-lyst comprised of (i) a metal selected from Groups VIB and vIII of the Periodic Table of the Elements and (ii) a refractory inorganic support material;
(c) subjecting tbe chargestock and catalysts to a temperature of about 700 to 900F, in the presence of a hydrogen-containing gas, and a hydrog-n partial pressure from about 100 to 5000 psig, th-reby produc-ing lower boiling products In a preferred ecbodim~nt of the present invention, prior to introducing the mixture of step (a) into the hydroconversion zone, it i~ fir~t heated in the presenc- of a ulfiding agent at a temperature of at least a~out 500F for an effective amount of time to convert the oil-dispersible or d-composable, metal compound to the coLLe~onding metal-containing catalyst in said hydrocarbonaceous oil In preferred embodiments of th- present invention, th- ulfiding ag-nt is selectQd from th-group con~i~ting of hydrogen sulfide, a blend of hyd~og-n and hydrogen sulfide, elemental sulfur, carbon di~ulfide and compo~n~fi that decompose to yi-ld sulfur ~oieties which will react with the cata-ly-t precursor Also suitable are plant streams con-taining hydrogen sulfide in mixture with other gases, and sulfur-rich hydrocarbon media con~A~ning more than 0 1 wt % sulfur In still other preferred embodiments of the pr-~ent invention, th- sulfiding agent i~ hydrogen _ 5 _ 1 3~ O
sulfide which is present in a ratio of H2S to ele-mental metal of from about 1 to 5.
In other preferred embodiments of the pre-sent invention, the concentration of oil dispersible metal compound is such that the concentration of metal is from about O.l to 2 wt. %, calculated as elemental metal.
In yet other preferred embodiments of the present invention the oil-dispersible metal compound is selected from the group consisting of inorganic metal compounds, salts of organic acids, organo-metallic compounds, salts of organic amines, and mix-ture~ thereof.
In still other preferred embodiments of the present invention the oil-dispersibl- ~etal compound i~ a phocphosmolybdic acid, and the hydroconversion is conducted in an expanded bed of supported catalyst comprised of Ni/Mo on alumina or Co/Mo on alumina.
BRI~F D~-~CRIPTION OF T~ DRAWING
Figur- 1 is a schematic flow plan of one embodiment of the invention.
Figure 2 is a plot of toluene insoluble coke vs. catalyst precursor concentrate composition.
The plot demonstrates the advantages of employing a precursor concentrate containing from about 22 to 85 wt.% heavier oil with the balance being lighter oil.
- 6 - 13 3 ~
DESCRIPTION OF THE PREFERRED EMBODIMENT
Referring to Figure 1 hereof, a heavy hydrocarbonaceoUs oil is introduced by line 10 into mixing zone 1 Suitable heavy hydrocarbonaceous oils for introduction into mixing zone 1, include hydro-carbonaceous oils comprising constituents boiling above about 1050F, pr-ferably having at least 10 weight percent con~tituent~ boiling above about 1050F, such a~ crude oil~, atmospheric residua boil-ing above about 650F, and vacuum residua boiling above about 1050F Preferably, the hydrocarbonace-ous oil ha~ an initial boiling point above at least 650F and comprise~ ~p~ltene- In~t-ad of u~ing one zone, ~uch a~ mixing zone 1 a~ both mixing and catalyst formation zone, a ~eparate cataly~t forma-tion zone 2 or vessel 2, can b- used after mixing zone 1, to prepare the cataly~t (i e , convert the cataly~t precur~or to the ~olid cataly~t) ~ost pre-ferably, the hydrocarbonaceous oils compri e a light-er boiling oil boiling b-low about 1050F and a heavier oil boiling above about 1050F in a blend compri~ing at lea~t about 10 weight percent, prefer-ably at least about 22 weight percent mat-rials boil-ing abov- 1050F Preferred concentrations of the 1050+F fraction in the blend include from 22 to 85 weight percent heavier oil, ~ore preferably about 30 to 85 weight percent heavi-r oil, still more prefer-ably about 40 to 85 weight percent heavier oil, and mo~t preferably about 45 to 75 weight percent heavier oil, based on the total weight of the blend (mixture of oilg). ThQ light oil may be a ga~ oil and the heavier oil may be a vacuu~ residuum Alternatively, an atmospheric residuum having the appropriat- amount of desired constituent~ may be used as the oil of 1~3~0 line 10. The hydrocarbonaceous oil carried in line 10 may be derived from any source such as petroleum, tarsand oil, shale oil, liquids derived from coal liquefaction processes, and mixtures thereof. Gener-ally these oils have a Conradson carbon content rang-ing from about 5 to about 50 weight percent (as to Conradson carbon content see ASTM Test D 189-65). An oil dispersible, or decomposable, metal compound (catalyst precursor) i- introduced into mixing zone 1 by line 12. The oil-dispersibl- metal compound may b- a compound that i~ solubl- in the hydrocarbonace-ou~ oil or a compound that i~ ~oluble in an organic compound (liquid medium) that can be disper~ed in the hydrocarbonaceous oil or a COmYOUJ~d that i~ water ~oluble and the aqueous solution di~persed in the hydrocarbonaceous material. For example, th- oil dispersible metal compound introduced by line 12 may b- in a phenolic medium, in wat-r, in alcohol, etc.
Suitable oil dispersible metal compolln~ convertible (under preparation condition~) to ~olid, metal-con-taining catalysts include: (1) inorganic metal com-pounds such a~ carbonyls, halides, oxyhalides; poly-acid~ such a~ i~opolyacid~ and heteropolyacids (e.g., r~o~omolybdic acid, and molybdosilicic acid); (2) metal salts of organic acid~ ~uch as acyclic and cyclic aliphatic carboxylic acids and thiocarboxylic acid~ containing two or more carbon atoms (e.g., naphthenic acids); aromatic carboxylic acids (e.g., toluic acid); sulfonic acids (e.g., toluenesulfonic acid); sulrinic acid~; mercaptans; xanthic acids;
phenols, di- and polyhydroxy aromatic componnd~; (3) organometallic compo~lnA~ ~uch as metal chelate~, e.g., with 1,3-diketones, ethylenediamine, ethylene-diaminetetraacetic acid, phthalocyanine~, etc.; (4) metal salt~ of organic a~ine~ such as aliphatic - 8 - 1~ 34 8 ~ ~
aoines, aromatic amines and quatenary ammonium com-pounds.
The metal constituent of the oil dispersi-ble metal compound that is convertible to a solid, metal-containing catalyst is selected from the group consisting of Groups II, III, IV, V, VIB, VIIB and VIII, and mixtures thereof of the Periodic Table of the Elements. Non-limiting examples include zinc, antimony, bismuth, titaniu~, cerium, vanadium, niobium, tantalu~, chromiuo, molybdenum, tungsten, manganese, rheniu~, iron, cobalt, nickel and the noble metals including platinu~, iridium, palladium, o~iuo, ruthenium, and rhodium. The preferred metal constituent of the oil dispersible compound i8 selected from the group consi~ting of molybdenum, tungsten, vanadium, chromiuc, cobalt, titanium, iron, nickel and mixtures thereof. Preferred compounds of the given metals include the salts of acyclic (~traight or branched chain) aliphatic carboxylic acids, salts of cyclic aliphatic carboxylic acids, polyacid~, carbonyls, phenolates and organoamine ~alts.
The Periodic Table of Elements referred to herein is published by Sergeant-Welch Scientific Company being copyrighted in 1979 and available from them as Catalog Number S-18806. Such oil dispersible metal compounds are described in U.S. Patent 4,295,995.
The preferred oil dispersible metal compounds are inorganic polyacids of metals selected from Groups VA, VIA, and mixtures thereof, that is, vanadium, niobium, chromium, molybdenum, tungsten and mixtures thereof. Suitable inorganic - 9 133~
polyacids include phosphomolybdic acid, phospho-tungstic acid, phosphovanadic acid, ~ilicomolybdic acid, silicotungstiC acid, silicovanadic acid and mixtures thereof The preferred polyacid is a phos-phomolybdic acid The terms "heteropolyacids" and ~isopolyacids" are used herein in accordance with the definitions given in Advanced Inorganic ChemistrY, 4th Edition, by S A Cotton and Geoffrey Wilkinson, Inter~cience Publishers, New York, pages 852-861 R-ferring to th- figur-, a sulfiding agent i- introduced into cataly-t for~ation zon- 2 by line 14 The sulfiding agent i~ selected fro~ the group con~isting of a hydrogen sulfid- conta~nin~ ga~
mental sulfur, or a compound that decompose~ to pro-vide sulfur for reaction with the metal of the cata-lyst precursor Non-limiting examples of such com-po~n~ include mercaptans, thioethers, dithioether~, and carbon disulfid- Al~o ~uitable ar- plant stream~ containing hydrogen sulfide in ~ixture with other gases and sulfur-rich hydrocarbonaceous media such as petroleu~ residua containing more than 0 1 wt % sulfur, in particular, crude oil, and atmo-spheric and vacuu~ residua Of course, if zon-serve~ a~ both the mixing zon- and the catalyst for-mation zon-, then the sulfiding agent i~ introduced into zone 1 Preferably the sulfiding agent com-pri~e~ hydrogen sulfide or a mixture of hydrogen and hydrogen ~ulfide comprised of at least about 1 mole %
hydrogen Qulfide, based on th- total mixture It is also preferred that th H2S/~etal ratio be from about l to 5 It is to be understood that in thos- cases wh-re th- hydrocarbon mediu~ in th- catalyst 13~S ~ O
precursor concentrate contains reactive sulfur moieties in a sUlfUr to metal ratio of at least 1 to 1, neither extraneous sulfiding agents nor hydrogen need be introduced in catalyst preparation zone 2 It i~ also to be understood that in those cases where the catalyst precursor concentrate of zone 1 is converted to a catalyst concentrate prior to introduction into th- hydroconversion zone, or when it i~ fed directly into the hydroconversion zone, without first forning a cataly~t concentrate, but the chargestock itself contain~ at l-ast the re-guired ~toichiometric amount of sulfur moieties that will react with the catalyst prscur~or, th~n extrane-ous ~ulfiding agent need not b~ introduced into the hydroconversion zone A sufficient amount of th- oil dispersible metal compound (catalyst precursor) i~ introduced into mixing zone 1 to form a catalyst precursor con-centrate, that is, a mixture comprising from 0 1 to 2, preferably from 0 2 to 2, mor- preferably from about 0 2 to 1, and most prof-rably from 0 3 to 1, weight percent metal, calculated a~ ele~ental metal, based on the weight of the hydrocarbonaceous oil in the mixtur- The mixtur- of oil di~porsibl- metal compound and hydrocarbonaceous oil ~catalyst precur-~or conc~ntrate) is heated in cataly~t formation zone 2 to a temperature ~ufficient to convert the oil dis-persiblQ metal compound (catalyst precursor) to the corresponding metal-contain~n~ solid catalyst Suit-able catalyst formation conditions include a tempera-ture of at least about 500F, pre~erably a tempera-ture ranging from 500F to 850F, mor- preferably from about 650F to 780F, most preferably from about 3 g ~ ,A~ o 680F to 730F, and a total pressure ranging from atmospheric to 5000 psig, preferably a pressure ranging from 10 to 2000 psig to convert the oil dis-per~ible metal compound to a solid catalyst compris-ing the metals corresponding to the metals of the catalyst precursor The resulting catalyst concen-trate (solid catalyst particles dispersed in the hydrocarbon oil) is removed by line 16 from catalyst formation zone 2 Of course, the precursor concen-trate of mixing zone 1 can be fed directly into line 18, or into hydroconversion zone 3, as long as enough sulfiding agent is present in the feedstock, or inde-pendently added to the feedstock or hydroconversion zone, to convert the precursor concentrate to the correspondend catalyst concentrate At least a portion c~ the catalyst concen-trat- i introduced, via line 16, into line 18 which carries a hydrocarbonaceous oil chargestock and is dispersed in the oil chargestock Suitable hydro-carbonaceous chargestocks include crude oils, mix-tures of hydrocarbons boiling above 430F, preferably above 650F, for example, gas oils, vacuum residua, atmospheric residua, and once through coker bottoms The hydrocarhonace;~~~ oil may be derived from any sourc- uch a~ petroleum, shale oil, tarsand oil, oils derived from coal liquefaction processes, in-cluding coal liquefaction bottoms, and mixtures thereof Preferably, th- hydrocarbonaceous oils have at least 10 weight percent material boiling above 1050F More preferably, th- hydrocarbonaceous oils have a Conradson carbon content ranging from about 5 to about 50 weight percent - 12 - 1 3 3l ~ ~ a A hydrogen-containing gas is introduced by line 20 into line 18 The mixture of hydrocarbo-naceous chargestock, catalyst concentrate, and hydrogen is passed by line 18 into hydroconversion zone 3 The catalyst concentrate of line 16 is added to the hydrocarbonaceous chargestock in an amount sufficient to provide fro- about 10 to about 2000 wppm metal, preferably from about 50 to about 1000 wppm metal, more preferably frou about 50 to about 300 wppm ~etal, calculated as elemental metal, based on the total hydroconversion zone chargestock, i,- , CG~ ntrate plu~ hydrocarbonaceous chargestock It i~ to b~ understood that the figure hereof i~ a general description of one pref-rred pro-cess scheme and that the components represented by lines such as 16, 20, and the line ~howing intermedi-at- liguid recycle, of line 40, can be introduced directly into the hydroconversion zone 3 instead of into feedstock line 18 For pUL~ of the present invention, the hydL~oo ~-r~ion of zone 3 can be accomplished by ei-ther a lurry t~hn~que or by an sY~a~-d (~bullated) b d t~:hnique If op-rated as a slurry, then sup-port d cataly~t need not b- present Suitable slurry hydroconv-r~ion operating condition~ are summarized b lo~
Condition~ Broad RangePreferred Range Temperature, F 700 to 900820 to 870 `Hydrogen Partial 100 to 5000300 to 3000 Pressure, psig If an ebullated bed process is used, the hydroconversion zon- may contain one or more reactors 1~4~'J
which contain an expanded bed of supported hydro-treating catalyst~. In expanded bed processes, a packed bed of sUpported catalysts is expanded and modi~ied by upflow of hydrocarbonaceous feed and hydrogen-containing gas at space velocities effective to provide adequate mobilization and expansion, and thereby promote contact between catalyst particles and reactants, without substantial carryover of sup-ported catalyst particl-s. Bulk density of the sup-ported catalyst i8 inportant from the standpoint of attaining appropriate bed expan~ion and mobilization at economically practical space velocities. Catalyst particle size and shape are al80 important in this regard. ~Preferred catalysts for ~Yr~Aed bed use are extrudates of about 0.02 to about 0.05 inch diameter, with about l/32-inch being preferred. A preferred expanded bed process, particularly for treatment of high metals or high metals and sulfur content feeds is an ebullated bed process. In such processes, cat-alyst i5 preferably present in an amount sufficient to occupy at least about 10 volume % of the expanded bed and is continuously added to the reaction zone to compensate for spent catalyst which is continuously withdrawn. Specific details with respect to ebullat-ed b~d proc~so~ are found in U.S. Patent Nos.
BACXGROUND OF THE l~v~N~lON
Field of the Invention This invention relates to an improvement in a catalytic hydroconversion process utilizing both an un~upported metal-containing catalyQt prepared from a catalyst precursor disper~ed in a hydrocarbonaceous oil and a supported catalyst co~po~ition.
Description of Infor~ation Di~closures There is ~ubstantial intere~t in the petro-leum industry for converting heavy hydrocarbonaceous feedstocks to lower boiling liquid~ and ga~e~. One type of proce~s is a ~lurry proce~s utilizing a cata-ly~t prepared in a hydrocarbon oil fro~ a thermally decomposable or oil ~oluble metal compound catalyst precursor. See, for exa~ple, U.S. Patents 4,226,742 and 4,244,839.
It i8 also known to u~e such catalysts in h~dLoco..~ersion p~_e ~r (i.e., coal liquefaction) in which coal particles are slurried in a hydrocarbo-naf E;"~ material. See, for example, U.S. Patents 4,077,867 and 4,111,787.
Another type of process used for converting heavy feedstocks is a process wherein the feedstock is sub~ected to hydroconversion conditions in an ex-panded, or ebullating, b-d of hydrotreating catalyst, 133~IO
such as Ni/Mo or Co/Mo on alumina See, for example, U S Patent Nos 4,549,957 and 4,657,665 The term ~hydroconversion" as used herein refers to a catalytic process conducted in the pres-ence of hydrogen in which at least a portion of the heavy constituents of a hydrocarbonaceous oil is con-verted to lower boiling products It may also simul-taneously reduce the c~ entration of nitrogenous compounds, and metallic constituents All boiling point~ referred to herein are at~ospheric pressure equivalent boiling points unles~
otherwi~- specified It has been found that introducing a cata-lyst precursor mixed in r-latively larg- amount~ in a hydrocarbonaceou~ oil (i , cataly~t pr-cursor con-centrate) into a hydroconversion zone containing a heavy hydrocarbonaceou~ chargestock ha~ certain advantages when compared with a process wherein the cataly~t pr-cur~or i~ introduced into th- hydrocon-version zon- without fir-t forming a concqntrate;
that is, by introducing th- cataly~t precur~or di-rectly into the feed in th- reactor The advantages includ- (i) ease of nixing the precursor with a ~all ~trean in~tead of the whole feed; (ii) the ability to store the precursor concentrate for future u~- and/or activity certification; and (iii) the abllity to u~e a hydrocarbonaceous oil, other than the feedstock, as di~persing m-diu~ for th- catalyst precur~or, which hydrocarbonaceou~ oil other than the feedstock can be more optimu~ for developing catalyst activity _ 3 _ 133~
Further, it has now been found that pre-treating a catalyst precursor mixed in relatively large amounts with a hydrocarbonaceous oil (i.e., cataly~t precursor concentrate) to convert the cata-lyst precursor to a ~olid catalyst in the oil, and subsequently introducing at least a portion of the resulting catalyst concentrate into the hydrocarbo-naceous chargestock to be hydroconverted will provide certain advantages. Such advantages include greater flexibility of conditions, for example, use of higher concentrations of sulfiding agent than the concentra-tions that would be used to treat the total charge-stock, flexibility of heat balance, and economy of energy. Treatment of only the catalyst precursor concentrate al o peroits reduction of ~ize of equip-ment needed compared to treatment of the catalyst precursor in the total chargestock. Furthermore, preparing a catalyst concentrate permits storing the catalyst concentrate to use as needed on-site or to send to another 6ite.
SUMMARY OF TU~ l~.v~r.~-~ON
In accordance with the present invention ther- is provided a process for converting heavy hydLG~arbonaceou~ feed~tocks to lower boiling pro-duct~. Th- prc~ comprise~:
(a) forning a ~ixture of a heavy hydrocarbonace-OU8 oil and a dispersible, or decomposable, metal compound, said metal being selected from the group consisting of Groups II, III, ~V, V, VIB, V$IB, and VIII and mixture~ thereof of the Periodic Table of th- Elements;
- 4 - 1 3 3~ 0 (b) introducing at least a portion of said mix-ture into a hydroconversion zone containing a heavy hydrocarbonaceOUS chargestoc~ and a supported cata-lyst comprised of (i) a metal selected from Groups VIB and vIII of the Periodic Table of the Elements and (ii) a refractory inorganic support material;
(c) subjecting tbe chargestock and catalysts to a temperature of about 700 to 900F, in the presence of a hydrogen-containing gas, and a hydrog-n partial pressure from about 100 to 5000 psig, th-reby produc-ing lower boiling products In a preferred ecbodim~nt of the present invention, prior to introducing the mixture of step (a) into the hydroconversion zone, it i~ fir~t heated in the presenc- of a ulfiding agent at a temperature of at least a~out 500F for an effective amount of time to convert the oil-dispersible or d-composable, metal compound to the coLLe~onding metal-containing catalyst in said hydrocarbonaceous oil In preferred embodiments of th- present invention, th- ulfiding ag-nt is selectQd from th-group con~i~ting of hydrogen sulfide, a blend of hyd~og-n and hydrogen sulfide, elemental sulfur, carbon di~ulfide and compo~n~fi that decompose to yi-ld sulfur ~oieties which will react with the cata-ly-t precursor Also suitable are plant streams con-taining hydrogen sulfide in mixture with other gases, and sulfur-rich hydrocarbon media con~A~ning more than 0 1 wt % sulfur In still other preferred embodiments of the pr-~ent invention, th- sulfiding agent i~ hydrogen _ 5 _ 1 3~ O
sulfide which is present in a ratio of H2S to ele-mental metal of from about 1 to 5.
In other preferred embodiments of the pre-sent invention, the concentration of oil dispersible metal compound is such that the concentration of metal is from about O.l to 2 wt. %, calculated as elemental metal.
In yet other preferred embodiments of the present invention the oil-dispersible metal compound is selected from the group consisting of inorganic metal compounds, salts of organic acids, organo-metallic compounds, salts of organic amines, and mix-ture~ thereof.
In still other preferred embodiments of the present invention the oil-dispersibl- ~etal compound i~ a phocphosmolybdic acid, and the hydroconversion is conducted in an expanded bed of supported catalyst comprised of Ni/Mo on alumina or Co/Mo on alumina.
BRI~F D~-~CRIPTION OF T~ DRAWING
Figur- 1 is a schematic flow plan of one embodiment of the invention.
Figure 2 is a plot of toluene insoluble coke vs. catalyst precursor concentrate composition.
The plot demonstrates the advantages of employing a precursor concentrate containing from about 22 to 85 wt.% heavier oil with the balance being lighter oil.
- 6 - 13 3 ~
DESCRIPTION OF THE PREFERRED EMBODIMENT
Referring to Figure 1 hereof, a heavy hydrocarbonaceoUs oil is introduced by line 10 into mixing zone 1 Suitable heavy hydrocarbonaceous oils for introduction into mixing zone 1, include hydro-carbonaceous oils comprising constituents boiling above about 1050F, pr-ferably having at least 10 weight percent con~tituent~ boiling above about 1050F, such a~ crude oil~, atmospheric residua boil-ing above about 650F, and vacuum residua boiling above about 1050F Preferably, the hydrocarbonace-ous oil ha~ an initial boiling point above at least 650F and comprise~ ~p~ltene- In~t-ad of u~ing one zone, ~uch a~ mixing zone 1 a~ both mixing and catalyst formation zone, a ~eparate cataly~t forma-tion zone 2 or vessel 2, can b- used after mixing zone 1, to prepare the cataly~t (i e , convert the cataly~t precur~or to the ~olid cataly~t) ~ost pre-ferably, the hydrocarbonaceous oils compri e a light-er boiling oil boiling b-low about 1050F and a heavier oil boiling above about 1050F in a blend compri~ing at lea~t about 10 weight percent, prefer-ably at least about 22 weight percent mat-rials boil-ing abov- 1050F Preferred concentrations of the 1050+F fraction in the blend include from 22 to 85 weight percent heavier oil, ~ore preferably about 30 to 85 weight percent heavi-r oil, still more prefer-ably about 40 to 85 weight percent heavier oil, and mo~t preferably about 45 to 75 weight percent heavier oil, based on the total weight of the blend (mixture of oilg). ThQ light oil may be a ga~ oil and the heavier oil may be a vacuu~ residuum Alternatively, an atmospheric residuum having the appropriat- amount of desired constituent~ may be used as the oil of 1~3~0 line 10. The hydrocarbonaceous oil carried in line 10 may be derived from any source such as petroleum, tarsand oil, shale oil, liquids derived from coal liquefaction processes, and mixtures thereof. Gener-ally these oils have a Conradson carbon content rang-ing from about 5 to about 50 weight percent (as to Conradson carbon content see ASTM Test D 189-65). An oil dispersible, or decomposable, metal compound (catalyst precursor) i- introduced into mixing zone 1 by line 12. The oil-dispersibl- metal compound may b- a compound that i~ solubl- in the hydrocarbonace-ou~ oil or a compound that i~ ~oluble in an organic compound (liquid medium) that can be disper~ed in the hydrocarbonaceous oil or a COmYOUJ~d that i~ water ~oluble and the aqueous solution di~persed in the hydrocarbonaceous material. For example, th- oil dispersible metal compound introduced by line 12 may b- in a phenolic medium, in wat-r, in alcohol, etc.
Suitable oil dispersible metal compolln~ convertible (under preparation condition~) to ~olid, metal-con-taining catalysts include: (1) inorganic metal com-pounds such a~ carbonyls, halides, oxyhalides; poly-acid~ such a~ i~opolyacid~ and heteropolyacids (e.g., r~o~omolybdic acid, and molybdosilicic acid); (2) metal salts of organic acid~ ~uch as acyclic and cyclic aliphatic carboxylic acids and thiocarboxylic acid~ containing two or more carbon atoms (e.g., naphthenic acids); aromatic carboxylic acids (e.g., toluic acid); sulfonic acids (e.g., toluenesulfonic acid); sulrinic acid~; mercaptans; xanthic acids;
phenols, di- and polyhydroxy aromatic componnd~; (3) organometallic compo~lnA~ ~uch as metal chelate~, e.g., with 1,3-diketones, ethylenediamine, ethylene-diaminetetraacetic acid, phthalocyanine~, etc.; (4) metal salt~ of organic a~ine~ such as aliphatic - 8 - 1~ 34 8 ~ ~
aoines, aromatic amines and quatenary ammonium com-pounds.
The metal constituent of the oil dispersi-ble metal compound that is convertible to a solid, metal-containing catalyst is selected from the group consisting of Groups II, III, IV, V, VIB, VIIB and VIII, and mixtures thereof of the Periodic Table of the Elements. Non-limiting examples include zinc, antimony, bismuth, titaniu~, cerium, vanadium, niobium, tantalu~, chromiuo, molybdenum, tungsten, manganese, rheniu~, iron, cobalt, nickel and the noble metals including platinu~, iridium, palladium, o~iuo, ruthenium, and rhodium. The preferred metal constituent of the oil dispersible compound i8 selected from the group consi~ting of molybdenum, tungsten, vanadium, chromiuc, cobalt, titanium, iron, nickel and mixtures thereof. Preferred compounds of the given metals include the salts of acyclic (~traight or branched chain) aliphatic carboxylic acids, salts of cyclic aliphatic carboxylic acids, polyacid~, carbonyls, phenolates and organoamine ~alts.
The Periodic Table of Elements referred to herein is published by Sergeant-Welch Scientific Company being copyrighted in 1979 and available from them as Catalog Number S-18806. Such oil dispersible metal compounds are described in U.S. Patent 4,295,995.
The preferred oil dispersible metal compounds are inorganic polyacids of metals selected from Groups VA, VIA, and mixtures thereof, that is, vanadium, niobium, chromium, molybdenum, tungsten and mixtures thereof. Suitable inorganic - 9 133~
polyacids include phosphomolybdic acid, phospho-tungstic acid, phosphovanadic acid, ~ilicomolybdic acid, silicotungstiC acid, silicovanadic acid and mixtures thereof The preferred polyacid is a phos-phomolybdic acid The terms "heteropolyacids" and ~isopolyacids" are used herein in accordance with the definitions given in Advanced Inorganic ChemistrY, 4th Edition, by S A Cotton and Geoffrey Wilkinson, Inter~cience Publishers, New York, pages 852-861 R-ferring to th- figur-, a sulfiding agent i- introduced into cataly-t for~ation zon- 2 by line 14 The sulfiding agent i~ selected fro~ the group con~isting of a hydrogen sulfid- conta~nin~ ga~
mental sulfur, or a compound that decompose~ to pro-vide sulfur for reaction with the metal of the cata-lyst precursor Non-limiting examples of such com-po~n~ include mercaptans, thioethers, dithioether~, and carbon disulfid- Al~o ~uitable ar- plant stream~ containing hydrogen sulfide in ~ixture with other gases and sulfur-rich hydrocarbonaceous media such as petroleu~ residua containing more than 0 1 wt % sulfur, in particular, crude oil, and atmo-spheric and vacuu~ residua Of course, if zon-serve~ a~ both the mixing zon- and the catalyst for-mation zon-, then the sulfiding agent i~ introduced into zone 1 Preferably the sulfiding agent com-pri~e~ hydrogen sulfide or a mixture of hydrogen and hydrogen ~ulfide comprised of at least about 1 mole %
hydrogen Qulfide, based on th- total mixture It is also preferred that th H2S/~etal ratio be from about l to 5 It is to be understood that in thos- cases wh-re th- hydrocarbon mediu~ in th- catalyst 13~S ~ O
precursor concentrate contains reactive sulfur moieties in a sUlfUr to metal ratio of at least 1 to 1, neither extraneous sulfiding agents nor hydrogen need be introduced in catalyst preparation zone 2 It i~ also to be understood that in those cases where the catalyst precursor concentrate of zone 1 is converted to a catalyst concentrate prior to introduction into th- hydroconversion zone, or when it i~ fed directly into the hydroconversion zone, without first forning a cataly~t concentrate, but the chargestock itself contain~ at l-ast the re-guired ~toichiometric amount of sulfur moieties that will react with the catalyst prscur~or, th~n extrane-ous ~ulfiding agent need not b~ introduced into the hydroconversion zone A sufficient amount of th- oil dispersible metal compound (catalyst precursor) i~ introduced into mixing zone 1 to form a catalyst precursor con-centrate, that is, a mixture comprising from 0 1 to 2, preferably from 0 2 to 2, mor- preferably from about 0 2 to 1, and most prof-rably from 0 3 to 1, weight percent metal, calculated a~ ele~ental metal, based on the weight of the hydrocarbonaceous oil in the mixtur- The mixtur- of oil di~porsibl- metal compound and hydrocarbonaceous oil ~catalyst precur-~or conc~ntrate) is heated in cataly~t formation zone 2 to a temperature ~ufficient to convert the oil dis-persiblQ metal compound (catalyst precursor) to the corresponding metal-contain~n~ solid catalyst Suit-able catalyst formation conditions include a tempera-ture of at least about 500F, pre~erably a tempera-ture ranging from 500F to 850F, mor- preferably from about 650F to 780F, most preferably from about 3 g ~ ,A~ o 680F to 730F, and a total pressure ranging from atmospheric to 5000 psig, preferably a pressure ranging from 10 to 2000 psig to convert the oil dis-per~ible metal compound to a solid catalyst compris-ing the metals corresponding to the metals of the catalyst precursor The resulting catalyst concen-trate (solid catalyst particles dispersed in the hydrocarbon oil) is removed by line 16 from catalyst formation zone 2 Of course, the precursor concen-trate of mixing zone 1 can be fed directly into line 18, or into hydroconversion zone 3, as long as enough sulfiding agent is present in the feedstock, or inde-pendently added to the feedstock or hydroconversion zone, to convert the precursor concentrate to the correspondend catalyst concentrate At least a portion c~ the catalyst concen-trat- i introduced, via line 16, into line 18 which carries a hydrocarbonaceous oil chargestock and is dispersed in the oil chargestock Suitable hydro-carbonaceous chargestocks include crude oils, mix-tures of hydrocarbons boiling above 430F, preferably above 650F, for example, gas oils, vacuum residua, atmospheric residua, and once through coker bottoms The hydrocarhonace;~~~ oil may be derived from any sourc- uch a~ petroleum, shale oil, tarsand oil, oils derived from coal liquefaction processes, in-cluding coal liquefaction bottoms, and mixtures thereof Preferably, th- hydrocarbonaceous oils have at least 10 weight percent material boiling above 1050F More preferably, th- hydrocarbonaceous oils have a Conradson carbon content ranging from about 5 to about 50 weight percent - 12 - 1 3 3l ~ ~ a A hydrogen-containing gas is introduced by line 20 into line 18 The mixture of hydrocarbo-naceous chargestock, catalyst concentrate, and hydrogen is passed by line 18 into hydroconversion zone 3 The catalyst concentrate of line 16 is added to the hydrocarbonaceous chargestock in an amount sufficient to provide fro- about 10 to about 2000 wppm metal, preferably from about 50 to about 1000 wppm metal, more preferably frou about 50 to about 300 wppm ~etal, calculated as elemental metal, based on the total hydroconversion zone chargestock, i,- , CG~ ntrate plu~ hydrocarbonaceous chargestock It i~ to b~ understood that the figure hereof i~ a general description of one pref-rred pro-cess scheme and that the components represented by lines such as 16, 20, and the line ~howing intermedi-at- liguid recycle, of line 40, can be introduced directly into the hydroconversion zone 3 instead of into feedstock line 18 For pUL~ of the present invention, the hydL~oo ~-r~ion of zone 3 can be accomplished by ei-ther a lurry t~hn~que or by an sY~a~-d (~bullated) b d t~:hnique If op-rated as a slurry, then sup-port d cataly~t need not b- present Suitable slurry hydroconv-r~ion operating condition~ are summarized b lo~
Condition~ Broad RangePreferred Range Temperature, F 700 to 900820 to 870 `Hydrogen Partial 100 to 5000300 to 3000 Pressure, psig If an ebullated bed process is used, the hydroconversion zon- may contain one or more reactors 1~4~'J
which contain an expanded bed of supported hydro-treating catalyst~. In expanded bed processes, a packed bed of sUpported catalysts is expanded and modi~ied by upflow of hydrocarbonaceous feed and hydrogen-containing gas at space velocities effective to provide adequate mobilization and expansion, and thereby promote contact between catalyst particles and reactants, without substantial carryover of sup-ported catalyst particl-s. Bulk density of the sup-ported catalyst i8 inportant from the standpoint of attaining appropriate bed expan~ion and mobilization at economically practical space velocities. Catalyst particle size and shape are al80 important in this regard. ~Preferred catalysts for ~Yr~Aed bed use are extrudates of about 0.02 to about 0.05 inch diameter, with about l/32-inch being preferred. A preferred expanded bed process, particularly for treatment of high metals or high metals and sulfur content feeds is an ebullated bed process. In such processes, cat-alyst i5 preferably present in an amount sufficient to occupy at least about 10 volume % of the expanded bed and is continuously added to the reaction zone to compensate for spent catalyst which is continuously withdrawn. Specific details with respect to ebullat-ed b~d proc~so~ are found in U.S. Patent Nos.
4,549,9S7; 3,188,286; 3,630,887; 2,987,465; 2,987,465 and Re. 25,770.
The hydrocarbonaceous oil is contacted with hydrogen in the ebullating bed of supported hydro-treating catalyst also at the above mentioned hydro-conversion temperature~ and pressures and at a hydrogen flow rate of about 1000 to about 20,000 SCFB
(-atandard cubic feet per barrel measured at 15.6C
1' ~
- 14 - 1 3 3 4 U ~ 0 and 101.3kPa), preferably from about l,oO0 to lo,oO0 SCFB, and LHSV (liquid hourly space velocity) of about 0.08 to about 1.5 volumes of hydrocarbonaceous oil per hour per volume of reactor. Preferred operating conditions comprise an average temperature of about 730 to about 8S0F, total pressure of about 1,000 to about 3,000 psig, hydrogen partial pressure of about 1,000 to about 2,000 psia, hydrogen flow rate of about 8,000 SCFB, and LHSV of about 0.10 to about 0.8 volumes of hydrocarbons per hour per volume of reactor.
It i8 alæo within the scope of this lnven-tion to employ a multi-stage hydroconversion p~-_e~
wherein the metals content of the feed is reduced in a first stage followed by one or more subsequent stages in which a catalyst having high hydrodesulfur-ization activity is used. Individual ~tages can be conducted in single or multiple zones. Hydrodesul-furization catalysts particularly suited for use in a multi-stage process are those catalysts disclosed in U.S. Patent Nos. 4,181,602; 4,321,729; 4,224,144;
4,297,242; and 4,306,965. U.S. Patent No.
4,549,957, teaches a catalyst particularly suited for a first stage where demetallation activity is preferred.
The hydrotreating supported catalysts of the present inventlon can be any catalyst suitable for hydrotreating purposes. That is, for the removal of undesirable species of the oil such as metals, sulfur, and nitrogen. Such catalyst~ contain an active component and an inorganic refractory support 133~ 10 material. The active component may be a metal or an oxide of a metal selected from Groups VIII or VIB of the PeriodiC Table of the Elements, or a combination thereof. The active component is deposited on, or admixed with, the inorganic refractory support, pref-erably an oxide, such as silica, alumina, or silica-alumina. The supported catalyst is subject to much variation and conseguently may be a sulfided cobalt or nickel-molybdenum-alumina catalyst, etc. Other possible carrier materials include zirconia, titania, bauxite, and bentonite. Preferred sUpported cata-lysts are nickel-molybdenum on alumina and cobalt-molybdenum on alumina. The preparation of such cata-lysts is well known in the art and will not be dis-c~oed in detail herein.
Returning now to the figure, the hydrocon-version zone effluent is r-moved from hydroconversion zone 3 by line 24 and pAsse~ to a hot-separator zone 4. The overhead of the hot separator is passed by line 26 to gas separator 5. A light liguid hydro-carbon stream is removed from the gas separator by line 28. A ga~, which comprises hydrogen, is removed by line 30 and a portion of it, preferably after re-moval of undesired constituents, may be recycled via lines 32 and 20. The normally liquid pha~e, which comprises unsupported catalytic solids in a hydrocon-verted hydrocarbonaceous oil product, is pAs~ by line 34 to distillation zone 6 for fractionation by conventional means such as distillation into various fractions such as light, medium boiling and heavy bottoms fractions. The light fraction is removed by line 36. If de~ired, solids may be removed from stream 34 prior to introduction into the distillation zone. An intermediate liguid hydrocarbonaceous 1~34~40 stream is removed from distillation zone 6 by line 38; at least a portion of this stream may be recycled via line 40. A heavy liquid hydrocarbonaceous stream, which may comprise solids (if the solids were not previously removed) is remcved from the distilla-tion via line 42. If desired, a portion of this strea~ from line 42 may be recycled to the hydrocon-version zone via line 44 or to mixing zone 1, or to lines 16 or 18 by lines not ~hown. Further, if de-sired, at least a portion of stream 34 may be recycled to the hydroconversion zone via line 46 and/or to mixing zone 1 either with or without inter-vening removal of solids. Furthermore, if desired, at least a portion of the solids removed from any of the hydroconver~ion effluent streams may be recycled to hydroconvers~on zone 3 or to mixing zone 1.
The following examples are presented to illustrate the invention.
CatalYst Precursor Concentrate Preparation A
(Run 410r) To a one liter Autoclave Engineers magneti-cally stirred autoclave was charged 300 g of Cold ~ak- Crude together with 46.16g of a 2.5 wt. % solu-tion of CrO3 in water. The autoclave was flushed with nitrogen and heated to 121C with stirring and with a flow of 3 liter/min. of nitrogen. After reaching 121C the nitrogen stripping was continued for 30 minutes to remove all of the water. The auto-clave was cooled and discharged to yield a catalyst precursor concentrate containing 2000 wppm Cr.
*Trade-mark 1334~1~
Catalyst Concentrate Preparation B (Run 412L~
A catalyst precursor concentrate was pre-pared according to the procedure of Preparation A, and, after cooling, the concentrate was given a treatment as follows.
The autoclave was flushed with H2, then pressurod to 125 psig with H2S, and then pressured to 1250 psig with H2 at room temperaturo. The autoclave wa~ then hoated to 380C with stirring and maintained at 380 to 385C for 30 inutes, then cooled, depre~-sured and discharged to yield an activated catalyst concentrate containing 2000 wppm Cr.
Catalyst Concentrate Preparation C (Run 318~) To a on- lit-r Autoclave Engineers auto-clave was charged 392g of Heavy Arabian atmospheric residuum and 8.00 g. of a 20 wt. % solution of phos-phomolybdic acid in phenol. The autoclave was flush-ed with H2, thon pres~ured to 125 psig with H2S and to 1250 p8ig with hydrogen. The autoclave was then heated to 380C with stirring and hold at 380C to 385C for 30 minut-~, after which it was cooled and ~sch-rged to yiold an activated catalyst concentrate containing 2000 wppm Mo.
- 1 (Run 1079~
To a 300cc Autoclave Engineers magnetically stirred autoclavo was charged 93.0 g. of Heavy Arabian vacuum ro~iduu~, 12.0 g. of Heavy Arabian atmospheric ro~iduum and 15.0 g. of catalyst concen-trate ~B~. The chromium concentration in this 1~3~8 '` ~
mixture was 250 wppm. The autoclave was flushed with H2, pressured to 100 p~ig with H2S then to 1550 psig with hydrogen at room temperature.
The autoclave was then heated with stirring to 830F, whereupon the pressure was ad~usted to 2200 psig and these conditions maintained for 3 hrs while flowing hydrogen to the autoclave so as to maintain an exit gas flow of 0.26 l./~in. as measured at room temperature with a wet test meter. The autoclave was cooled and depressured. The ga~e~ were collected and analyzed by mass spectrometry to deteroine gas forma-tion. The autoclave contents were recovered in toluene solution and filtered to isolate th- solids, which solids were washed with toluene and dried for 1 hr in a vacuum oven at 100C.
The toluene solution of liguid product was di~tilled by 15/5 distillation to remove the solvent and light liquid followed by a Hivac-C distillation to i~olate th- unconverted 975+F material. The 975+F material was analyzed for Conradson carbon to determine the Conradson carbon conversion.
By these means the toluen- insoluble coke yi-ld based on the 975+F content of the charge was determined to b- 2.78 wt. %, the 975+F conversion 87.4%, the Cl-C3 gas yield on total feed 6.77%, and the Conradson carbon conversion to oil + gas 58.9%.
Exampl- 2 ~Run 1066) An experiment was conducted according to the p~ocad~re of Exampl- 1, except that the catalyst precursor concentrate of Preparation ~A~ was used.
- 19 - 1~8S~
The toluene insoluble coke yield based on the 975+F content o~ the charge was 3 61%, the 975+F conversion 83 9%, the Cl-C3 gas yield on total feed 7 63%, and the Conradson carbon conversion to oil I gas 51 9%
Example 3 (Run 927~
An experinent was carried out according to the procedure o~ Exa~ple 1, except that the activated catalyst concentrate of Preparation ~C~ was u~ed The toluene insoluble coke yield based on th- 975+F content of th- charg- was 2 3S wt %, the 975l or conver~ion 85 2~, the Cl-C3 ga- ~ake on total feed 7 17%, and the Conrad~on carbon conversion to oil + gas 56%
The re~ult~ o~ these experinent~ are shown in Table I
T~RT~ T
Exanple 1 ~ le 2 ~Y~mple 3 Toluen- Insolu-bl- Cok-, Wt %
on 975+F
Mat-rlal in Feed 2 78 3 61 2 35 Conver~ion o~
975+F Material in Feed to 975-F Product 87 4 83 9 85 2 Cl-C3 Gas, Wt %
on Total Feed 6 77 7 63 7 17 Con Carbon Con-ver~ion to Oil +
Ga~, % 58 9 51 9 56 0 - 20 - 1 33 4 ~ ~ O
Catalyst PrecursOr Concentrate Preparation D
~Run 424L~
A catalyst precursor concentrate was prepared according to the procedure o~ preparation ~A~ except that Heavy Arabian atmospheric residuum was used as the hydrocarbon medium rather than Cold Lake crude Catalyst Concentrate Pre~aration ~ (Run 426nl A catalyst precursor ~ ntrate was prepared according to the procedure of preparation "D~, and, after cooling, the concentrate was given a treatment as follows The autoclave was flushed with R2, th-n pres-sured to 150 psig with H2S, and then pr-ssured to 1400 psig with H2 at roou temperature The autoclave was then heated to 380C with stirring and ~aintained at 380C to 385C for 30 minutes, then cooled, depressured and discharg-d to yield an activated catalyst ro~c~ntrate conta~n~ng 2000 wpp~ Cr 4 (R~ 117 ) To a 300cc Autoclave Engineers magnetically stirred autoclave was charged 105 0 g of topped Cold Lake crude and 15 0 g of catalyst precursor concen-trate ~D~ The chromium concentration in this mixture wa~ 250 wppm The autoclav- wa~ flushed with H2, pressured to 50 psig with H2S th-n to 1400 psig with hydrogen at room temperature 1334~0 The autoclave was then heated with stirring to 380C and held at 380C to 385C for 20 min at which ti~e the autoclave was further heated to 443C, wheLeu~, the pressure was ad~u~ted to 2100 psig and these conditions maintained for 3 hrs while flowing hydrogen to the autoclave ~o as to maintain an exit ga~ flow of 0 36 liter/~in a~ measured at room temperature with a wet test meter The autoclave was cooled and depressured Th- gases were collected and analyzed by nass ~pectrometry to determine gas for~ation Th- autoclave content~ were r-covered in toluene ~olution and filtered to i~olat- solids, which solids were washed with toluene and dried for 1 hr in a vacuu~ oven at 100C
Th- toluene solution of liguid product was distilled by lS/5 di~tillation to remove th- solvent and light liquid followed by a Hivac-C distillation to isolate the unconverted 975+F material By these ~eans the toluene insoluble coke yield based on the 975+F content of the charge was deter~ined to b- 5 28 wt %
E~ l~ 5 ~tn 1118) An xperi~ent was conducted according to th- p~ooelure of Exa~ple 4 except that the catalyst c. _~trat- of Preparation ~E~ was used Th- toluene insoluble coke yield based on the 975+F content of th- charge was 1 95$
1~3~
Catalyst Precursor Concentrate Preparations F - r To a 1 liter magnetically stirred autoclave was charged 392g of a hydrocarbonaceous medium com-pri~ed of various percentage compositions of 1050-F
fraction and 1050+F ~raction a~ set forth in Table II below. These compo~ition~ were prepared by blend-ing together the requisite proportions of ~eavy Arabian vacuum gas oil and Heavy Arabian vacuum residuum. The autoclave was flushed with nitrogen and heated with stirring to 335F. At thi~ tempera-ture, 8.0 g. o~ 20 wt. % MCB phosphouolybdic acid in phenol was in~ected and ~tirring continued for 40 min., aft-r which the autocla~- wa~ cooled and ~chArged to giv- a cataly~t precur~or conc-ntrate containing 2000 wppm ~o.
Catalyst Precursor Concentrate Pr~arat~on M
n 3 7 9 T I) A catalyst precursor concentrate containing 1400 wppm Mo was prepared according to the procedure of preparation~ F - L except that 394.4g o~ a heavy oil blend containing 85.4 wt. % material boiling above 1050F and 5.6g of 20 wt. % MCB phosphomolybdic acid in phenol was employed.
~taly~t Precursor Concentrate Preparation N
(P~ln 376r~
A catalyst precursor concentrate containing 4000 wppu Mo wa~ prepared according to the procedure for preparations F - ~ except that 384g of a heavy oil blend cont~ ng 85.4 wt. % material boiling - 23 - 1 ~ 3 ~
above 1050F and 16.0 g. of 20 wt. % MCB phospho-molybdic acid in phenol was employed.
ComDarative FY~mDle I and ~YAmDles 6 to 11 The catalyst concentrate preparations F - L
were tested for activity in suppressing coke forma-tion under hydroconversion conditions as follows:
To a 300cc magnetically stirred autoclave was charged 105.0 g. of Heavy Arabian Vacuum residuum containing 85.4 wt. % ~aterial boilinq above 1050F
and 15.0 g. of the respective catalyst precursor concentrate to give a Mo concentration of 2S0 wppm in the reaction medium. Th- autoclave was pressure tested with H2, vented and charged ~ith 100 psia ~2S
and then pressured to 1550 p~ig with H2. The auto-clave was heated with stirring to 830F and main-tained at this temperature for 3 hr~. During the 3 hr reaction time the pressure was maintained at 2200 psig and H2 flowed through the autoclave to maintain an exit ga- rat- of 0.26 l/min. as measured at room temperature by a wet test meter.
The autoclav- was cooled and th- contents wash d out with 360 g. of toluene. Th- toluene solution was filtered to recover the toluene insolu-ble coke which was then dried in a vacuum oven at 160C for 1 hr.
The toluene insoluble coke yields for the several tests, expressed as wt. % cok~ on 975+F
material in the charged feedstock (including that in the catalyst precursor concentrate), are tabulated in Table II b~low.
- 24 - 1~3~
FYAmple 12 Catalyst precursor concentrate preparation M was te~ted according to the procedure o~ Compara-tive Example I and Examples 6 to 11, except that 21 43g of the cataly~t precur~or conc-ntrate and 98 57g of Heavy Arabian vacuu~ residuum were charged to provide a ~olybdenuJ concentration of 250 wppm in th- reaction mediu~ Th- toluen- insoluble coke yield was 3 31 wt % on 97S~F ~aterial in the feed and is set ~orth in Tabl- II below ~m~le 13 Catalyst precur~or co _antrat- preparation N was te~ted according to the procedur- o~ co~para-tive Example I and Examples 6 to 11, except that 7 5g of the cataly~t precursor concentrate and 112 5g of Heavy Arabian vacuu~ residuum were charged to provide a molybdenum concentration of 250 wpp~ in the reac-tion mediu~ Th- toluene insoluble coke yield was 3 39 wt % on 975+F ~aterial in the feed, which is set forth in Table II below - 25 - 1~ 34~O
, ~, .o c ~a ~ + ~ ~ o ~ 0 ~r ~ ~ ,~ ~ o ~ c x 8 ~ ~
~, ~
o ~ C
Z o o o ~ ~ o o ,~ ~ ~ ~ ~ ~r ~ ~ I
~ oc~ o~
V
~1 ~ o ~ o u~ o ~ ~ o C ~ 6 ~'~C~
C _1 L
3 ~1 c V L ~.~ O O O O O O O O O
O O o O O o O O O
U o o o o o o o ~r o tJ ~ N ~ ~ ~ ~ ~ ~O
O ~ ~
3~ _ _ __ _o o ~ ~ ~ ~ t~
a ~ t~
e ~, _ ________ ~, ~
~_ ~ ~ ~Z~
E~ J ~O t~ CO 0~ 0 ~
- 26 - 1~34~
ample 14 (Run 14891 To a 300cc magnetically stirred Autoclave Engineers autoclave wa~ charged 114.45 g. of Cold Lake residuum containing 94.84% 975+F material and 23.76% of Conradson carbon, together with 5.5s g. of a catalyst concentrate containing 0.4320 wt.% molyb-denum prepared according to the procedure of U.S.
Patent 4,740,489. The catalyst concentrate was prepared in Cold Lake crude containing 53.84% 975+F
material and 11.08% Conradson carbon. The combined mixture thus contained 200 wppm of molybdenu~. The autoclave was flushed with H2 then pressured to 50 psig wit~ H2S and then to 1400 p-ig with R2. The autoclave was then heated to 380C with ~tirring ov-r a period of 45 minutes and held at 380-38SC for 20 minutes after which time a flow of H2 wa~ started such as to g$ve effluent gas of 0.36 liter/min. as measured at atmospheric pressure by a wet test meter, and also at which tine the autoclave wa~ heated to r-action temperature over a period of 21 min. The reaction temperature of 443C (830F) was maintained with continued ~tirring for 3 hr. The autoclave was quickly cooled (70C/min. for the fir~t minute) to 150C whe~e~o.. the ga~ was vented, measured and analyz-d by mas~ spectL~-ccopy.
The autoclave content~ were then washed from the autoclave with 360 g. of toluene and fil-t-red to recover toluen- insoluble ~olids. After drying in a vacuum oven at 160C for 1 hr. the solids weighed 3.55 g. or 2.96 wt.% on feed. The liquid filtrate was distilled to r-mov- solv-nt and liquids boiling below 975F. The 975+F bottom~ weighed 11.9 g. and contained 61.34% Conrad~on carbon. This - 27 - 1334~
corresponds to 86-1% conversion of 975+F material to s7s-oF products and 60.9% conversion of Conradson carbon to 975-F oil plus gas. The Cl-C3 gas yield was 10.17%. Conversions and yields are given in Table III.
mple 15 (Run 1490) The procedur- of Example 14 was followed except that 1.40 g. of a supported catalyst was also employed. The support d catalyst was comprised of 3 wt.% NiO, 18 wt.% MoO3 and 3.0 wt. % P on a gamma alumina support having a surface area of 100 m2/g and a pore volume of O.S cc/g. The support d catalyst was sulfided and ~L-V~ to a particle SiZQ less than 20 ~ with most of the particles being less than 10 p.
In this experiment only 1.53 g. (1.28 wt.% on feed) of toluen- insoluble solid was formed (excluding the supported catalyst charged) and the 97S+F bottoms weighed 8.9 g. and contained 63.48 wt.% Conradson carbon. This corresponds to 90.3% conversion of 975+F material to 975-0F products and 74.2% conver-sion of Conradson carbon to 975-F oil plus qas. The Cl-C3 gas yield wa~ 8.34%. Conversions and yields are given in Table III.
Comparative Exam~le II (~ln 1494) The pLocedure of Example 15 was followed except that in place of the catalyst concentrate 5.55 g. of Cold ~ake crud- containing no molybdenum was charged. In this experiment 4.62 g. (3.85 wt.%
on feed) of toluene in~oluble solids were formed (ex-cluding the supported catalyst charged) and the 975+F bottoms product weighed 11.4 g. and contained - 28 - 1 334~
63.05 wt.% Conradson carbon. This corresponds to 85.6% conversion of 975+P material to 975-F pro-ducts and 57.5% conversion of Conradson carbon to 975-F oil plus gas. The Cl-C3 gas yield was 10.25%.
Conversions and yieldQ are given in Table III below.
T~hl~
Pretreat: 380-385C, 20 ~in.
Run: 830F, 3 hr., 2100t Co~parativ-Exampl- E~pl- TT 15 14 Feed, Cold Lake 114.45 114.45 114.45 Vac. Resid FS 6180, g Supported Catalyst, Sul~ided Powdered, g. 1.43 1.40 --Cold Lake Crude, g. 5.55 -- --Unsupported Catalyst fided Preformed PHC Prep 133 (4320 ppm Mo) in Cold Lake Crude, g. -- 5.5S 5.55 Mo, wpp~ -- 200 200 Toluene insolubl-solid~ formation (excluding solid catalyst charged), wt. % on feed 3.85 1.28 2.96 97S+F Conv. 85.6 90.3 86.1 Con. C Conv. to 975-F Oil + Gas, % 57.5 74.2 60.9 Cl-C3 Ga~, Wt.% 10.25 8.34 10.17 .
1 3 3 ~
Catalyst Concentrate PreDaration 0 (R-2226-CP~
To a 300 cc ~agnetically stirred Autoclave Engineer's autoclave ~as charged 90.0 g. of a whole Cold Lake crude oil that comprised 50 wt. % of material that boiled above 975F. ThQ autoclave was then heated to 176F and, while stirring at 176F, was in~ected with 10.0 gra~s of an aqueous solution of phosphomolybdic acid that had been prepared by dis~olving 1.60 g. of Fisher' 8 rQagent-grade phospho-molybdic acid (50 wt. % ~o) in 18.~0 g. deionized water. Stirring wa~ continued at 176F for 10 min-utes, whereupon the autoclave temperaturQ wa~ in-creased to 300F for a ~h~uent 10 minut~ p~riod with nitrogen flow-through to remove water. at this point the autoclave was sealed, heated to 698-700F, vented, and then charged with 30 p~ia of R2S. After an ensuing 30 min. pQriod of ~tirring at 725F, the autoclave was again vented, nitrogen flu~hed and cooled to room temperature. There was recovered 78.0 grams of catalyst concentrate which contained 0.51 wt. % Mo.
talvst Concentrate Pre~Arat~on P tR-2208-CP~
Thi~ cataly~t concsntrate preparation was c~rried out according to thQ p~G~ed~re used for Preparation 0, except that the charge of H2S added at 700F wa~ 60 psia. There was obtained 78 g. of concentrate that contained 0.51 wt. % Mo.
Cataly~t Concentrate PreDaration Q (R-2222-CP) This catalyst concentrat~ was prepared according to the p.oced~re us~d for Preparation O, *Trad e-mark _ 30 - 133~
except that the charge of H2S added at 700F was l5o psia There was obtained 80 g of concentrate that contained 0 50 wt % Mo CatalYst Concentrate Preparation R (R-2213-CP~
This preparation was carried out accordlng to the procedure used for Preparation 0, xcept that H2S was not added There was obtained 80 g of catalyst concentrate that contained O S0 wt % Mo ~ple 16 (R-2227-FT~
Catalyst concentrate Preparation 0 was te~ted for activity in suppressing cok rormation under hydroconversion conditions a~ follows To a 300 cc magnotically stirr d autoclave was charged 109 5 g of vacuum Cold Lak- resid containing 94 8 wt % material boiling above 975F, 5 62 g of whole Cold Lak- crude containing 50 wt %
material boiling above 975F and 4 88 g of Catalyst Con~ntrat- o to giv- a Mo ronr-ntration of 208 wppm in the reaction medium The autoclavo wa~ pressure tested with hydrogen, vented and th-n pL~s~red to 1350 p~ig at room temperatur- with hydrogen Th-autoclave was then heated with stirring to 725F for a 20 ninute stirred contact and then heated to 830F
and maintained at this temperature with stirring for 3 hrs During the three hour period the pressure was maintained at 2100 psig and H2 flowed through the autoclave to maintain an exit ga~ rate o~ 0 36 l /~in as measured at room temperature by a wet test meter 133~
Upon completion of the 3 hr contact the autoclave was cooled, gaSeoUs products were vented and the remaininq content~ were washed out with 360 g. of toluene. The toluene wash was filtered to recover the toluene in~oluble coke, which was dried at 100C for 2 hr. in a vacuum oven. There was recovered 1.81 g. of toluene insoluble ~olids, which anounted to a yield of 1.65 wt. % on the 975+F
fraction of the f-ed.
~Y~ l7 (R-2209-PT) Catalyst Con:entrate Preparation P was tested for activity in ~uppre~ing the for~ation of toluene inQoluble cok- according to th~ procedure described in Example 18. Th~ reactor charge, which contained 208 wppn Mo, wa~ made up of 109.5 g. of vacuun Cold Lake re~id, S.62 g. of whol- Cold Lake Crude and 4.88 g. of Catalyst Concentrate Prepara-tion P.
Ther- was recovered 1.68 g. of toluene insoluble coke, which amounted to a yield of 1.53 wt. % based on the 975+F fraction of th~ reactor fe~d.
Example t8 ~R-2223-FT) Cataly~t Concentrate Preparation Q wa~
te~t~d for activity according to the procedure described in Example 18. The reactor charge, which contained 208 wpp~ Mo, wa~ made up of 109.5 g. of vacuu~ Cold Lake re~id, 5.S g. o~ whole Cold Lake crude and 5.0 g. of Catalyst Conc-ntrate Prepara-tion Q.
133~g~
There was recovered 1 90 g of toluene insoluble coke, which amounted to a yield of 1 73 wt % on the 97S+F ~raction Or the ~eed FY~m~le 19 (R-2214-FT) Catalyst Concentrat- Preparation R was tested for activity according to th- procedure de~cribed in Example 18 Th- reactor charge, which contained 208 wppm Mo, wa- ~ade up of 109 S g vacuum Cold Lak- r--id, 5 S g of whol~ Cold ~ak- Crud- and S O g o~ Cataly~t Con~ntrate Pr-paration R
There was r-covered 2 09 g of toluene insolubl- coke, which a~ounted to ~ yield of 1 91 wt % on the 975+F fraction of th- fe~d Th- result~ of th- exp ri~ent~ d-~crib~d in Examples 18-21 ar- summarized in Tabl- IV
Table TV
~r~-. OF H~S pRFCCU~ ON CAT~YST FOR~TION
H2S rU~P~Fn IN
CAT P~P~ATTON Toluene Insol Exampl- p~ia at appx. H2S/Mo Coke Yield, Wt %
No 700F Mole Pat~oon 975+F Feed 19 0 0.00 1.91
The hydrocarbonaceous oil is contacted with hydrogen in the ebullating bed of supported hydro-treating catalyst also at the above mentioned hydro-conversion temperature~ and pressures and at a hydrogen flow rate of about 1000 to about 20,000 SCFB
(-atandard cubic feet per barrel measured at 15.6C
1' ~
- 14 - 1 3 3 4 U ~ 0 and 101.3kPa), preferably from about l,oO0 to lo,oO0 SCFB, and LHSV (liquid hourly space velocity) of about 0.08 to about 1.5 volumes of hydrocarbonaceous oil per hour per volume of reactor. Preferred operating conditions comprise an average temperature of about 730 to about 8S0F, total pressure of about 1,000 to about 3,000 psig, hydrogen partial pressure of about 1,000 to about 2,000 psia, hydrogen flow rate of about 8,000 SCFB, and LHSV of about 0.10 to about 0.8 volumes of hydrocarbons per hour per volume of reactor.
It i8 alæo within the scope of this lnven-tion to employ a multi-stage hydroconversion p~-_e~
wherein the metals content of the feed is reduced in a first stage followed by one or more subsequent stages in which a catalyst having high hydrodesulfur-ization activity is used. Individual ~tages can be conducted in single or multiple zones. Hydrodesul-furization catalysts particularly suited for use in a multi-stage process are those catalysts disclosed in U.S. Patent Nos. 4,181,602; 4,321,729; 4,224,144;
4,297,242; and 4,306,965. U.S. Patent No.
4,549,957, teaches a catalyst particularly suited for a first stage where demetallation activity is preferred.
The hydrotreating supported catalysts of the present inventlon can be any catalyst suitable for hydrotreating purposes. That is, for the removal of undesirable species of the oil such as metals, sulfur, and nitrogen. Such catalyst~ contain an active component and an inorganic refractory support 133~ 10 material. The active component may be a metal or an oxide of a metal selected from Groups VIII or VIB of the PeriodiC Table of the Elements, or a combination thereof. The active component is deposited on, or admixed with, the inorganic refractory support, pref-erably an oxide, such as silica, alumina, or silica-alumina. The supported catalyst is subject to much variation and conseguently may be a sulfided cobalt or nickel-molybdenum-alumina catalyst, etc. Other possible carrier materials include zirconia, titania, bauxite, and bentonite. Preferred sUpported cata-lysts are nickel-molybdenum on alumina and cobalt-molybdenum on alumina. The preparation of such cata-lysts is well known in the art and will not be dis-c~oed in detail herein.
Returning now to the figure, the hydrocon-version zone effluent is r-moved from hydroconversion zone 3 by line 24 and pAsse~ to a hot-separator zone 4. The overhead of the hot separator is passed by line 26 to gas separator 5. A light liguid hydro-carbon stream is removed from the gas separator by line 28. A ga~, which comprises hydrogen, is removed by line 30 and a portion of it, preferably after re-moval of undesired constituents, may be recycled via lines 32 and 20. The normally liquid pha~e, which comprises unsupported catalytic solids in a hydrocon-verted hydrocarbonaceous oil product, is pAs~ by line 34 to distillation zone 6 for fractionation by conventional means such as distillation into various fractions such as light, medium boiling and heavy bottoms fractions. The light fraction is removed by line 36. If de~ired, solids may be removed from stream 34 prior to introduction into the distillation zone. An intermediate liguid hydrocarbonaceous 1~34~40 stream is removed from distillation zone 6 by line 38; at least a portion of this stream may be recycled via line 40. A heavy liquid hydrocarbonaceous stream, which may comprise solids (if the solids were not previously removed) is remcved from the distilla-tion via line 42. If desired, a portion of this strea~ from line 42 may be recycled to the hydrocon-version zone via line 44 or to mixing zone 1, or to lines 16 or 18 by lines not ~hown. Further, if de-sired, at least a portion of stream 34 may be recycled to the hydroconversion zone via line 46 and/or to mixing zone 1 either with or without inter-vening removal of solids. Furthermore, if desired, at least a portion of the solids removed from any of the hydroconver~ion effluent streams may be recycled to hydroconvers~on zone 3 or to mixing zone 1.
The following examples are presented to illustrate the invention.
CatalYst Precursor Concentrate Preparation A
(Run 410r) To a one liter Autoclave Engineers magneti-cally stirred autoclave was charged 300 g of Cold ~ak- Crude together with 46.16g of a 2.5 wt. % solu-tion of CrO3 in water. The autoclave was flushed with nitrogen and heated to 121C with stirring and with a flow of 3 liter/min. of nitrogen. After reaching 121C the nitrogen stripping was continued for 30 minutes to remove all of the water. The auto-clave was cooled and discharged to yield a catalyst precursor concentrate containing 2000 wppm Cr.
*Trade-mark 1334~1~
Catalyst Concentrate Preparation B (Run 412L~
A catalyst precursor concentrate was pre-pared according to the procedure of Preparation A, and, after cooling, the concentrate was given a treatment as follows.
The autoclave was flushed with H2, then pressurod to 125 psig with H2S, and then pressured to 1250 psig with H2 at room temperaturo. The autoclave wa~ then hoated to 380C with stirring and maintained at 380 to 385C for 30 inutes, then cooled, depre~-sured and discharged to yield an activated catalyst concentrate containing 2000 wppm Cr.
Catalyst Concentrate Preparation C (Run 318~) To a on- lit-r Autoclave Engineers auto-clave was charged 392g of Heavy Arabian atmospheric residuum and 8.00 g. of a 20 wt. % solution of phos-phomolybdic acid in phenol. The autoclave was flush-ed with H2, thon pres~ured to 125 psig with H2S and to 1250 p8ig with hydrogen. The autoclave was then heated to 380C with stirring and hold at 380C to 385C for 30 minut-~, after which it was cooled and ~sch-rged to yiold an activated catalyst concentrate containing 2000 wppm Mo.
- 1 (Run 1079~
To a 300cc Autoclave Engineers magnetically stirred autoclavo was charged 93.0 g. of Heavy Arabian vacuum ro~iduu~, 12.0 g. of Heavy Arabian atmospheric ro~iduum and 15.0 g. of catalyst concen-trate ~B~. The chromium concentration in this 1~3~8 '` ~
mixture was 250 wppm. The autoclave was flushed with H2, pressured to 100 p~ig with H2S then to 1550 psig with hydrogen at room temperature.
The autoclave was then heated with stirring to 830F, whereupon the pressure was ad~usted to 2200 psig and these conditions maintained for 3 hrs while flowing hydrogen to the autoclave so as to maintain an exit gas flow of 0.26 l./~in. as measured at room temperature with a wet test meter. The autoclave was cooled and depressured. The ga~e~ were collected and analyzed by mass spectrometry to deteroine gas forma-tion. The autoclave contents were recovered in toluene solution and filtered to isolate th- solids, which solids were washed with toluene and dried for 1 hr in a vacuum oven at 100C.
The toluene solution of liguid product was di~tilled by 15/5 distillation to remove the solvent and light liquid followed by a Hivac-C distillation to i~olate th- unconverted 975+F material. The 975+F material was analyzed for Conradson carbon to determine the Conradson carbon conversion.
By these means the toluen- insoluble coke yi-ld based on the 975+F content of the charge was determined to b- 2.78 wt. %, the 975+F conversion 87.4%, the Cl-C3 gas yield on total feed 6.77%, and the Conradson carbon conversion to oil + gas 58.9%.
Exampl- 2 ~Run 1066) An experiment was conducted according to the p~ocad~re of Exampl- 1, except that the catalyst precursor concentrate of Preparation ~A~ was used.
- 19 - 1~8S~
The toluene insoluble coke yield based on the 975+F content o~ the charge was 3 61%, the 975+F conversion 83 9%, the Cl-C3 gas yield on total feed 7 63%, and the Conradson carbon conversion to oil I gas 51 9%
Example 3 (Run 927~
An experinent was carried out according to the procedure o~ Exa~ple 1, except that the activated catalyst concentrate of Preparation ~C~ was u~ed The toluene insoluble coke yield based on th- 975+F content of th- charg- was 2 3S wt %, the 975l or conver~ion 85 2~, the Cl-C3 ga- ~ake on total feed 7 17%, and the Conrad~on carbon conversion to oil + gas 56%
The re~ult~ o~ these experinent~ are shown in Table I
T~RT~ T
Exanple 1 ~ le 2 ~Y~mple 3 Toluen- Insolu-bl- Cok-, Wt %
on 975+F
Mat-rlal in Feed 2 78 3 61 2 35 Conver~ion o~
975+F Material in Feed to 975-F Product 87 4 83 9 85 2 Cl-C3 Gas, Wt %
on Total Feed 6 77 7 63 7 17 Con Carbon Con-ver~ion to Oil +
Ga~, % 58 9 51 9 56 0 - 20 - 1 33 4 ~ ~ O
Catalyst PrecursOr Concentrate Preparation D
~Run 424L~
A catalyst precursor concentrate was prepared according to the procedure o~ preparation ~A~ except that Heavy Arabian atmospheric residuum was used as the hydrocarbon medium rather than Cold Lake crude Catalyst Concentrate Pre~aration ~ (Run 426nl A catalyst precursor ~ ntrate was prepared according to the procedure of preparation "D~, and, after cooling, the concentrate was given a treatment as follows The autoclave was flushed with R2, th-n pres-sured to 150 psig with H2S, and then pr-ssured to 1400 psig with H2 at roou temperature The autoclave was then heated to 380C with stirring and ~aintained at 380C to 385C for 30 minutes, then cooled, depressured and discharg-d to yield an activated catalyst ro~c~ntrate conta~n~ng 2000 wpp~ Cr 4 (R~ 117 ) To a 300cc Autoclave Engineers magnetically stirred autoclave was charged 105 0 g of topped Cold Lake crude and 15 0 g of catalyst precursor concen-trate ~D~ The chromium concentration in this mixture wa~ 250 wppm The autoclav- wa~ flushed with H2, pressured to 50 psig with H2S th-n to 1400 psig with hydrogen at room temperature 1334~0 The autoclave was then heated with stirring to 380C and held at 380C to 385C for 20 min at which ti~e the autoclave was further heated to 443C, wheLeu~, the pressure was ad~u~ted to 2100 psig and these conditions maintained for 3 hrs while flowing hydrogen to the autoclave ~o as to maintain an exit ga~ flow of 0 36 liter/~in a~ measured at room temperature with a wet test meter The autoclave was cooled and depressured Th- gases were collected and analyzed by nass ~pectrometry to determine gas for~ation Th- autoclave content~ were r-covered in toluene ~olution and filtered to i~olat- solids, which solids were washed with toluene and dried for 1 hr in a vacuu~ oven at 100C
Th- toluene solution of liguid product was distilled by lS/5 di~tillation to remove th- solvent and light liquid followed by a Hivac-C distillation to isolate the unconverted 975+F material By these ~eans the toluene insoluble coke yield based on the 975+F content of the charge was deter~ined to b- 5 28 wt %
E~ l~ 5 ~tn 1118) An xperi~ent was conducted according to th- p~ooelure of Exa~ple 4 except that the catalyst c. _~trat- of Preparation ~E~ was used Th- toluene insoluble coke yield based on the 975+F content of th- charge was 1 95$
1~3~
Catalyst Precursor Concentrate Preparations F - r To a 1 liter magnetically stirred autoclave was charged 392g of a hydrocarbonaceous medium com-pri~ed of various percentage compositions of 1050-F
fraction and 1050+F ~raction a~ set forth in Table II below. These compo~ition~ were prepared by blend-ing together the requisite proportions of ~eavy Arabian vacuum gas oil and Heavy Arabian vacuum residuum. The autoclave was flushed with nitrogen and heated with stirring to 335F. At thi~ tempera-ture, 8.0 g. o~ 20 wt. % MCB phosphouolybdic acid in phenol was in~ected and ~tirring continued for 40 min., aft-r which the autocla~- wa~ cooled and ~chArged to giv- a cataly~t precur~or conc-ntrate containing 2000 wppm ~o.
Catalyst Precursor Concentrate Pr~arat~on M
n 3 7 9 T I) A catalyst precursor concentrate containing 1400 wppm Mo was prepared according to the procedure of preparation~ F - L except that 394.4g o~ a heavy oil blend containing 85.4 wt. % material boiling above 1050F and 5.6g of 20 wt. % MCB phosphomolybdic acid in phenol was employed.
~taly~t Precursor Concentrate Preparation N
(P~ln 376r~
A catalyst precursor concentrate containing 4000 wppu Mo wa~ prepared according to the procedure for preparations F - ~ except that 384g of a heavy oil blend cont~ ng 85.4 wt. % material boiling - 23 - 1 ~ 3 ~
above 1050F and 16.0 g. of 20 wt. % MCB phospho-molybdic acid in phenol was employed.
ComDarative FY~mDle I and ~YAmDles 6 to 11 The catalyst concentrate preparations F - L
were tested for activity in suppressing coke forma-tion under hydroconversion conditions as follows:
To a 300cc magnetically stirred autoclave was charged 105.0 g. of Heavy Arabian Vacuum residuum containing 85.4 wt. % ~aterial boilinq above 1050F
and 15.0 g. of the respective catalyst precursor concentrate to give a Mo concentration of 2S0 wppm in the reaction medium. Th- autoclave was pressure tested with H2, vented and charged ~ith 100 psia ~2S
and then pressured to 1550 p~ig with H2. The auto-clave was heated with stirring to 830F and main-tained at this temperature for 3 hr~. During the 3 hr reaction time the pressure was maintained at 2200 psig and H2 flowed through the autoclave to maintain an exit ga- rat- of 0.26 l/min. as measured at room temperature by a wet test meter.
The autoclav- was cooled and th- contents wash d out with 360 g. of toluene. Th- toluene solution was filtered to recover the toluene insolu-ble coke which was then dried in a vacuum oven at 160C for 1 hr.
The toluene insoluble coke yields for the several tests, expressed as wt. % cok~ on 975+F
material in the charged feedstock (including that in the catalyst precursor concentrate), are tabulated in Table II b~low.
- 24 - 1~3~
FYAmple 12 Catalyst precursor concentrate preparation M was te~ted according to the procedure o~ Compara-tive Example I and Examples 6 to 11, except that 21 43g of the cataly~t precur~or conc-ntrate and 98 57g of Heavy Arabian vacuu~ residuum were charged to provide a ~olybdenuJ concentration of 250 wppm in th- reaction mediu~ Th- toluen- insoluble coke yield was 3 31 wt % on 97S~F ~aterial in the feed and is set ~orth in Tabl- II below ~m~le 13 Catalyst precur~or co _antrat- preparation N was te~ted according to the procedur- o~ co~para-tive Example I and Examples 6 to 11, except that 7 5g of the cataly~t precursor concentrate and 112 5g of Heavy Arabian vacuu~ residuum were charged to provide a molybdenum concentration of 250 wpp~ in the reac-tion mediu~ Th- toluene insoluble coke yield was 3 39 wt % on 975+F ~aterial in the feed, which is set forth in Table II below - 25 - 1~ 34~O
, ~, .o c ~a ~ + ~ ~ o ~ 0 ~r ~ ~ ,~ ~ o ~ c x 8 ~ ~
~, ~
o ~ C
Z o o o ~ ~ o o ,~ ~ ~ ~ ~ ~r ~ ~ I
~ oc~ o~
V
~1 ~ o ~ o u~ o ~ ~ o C ~ 6 ~'~C~
C _1 L
3 ~1 c V L ~.~ O O O O O O O O O
O O o O O o O O O
U o o o o o o o ~r o tJ ~ N ~ ~ ~ ~ ~ ~O
O ~ ~
3~ _ _ __ _o o ~ ~ ~ ~ t~
a ~ t~
e ~, _ ________ ~, ~
~_ ~ ~ ~Z~
E~ J ~O t~ CO 0~ 0 ~
- 26 - 1~34~
ample 14 (Run 14891 To a 300cc magnetically stirred Autoclave Engineers autoclave wa~ charged 114.45 g. of Cold Lake residuum containing 94.84% 975+F material and 23.76% of Conradson carbon, together with 5.5s g. of a catalyst concentrate containing 0.4320 wt.% molyb-denum prepared according to the procedure of U.S.
Patent 4,740,489. The catalyst concentrate was prepared in Cold Lake crude containing 53.84% 975+F
material and 11.08% Conradson carbon. The combined mixture thus contained 200 wppm of molybdenu~. The autoclave was flushed with H2 then pressured to 50 psig wit~ H2S and then to 1400 p-ig with R2. The autoclave was then heated to 380C with ~tirring ov-r a period of 45 minutes and held at 380-38SC for 20 minutes after which time a flow of H2 wa~ started such as to g$ve effluent gas of 0.36 liter/min. as measured at atmospheric pressure by a wet test meter, and also at which tine the autoclave wa~ heated to r-action temperature over a period of 21 min. The reaction temperature of 443C (830F) was maintained with continued ~tirring for 3 hr. The autoclave was quickly cooled (70C/min. for the fir~t minute) to 150C whe~e~o.. the ga~ was vented, measured and analyz-d by mas~ spectL~-ccopy.
The autoclave content~ were then washed from the autoclave with 360 g. of toluene and fil-t-red to recover toluen- insoluble ~olids. After drying in a vacuum oven at 160C for 1 hr. the solids weighed 3.55 g. or 2.96 wt.% on feed. The liquid filtrate was distilled to r-mov- solv-nt and liquids boiling below 975F. The 975+F bottom~ weighed 11.9 g. and contained 61.34% Conrad~on carbon. This - 27 - 1334~
corresponds to 86-1% conversion of 975+F material to s7s-oF products and 60.9% conversion of Conradson carbon to 975-F oil plus gas. The Cl-C3 gas yield was 10.17%. Conversions and yields are given in Table III.
mple 15 (Run 1490) The procedur- of Example 14 was followed except that 1.40 g. of a supported catalyst was also employed. The support d catalyst was comprised of 3 wt.% NiO, 18 wt.% MoO3 and 3.0 wt. % P on a gamma alumina support having a surface area of 100 m2/g and a pore volume of O.S cc/g. The support d catalyst was sulfided and ~L-V~ to a particle SiZQ less than 20 ~ with most of the particles being less than 10 p.
In this experiment only 1.53 g. (1.28 wt.% on feed) of toluen- insoluble solid was formed (excluding the supported catalyst charged) and the 97S+F bottoms weighed 8.9 g. and contained 63.48 wt.% Conradson carbon. This corresponds to 90.3% conversion of 975+F material to 975-0F products and 74.2% conver-sion of Conradson carbon to 975-F oil plus qas. The Cl-C3 gas yield wa~ 8.34%. Conversions and yields are given in Table III.
Comparative Exam~le II (~ln 1494) The pLocedure of Example 15 was followed except that in place of the catalyst concentrate 5.55 g. of Cold ~ake crud- containing no molybdenum was charged. In this experiment 4.62 g. (3.85 wt.%
on feed) of toluene in~oluble solids were formed (ex-cluding the supported catalyst charged) and the 975+F bottoms product weighed 11.4 g. and contained - 28 - 1 334~
63.05 wt.% Conradson carbon. This corresponds to 85.6% conversion of 975+P material to 975-F pro-ducts and 57.5% conversion of Conradson carbon to 975-F oil plus gas. The Cl-C3 gas yield was 10.25%.
Conversions and yieldQ are given in Table III below.
T~hl~
Pretreat: 380-385C, 20 ~in.
Run: 830F, 3 hr., 2100t Co~parativ-Exampl- E~pl- TT 15 14 Feed, Cold Lake 114.45 114.45 114.45 Vac. Resid FS 6180, g Supported Catalyst, Sul~ided Powdered, g. 1.43 1.40 --Cold Lake Crude, g. 5.55 -- --Unsupported Catalyst fided Preformed PHC Prep 133 (4320 ppm Mo) in Cold Lake Crude, g. -- 5.5S 5.55 Mo, wpp~ -- 200 200 Toluene insolubl-solid~ formation (excluding solid catalyst charged), wt. % on feed 3.85 1.28 2.96 97S+F Conv. 85.6 90.3 86.1 Con. C Conv. to 975-F Oil + Gas, % 57.5 74.2 60.9 Cl-C3 Ga~, Wt.% 10.25 8.34 10.17 .
1 3 3 ~
Catalyst Concentrate PreDaration 0 (R-2226-CP~
To a 300 cc ~agnetically stirred Autoclave Engineer's autoclave ~as charged 90.0 g. of a whole Cold Lake crude oil that comprised 50 wt. % of material that boiled above 975F. ThQ autoclave was then heated to 176F and, while stirring at 176F, was in~ected with 10.0 gra~s of an aqueous solution of phosphomolybdic acid that had been prepared by dis~olving 1.60 g. of Fisher' 8 rQagent-grade phospho-molybdic acid (50 wt. % ~o) in 18.~0 g. deionized water. Stirring wa~ continued at 176F for 10 min-utes, whereupon the autoclave temperaturQ wa~ in-creased to 300F for a ~h~uent 10 minut~ p~riod with nitrogen flow-through to remove water. at this point the autoclave was sealed, heated to 698-700F, vented, and then charged with 30 p~ia of R2S. After an ensuing 30 min. pQriod of ~tirring at 725F, the autoclave was again vented, nitrogen flu~hed and cooled to room temperature. There was recovered 78.0 grams of catalyst concentrate which contained 0.51 wt. % Mo.
talvst Concentrate Pre~Arat~on P tR-2208-CP~
Thi~ cataly~t concsntrate preparation was c~rried out according to thQ p~G~ed~re used for Preparation 0, except that the charge of H2S added at 700F wa~ 60 psia. There was obtained 78 g. of concentrate that contained 0.51 wt. % Mo.
Cataly~t Concentrate PreDaration Q (R-2222-CP) This catalyst concentrat~ was prepared according to the p.oced~re us~d for Preparation O, *Trad e-mark _ 30 - 133~
except that the charge of H2S added at 700F was l5o psia There was obtained 80 g of concentrate that contained 0 50 wt % Mo CatalYst Concentrate Preparation R (R-2213-CP~
This preparation was carried out accordlng to the procedure used for Preparation 0, xcept that H2S was not added There was obtained 80 g of catalyst concentrate that contained O S0 wt % Mo ~ple 16 (R-2227-FT~
Catalyst concentrate Preparation 0 was te~ted for activity in suppressing cok rormation under hydroconversion conditions a~ follows To a 300 cc magnotically stirr d autoclave was charged 109 5 g of vacuum Cold Lak- resid containing 94 8 wt % material boiling above 975F, 5 62 g of whole Cold Lak- crude containing 50 wt %
material boiling above 975F and 4 88 g of Catalyst Con~ntrat- o to giv- a Mo ronr-ntration of 208 wppm in the reaction medium The autoclavo wa~ pressure tested with hydrogen, vented and th-n pL~s~red to 1350 p~ig at room temperatur- with hydrogen Th-autoclave was then heated with stirring to 725F for a 20 ninute stirred contact and then heated to 830F
and maintained at this temperature with stirring for 3 hrs During the three hour period the pressure was maintained at 2100 psig and H2 flowed through the autoclave to maintain an exit ga~ rate o~ 0 36 l /~in as measured at room temperature by a wet test meter 133~
Upon completion of the 3 hr contact the autoclave was cooled, gaSeoUs products were vented and the remaininq content~ were washed out with 360 g. of toluene. The toluene wash was filtered to recover the toluene in~oluble coke, which was dried at 100C for 2 hr. in a vacuum oven. There was recovered 1.81 g. of toluene insoluble ~olids, which anounted to a yield of 1.65 wt. % on the 975+F
fraction of the f-ed.
~Y~ l7 (R-2209-PT) Catalyst Con:entrate Preparation P was tested for activity in ~uppre~ing the for~ation of toluene inQoluble cok- according to th~ procedure described in Example 18. Th~ reactor charge, which contained 208 wppn Mo, wa~ made up of 109.5 g. of vacuun Cold Lake re~id, S.62 g. of whol- Cold Lake Crude and 4.88 g. of Catalyst Concentrate Prepara-tion P.
Ther- was recovered 1.68 g. of toluene insoluble coke, which amounted to a yield of 1.53 wt. % based on the 975+F fraction of th~ reactor fe~d.
Example t8 ~R-2223-FT) Cataly~t Concentrate Preparation Q wa~
te~t~d for activity according to the procedure described in Example 18. The reactor charge, which contained 208 wpp~ Mo, wa~ made up of 109.5 g. of vacuu~ Cold Lake re~id, 5.S g. o~ whole Cold Lake crude and 5.0 g. of Catalyst Conc-ntrate Prepara-tion Q.
133~g~
There was recovered 1 90 g of toluene insoluble coke, which amounted to a yield of 1 73 wt % on the 97S+F ~raction Or the ~eed FY~m~le 19 (R-2214-FT) Catalyst Concentrat- Preparation R was tested for activity according to th- procedure de~cribed in Example 18 Th- reactor charge, which contained 208 wppm Mo, wa- ~ade up of 109 S g vacuum Cold Lak- r--id, 5 S g of whol~ Cold ~ak- Crud- and S O g o~ Cataly~t Con~ntrate Pr-paration R
There was r-covered 2 09 g of toluene insolubl- coke, which a~ounted to ~ yield of 1 91 wt % on the 975+F fraction of th- fe~d Th- result~ of th- exp ri~ent~ d-~crib~d in Examples 18-21 ar- summarized in Tabl- IV
Table TV
~r~-. OF H~S pRFCCU~ ON CAT~YST FOR~TION
H2S rU~P~Fn IN
CAT P~P~ATTON Toluene Insol Exampl- p~ia at appx. H2S/Mo Coke Yield, Wt %
No 700F Mole Pat~oon 975+F Feed 19 0 0.00 1.91
Claims (41)
1. A hydroconversion process for converting a heavy hydrocarbonaceous oil to lower boiling products, which process comprises the steps of:
(a) forming a mixture of a heavy hydrocarbonaceous oil and an oil dispersible metal compound in an amount ranging from about 0.1 to about 2 weight percent, calculated as elemental metal, based on the weight of said hydrocarbonaceous oil, said metal being selected from the group consisting of Groups II, III, IV, V, VIB, VIIB, and VIII and mixtures thereof, of the Periodic Table of the Elements;
(b) introducing at least a portion of said mixture into a hydroconversion zone containing a heavy hydrocarbonaceous chargestock and a supported catalyst comprised of: (i) a metal selected from Groups VIB and VIII of the Periodic Table of the Elements; and (ii) a refractory inorganic support material;
(c) subjecting the mixture in the hydroconversion zone to a temperature of about 700 to 900°F, in the presence of an effective amount of a sulfiding agent and a hydrogen-containing gas, at a hydrogen partial pressure from about 100 to 5000 psig, thereby producing lower boiling hydrocarbonaceous products.
(a) forming a mixture of a heavy hydrocarbonaceous oil and an oil dispersible metal compound in an amount ranging from about 0.1 to about 2 weight percent, calculated as elemental metal, based on the weight of said hydrocarbonaceous oil, said metal being selected from the group consisting of Groups II, III, IV, V, VIB, VIIB, and VIII and mixtures thereof, of the Periodic Table of the Elements;
(b) introducing at least a portion of said mixture into a hydroconversion zone containing a heavy hydrocarbonaceous chargestock and a supported catalyst comprised of: (i) a metal selected from Groups VIB and VIII of the Periodic Table of the Elements; and (ii) a refractory inorganic support material;
(c) subjecting the mixture in the hydroconversion zone to a temperature of about 700 to 900°F, in the presence of an effective amount of a sulfiding agent and a hydrogen-containing gas, at a hydrogen partial pressure from about 100 to 5000 psig, thereby producing lower boiling hydrocarbonaceous products.
2. The process of claim 1 wherein said heavy hydrocarbonaceous oil of step (a) comprises materials boiling above 1050°F.
3. The process of claim 2 wherein said heavy hydrocarbonaceous oil of step (a) is a blend of a lighter oil and at least about 10 wt.% heavier oil, said lighter oil boiling below about 1050°F
and said heavier oil boiling above about 1050°F.
and said heavier oil boiling above about 1050°F.
4. The process of claim 3 wherein the blend contains from about 22 to 85 wt.% heavier oil.
5. The process of claim 4 wherein the blend contains from about 30 to 85 wt.% heavier oil.
6. The process of claim 5 wherein the blend contains from about 45 to 75 wt.% heavier oil.
7. The process of claim 1 wherein said heavy hydrocarbonaceous oil of step (a) comprises a blend of a gas oil and a vacuum residuum.
8. The process of claim 1 wherein said heavy hydrocarbonaceous oil of step (a) is an atmospheric distillation residuum.
9. The process of claim 1 wherein said oil dispersible metal compound is mixed with said heavy oil in step (a) in an amount ranging from about 0.2 to about 1 wt.%, calculated as elemental metal, based on said heavy oil.
10. The process of claim 1 wherein said oil dispersible metal compound is selected from the group consisting of inorganic metal compouds, salts of organic acids, organometallic compounds, salts of organic amines, and mixtures thereof.
11. The process of claim 1 wherein said metal of said oil dispersible metal compound is selected from the group consisting of molybdenum, chromium, vanadium, and mixtures thereof.
12. The process of claim 1 wherein said oil dispersible metal compound is a phosphomolybdic acid.
13. The process of Claim 1 wherein the refractory inorganic support of step (b) is selected from the group consisting of alumina, silica, and alumina-silica.
14. The process of claim 1 wherein the sulfiding agent is selected from the group consisting of a hydrogen sulfide containing stream, elemental sulfur, carbon disulfide, compounds that decompose to yield sulfur moieties, and a hydrocarbon stream containing more than 0.1 wt. % sulfur.
15. The process of claim 14 wherein: the sulfiding agent is a hydrogen sulfide containing stream containing at least 1 mole % hydrogen sulfide.
16. The process of claim 1 wherein: (i) prior to introducing the mixture of step (a) into the hydroconversion zone it is first heated in the presence of sulfiding agent at a temperature of at least about 500°F for an effective amount of time to convert the oil-dispersible, or decomposable, metal compound to the corresponding metal-containing catalyst in said hydrocarbonaceous oil, and (ii) conducting the hydroconversion zone in the substan-tial absence of sulfiding agent other than that found in the chargestock.
17. The process of claim 16 wherein the sulfiding agent is selected from the group consisting of hydrogen sulfide containing streams, elemental sulfur, carbon disulfide, compounds that decompose to yield sulfide moieties, and a hydrocarbon stream containing more than 0.1 wt. % sulfur.
18. The process of claim 17 wherein the sulfiding agent is a hydrogen sulfide containing stream containing at least 1 mole % hydrogen sulfide.
19. The process of claim 18 wherein the H2S/metal ratio is from about 1 to 5.
20. The process of claim 16 wherein in step (a): (i) the heavy hydrocarbonaceous oil is a blend of a lighter oil boiling below about 1050°F and a heavier oil boiling above about 1050°F which blend contains about 22 to 85 wt. % of heavier oil, (ii) the concentration of oil dispersible metal compound is such that about 0.2 to 1 wt. % calculated as elemental metal is present, based on said oil blend.
21. The process of claim 20 wherein the oil dispersible, or decomposable, metal compound is selected from the group consisting of inorganic metal compounds, salts of organic acids, organometallic compounds, salts of organic amines.
22. The process of claim 21 wherein the metal is selected from the group consisting of molybdenum, chromium, vanadium, and mixtures thereof.
23. The process of claim 22 wherein the oil dispersible metal compound is phosphomolybdic acid.
24. The process of claim 16 wherein the refractory inorganic support of step (b) is selected from the group consisting of alumina, silica, and alumina-silica.
25. The process of claim 1 wherein the hydroconversion zone is comprised of one or more reactors which contain an expanded bed of the supported hydrotreating catalyst, which reactors are operated: (i) with a hydrogen flow rate of about 1,000 to 20,000 SCFB; (ii) at a liquid hourly space velocity of about 0.08 to about 1.5 volumes of chargestock per hour per volume of reactor; (iii) at a temperature from about 730°F to about 850°F; and (iv) at a hydrogen partial pressure of about 1,000 to about 3,000 psia.
26. The process of claim 25 wherein: (i) prior to introducing the mixture of step (a) into the hydroconversion zone it is first heated in the presence of a sulfiding agent at a temperature of at least about 500°F
for an effective amount of time to convert the oil-dispersible, or decomposable, metal compound to the corresponding metal-containing catalyst in said hydrocarbonaceous oil; and (ii) conducting the hydroconversion zone in the substantial absence of sulfiding agent other than that found in the chargestock.
for an effective amount of time to convert the oil-dispersible, or decomposable, metal compound to the corresponding metal-containing catalyst in said hydrocarbonaceous oil; and (ii) conducting the hydroconversion zone in the substantial absence of sulfiding agent other than that found in the chargestock.
27. The process of claim 26 wherein the sulfiding agent is selected from the group consisting of a hydrogen sulfide containing stream, elemental sulfur, carbon disulfide, and compounds that decompose to yield sulfide moieties.
28. The process of claim 27 wherein a hydrogen sulfide containing stream is used as the sulfiding agent wherein the H2S/metal mole ratio is from about 1 to 5.
29. The process of claim 26 wherein in step (a): (i) the heavy hydrocarbonaceous oil is a blend of a lighter oil boiling below about 1050°F and a heavier oil boiling above about 1050°F which blend contains about 22 to 85 wt.% of heavier oil, (ii) the concentration of oil dispersible metal compound is such that about 0.2 to 1 wt.%, calculated as elemental metal, is present, based on said oil blend.
30. The process of claim 29 wherein the oil dispersible, or decomposable, metal compound is selected from the group consisting of inorganic metal compounds, salts of organic acids, organometallic compounds, salts of organic amines.
31. The process of claim 30 wherein metal is selected from the group consisting of molybdenum, chromium, vanadium, and mixtures thereof.
32. The process of claim 31 wherein the oil dispersible metal compound is phosphomolybdic acid.
33. The process of claim 25 wherein the refractory inorganic oxide of step (b) is selected from the group consisting of alumina, silica, and alumina-silica.
34. The process of claim 1 wherein the hydroconversion zone is operated in a slurry mode in the substantial absence of supported catalysts.
35. The process of claim 16 wherein the hydroconversion zone is operated in a slurry mode in the substantial absence of supported catalysts.
36. A catalyst precursor concentrate comprised of: (i) a heavy hydrocarbonaceous oil; (ii) a dispersible, or decomposable, metal compound, said metal being selected from the group consisting of Groups II, III, IV, V, VIB, VIIB, VIII, and mixtures thereof, of the Periodic Table of Elements, in an amount ranging from about 0.1 to about 2 weight percent, calculated as elemental metal, based on said carbonaceous oil; and (iii) a supported catalyst composition comprised of an active metal component and an inorganic refractory support material wherein the active component is a metal, or metal oxide, selected from those metals of Groups VIB and VIII of the Periodic Table of the Elements, and the refractory support material is selected from silica, alumina, or silica-alumina.
37. The concentrate of claim 36: (i) wherein the oil dispersible, or decomposable, metal compound is selected from the group consisting of inorganic metal compounds, salts of organic acids, organometallic compounds, salts of organic amines, and mixtures thereof; (ii) wherein the metal of the oil dispersible, or decomposable, compound is select-ed from chromium, molybdenum, and vanadium; (iii) wherein the heavy hydrocarbonaceous oil is a blend of lighter oil boiling below about 1050°F and from about 22 to 85 wt. % of a heavier oil boiling above about 1050°F, said wt. % based on the total weight of the blend; and (iv) wherein the supported catalyst is nickel and molybdenum or cobalt and molybdenum, on alumina.
38. The concentrate of claim 37 wherein an oil dispersible metal compound is used which is phosphomolybdic acid.
39. The concentrate of claim 36 which is converted to its respective catalyst concentrate by treatment with a sulfiding agent at a temperature of at least about 500°F, for an effective amount of time, thereby converting the catalyst precursor concentrate to its respective catalyst concentrate.
40. The concentrate of claim 37 which is converted to its respective catalyst concentrate by treatment with a sulfiding agent at a temperature of at least about 500°F, for an effective amount of time, thereby converting the catalyst precursor concentrate to its respective catalyst concentrate.
41. The concentrate of claim 38 which is converted to its respective catalyst concentrate by treatment with a sulfiding agent at a temperature of at least about 500°F, for an effective amount of time, thereby converting the catalyst precursor concentrate to its respective catalyst concentrate.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US24337688A | 1988-09-12 | 1988-09-12 | |
| US243,376 | 1988-09-12 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1334840C true CA1334840C (en) | 1995-03-21 |
Family
ID=22918520
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 609476 Expired - Fee Related CA1334840C (en) | 1988-09-12 | 1989-08-25 | Hydroconversion of heavy feeds by use of both supported and unsupported catalysts |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1334840C (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023280624A1 (en) * | 2021-07-08 | 2023-01-12 | IFP Energies Nouvelles | Hydroconversion of a hydrocarbon-based heavy feedstock in a hybrid ebullated-entrained bed, comprising premixing said feedstock with an organic additive |
| WO2023280626A1 (en) * | 2021-07-08 | 2023-01-12 | IFP Energies Nouvelles | Hydroconversion of a hydrocarbon-based heavy feedstock in a hybrid ebullated-entrained bed, comprising mixing said feedstock with a catalyst precursor containing an organic additive |
-
1989
- 1989-08-25 CA CA 609476 patent/CA1334840C/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023280624A1 (en) * | 2021-07-08 | 2023-01-12 | IFP Energies Nouvelles | Hydroconversion of a hydrocarbon-based heavy feedstock in a hybrid ebullated-entrained bed, comprising premixing said feedstock with an organic additive |
| WO2023280626A1 (en) * | 2021-07-08 | 2023-01-12 | IFP Energies Nouvelles | Hydroconversion of a hydrocarbon-based heavy feedstock in a hybrid ebullated-entrained bed, comprising mixing said feedstock with a catalyst precursor containing an organic additive |
| FR3125059A1 (en) * | 2021-07-08 | 2023-01-13 | IFP Energies Nouvelles | HYDROCONVERSION INTO A BUBBLE-DRIVEN HYBRID BED OF A HEAVY HYDROCARBON CHARGER COMPRISING MIXING SUCH CHARGER WITH A CATALYST PRECURSOR CONTAINING AN ORGANIC ADDITIVE |
| FR3125057A1 (en) * | 2021-07-08 | 2023-01-13 | IFP Energies Nouvelles | HYDROCONVERSION INTO A BUBBLE-ENCOURAGED HYBRID BED OF A HEAVY HYDROCARBON CHARGER COMPRISING PREMIXING SAID CHARGER WITH AN ORGANIC ADDITIVE |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US5108581A (en) | Hydroconversion of heavy feeds by use of both supported and unsupported catalysts | |
| US5039392A (en) | Hydroconversion process using a sulfided molybdenum catalyst concentrate | |
| US4740295A (en) | Hydroconversion process using a sulfided molybdenum catalyst concentrate | |
| US4313818A (en) | Hydrocracking process utilizing high surface area catalysts | |
| US4244839A (en) | High surface area catalysts | |
| CA1079665A (en) | Hydroconversion of an oil-coal mixture | |
| CA1094004A (en) | Process for catalytically hydrocracking a heavy hydrocarbon oil | |
| US4637870A (en) | Hydrocracking with phosphomolybdic acid and phosphoric acid | |
| US5171727A (en) | Method of preparing a catalyst for the hydroconversion of asphaltene-containing hydrocarbonaceous charge stocks | |
| US4066530A (en) | Hydroconversion of heavy hydrocarbons | |
| US4357229A (en) | Catalysts and hydrocarbon treating processes utilizing the same | |
| US4226742A (en) | Catalyst for the hydroconversion of heavy hydrocarbons | |
| US4370221A (en) | Catalytic hydrocracking of heavy oils | |
| US4820677A (en) | Amorphous, iron promoted Mo and W sulfide hydroprocessing catalysts and process for their preparation | |
| US5300212A (en) | Hydroconversion process with slurry hydrotreating | |
| Ohtsuka | Catalyst for hydrodesulfurization of petroleum residua | |
| CA1163222A (en) | Simultaneous demetalization and hydrocracking of heavy hydrocarbon oils | |
| US4632747A (en) | Hydrotreating process employing catalysts comprising a supported, mixed metal sulfide iron promoted Mo and W | |
| US5053376A (en) | Method of preparing a sulfided molybdenum catalyst concentrate | |
| US4548700A (en) | Hydroconversion process | |
| US4348270A (en) | Catalysts and hydrocarbon treating processes utilizing the same | |
| US4740489A (en) | Method of preparing a hydroconversion sulfided molybdenum catalyst concentrate | |
| US4560465A (en) | Presulfided red mud as a first-stage catalyst in a two-stage, close-coupled thermal catalytic hydroconversion process | |
| GB1584785A (en) | Hydroconversion of heavy hydrocarbons | |
| US4295995A (en) | Catalysts hydrocarbon treating processes |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKLA | Lapsed |