US3213012A - Starting up procedure in the hydrocaracking of hydrocarbons - Google Patents

Starting up procedure in the hydrocaracking of hydrocarbons Download PDF

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Publication number
US3213012A
US3213012A US226090A US22609062A US3213012A US 3213012 A US3213012 A US 3213012A US 226090 A US226090 A US 226090A US 22609062 A US22609062 A US 22609062A US 3213012 A US3213012 A US 3213012A
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Prior art keywords
sulfur
catalyst
feed
percent
hydrogen
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US226090A
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Robert E Kline
Joseph B Mckinley
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Gulf Research and Development Co
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Gulf Research and Development Co
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Priority to GB1050968D priority Critical patent/GB1050968A/en
Priority to NL298382D priority patent/NL298382A/xx
Application filed by Gulf Research and Development Co filed Critical Gulf Research and Development Co
Priority to US226090A priority patent/US3213012A/en
Priority to FR948103A priority patent/FR1374581A/fr
Priority to NL129111D priority patent/NL129111C/xx
Priority to DEP1267A priority patent/DE1267772B/de
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G49/00—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00
    • C10G49/24—Starting-up hydrotreatment operations

Definitions

  • Hydrocracking of distillate hydrocarbons in certain respects is a relatively expensive operation.
  • one of the main requirements is to use a highly active catalyst which will retain high activity over a long period of time. While highly active catalysts have been employed, there is still room for improvement in this regard. Furthermore it is frequently found that the more active the catalyst the shorter the onstream period. This is not due to any inherent defect in the catalyst but to improper procedure in employing the catalyst or in controlling the reaction conditions.
  • This invention has for its object to provide improved hydrocracking procedure. Another object is to provide improved hydrocracking procedure wherein a catalyst containing nickel-tungsten is employed. A still further object is to provide an improved procedure for hydrocracking distillate stocks whereby the hydrocracking process can be carried out over longer periods of time at high conversion rates. Another object is to provide improved start-up procedure. Other objects will appear hereinafter.
  • our invention includes subjecting a distillate feed stock composed primarily of hydrocarbons boiling in the range be tween about 350 and 800 F. to treatment with hydrogen in the presence of a nickel-tungsten sulfide catalyst composited with a siliceous carrier having a cracking activity index of at least 40.
  • a nickel-tungsten sulfide catalyst composited with a siliceous carrier having a cracking activity index of at least 40 See J. Alexander et a1. Laboratory Method for Determining the Activity of Cracking Catalysts, National Petroleum News, vol. 36, 1944, p. R537.
  • the catalyst and feed stock are initially contacted at below 500 F. and while the nickel and tungsten are substantially unsulfided, i.e. in the reduced, partially reduced or preferably in the oxide form.
  • the catalyst utilized in our process may contain between about and 40 percent and preferably 10 to 25 .percent of nickel plus tungsten (determined as metals).
  • ice atomic ratio may be between 1 atom of tungsten to 0.1 atom of nickel to 1 atom of tungsten to 5 atoms of nickel. We prefer a range of between 1 atom of tungsten to 0.3 atom to 4 atoms of nickel.
  • Any siliceous carrier may be employed which has .an activity index of at least 40. We preferably employ a siliceous carrier which has an activity index above 45.
  • Such siliceous carriers are known in the catalytic cracking art, a typical example being silica-alumina cracking catalysts.
  • the catalyst employed in our invention may be prepared using any known procedure for manufacture of such multi-component catalysts.
  • the nickel and tungsten components may be deposited upon the cracking carrier by co-precipitation. Alternatively they may be deposited in sequence with or without intervening calcining. Simultaneous impregnation from a two-component solution containing the two metals may also be employed. Thus the procedure described in McKinley et al. Patent 2,703,789 would be entirely satisfactory.
  • These components may be present as mixtures and/or as chemical compounds.
  • the nickel and tungsten components of the catalyst employed in our invention be largely unsulfided, i.e. largely in the reduced, partially reduced and/or oxide form. It is preferable to start out with a catalyst which is substantially in the oxide form. If a presulfided catalyst is used initially and kept in that form by sulfur addition to the feed, we have found that the useful life of the catalyst is substantially shorter than if a substantially unsulfied catalyst is initially employed. However, it is to be understood that a presulfided and subsequently reduced or largely reduced catalyst is satisfactory to use in the process of our invention.
  • Sulfiding of the catalyst may be accomplished by adding elemental sulfur or suitable sulfur compounds to the fresh feed, recycle feed, make-up hydrogen and/or the recycle hydrogen rich gas stream.
  • the sulfur added includes the relatively small amount usually present in normally hydrogen refined or other feed and the relatively large amount which builds up in any hydrogen rich recycle gas stream when employing sulfur addition. Normally there is no sulfur in the liquid recycle but if any is present it is also included.
  • the operation may be single pass, in which case only sulfur added to and in the fresh feed and the process gas comes into consideration.
  • Any organic or inorganic sulfur compound having a hydrogen-to-sulfur or a carbon-to-sulfur linkage as well as elemental sulfur can be used such as butyl mercaptan, thiophene, hydrogen sulfide, carbon disulfide, etc. It is convenient and often preferable to obtain rapid initial sulfiding and therefore it is advantageous to use large amounts of sulfur (to be hereinafter understood as designating elemental sulfur or any sulfur compound having carbonor hydrogen-to-sulfur linkage) during the early low temperature stages and then reduce the amount of sulfur to that which will maintain the catalyst in substantially sulfided condition.
  • Conversion means the actual percent conversion of feed to material boiling below the initial boiling point of the feed, which term includes unconverted feed recycle in recycle operation.
  • Conversion means the actual percent conversion of feed to material boiling below the initial boiling point of the feed, which term includes unconverted feed recycle in recycle operation.
  • any sulfur content in feed, recycle hydrogen, make-up hydrogen and/or recycle feed which will result in substantial sulfiding and conditioning of the catalyst after intial contact of feed and catalyst but prior to expiration of the major portion of the conversion period. This of course includes simultaneous initial feed contact and sulfiding.
  • Sulfur contents in the feed, hydrogen, etc. based on total liquid hydrocarbon feed may vary from about 40 p.p.m. to 2.0 percent.
  • a space velocity liquid volumes of feed, which include fresh feed and unconverted recycle feed in recycle operation, per volume of catalyst per hour
  • a hydrogen (i.e. actual hydrogen content) rate of between 4,000 and 25,000 s.c.f./bbl. of feed and preferably between 7,000 and 18,000 s.c.f./bbl. of feed may be employed in the hydrocracking process.
  • EXAMPLE I This example shows the advantage of starting up with the catalyst initially in the oxide state as compared to starting with a presulfided catalyst and maintaining it in the sulfided condition by sulfur addition.
  • the catalyst used was a pelleted 6 percent nickel-19 percent tungsten2 percent fluorine on Triple A silica-alumina catalyst.
  • the feed was a hydrogen refined FCC furnace oil. In the first operation the start-up was with unpresulfided catalyst at below 450 F.
  • the feed had the properties given in Table I, Column A. It was fortified to 2600 p.p.m. sulfur added as dimethyl disulfide and was charged along with 10,000 s.c.f. of 75 percent hydrogen/bbl.
  • the temperature had been increased to 648 F. to maintain the desired 70 percent conversion of fresh feed plus recycle and the carbon on the catalyst was 2.72 percent.
  • the total sulfur charged to the reactor 6 was about 0.79 percent based on total liquid reactor feed.
  • the same catalyst was presulfided to the lined-out sulfur content of about 5.5 percent by subjecting it to an GHSV flow of an 82 percent hydrogen-18 percent H S mixture at 580 F. and 1200 p.s.i.g. for three hours.
  • This catalyst was then used to process a hydrogen refined FCC furnace oil having the properties given in Table I, Column B, together with 1.38 percent sulfur added as tertiary butyl mercaptan and 10,000 s.c.f. of percent hyrogen/bbl. at 1000 p.s.i.g. and 1 LHSV in a single-pass operation.
  • This amount of added sulfur made the reactor feed sulfur level about the same in this single-pass operation as it was at the end of two days in the preceding operation. Starting up was at 500 F. and no hot spot trouble was noted even in spite of the use of this relatively high temperature. At the end of two days the conversion of feed stock to gasoline at a temperature of 600 to 605 F. was only about 57 percent.
  • the catalyst contained 13.39 percent carbon (after 4% days on stream).
  • the amount of sulfur in the feed was theoretically adequate to cause catalyst sulfiding to the lined-out level of about 5.5 percent (coke free basis) in about 40 hours.
  • the amount of sulfur in fresh feed was cut to about 54 p.p.m. and after 19 days the source of added sulfur was changed from dimethyl disulfide to carbon disulfide which has been found to be the equivalent of dimethyl disulfide in this application.
  • the 54 p.p.m. sulfur, added to fresh feed and that returning as hydrogen sulfide in the recycle gas stream gave a total liquid reactor feed sulfur level of about 270 p.p.m.
  • fluorine was added as ortho-fiuorotoluene to the fresh feed for the first 19 days of operation and thereafter fluorine addition was cut to 4 p.p.m. for catalyst activity and fluorine content maintenance. These amounts of fluorine amounted to 6.7 and 2.7 p.p.m. respectively based on total liquid reactor feed during recycle operation. It can be noticed that the operation with sulfur addition resulted in higher activity for the catalyst and a lower catalyst aging rate. Thus, not only is our proposed method more advantageous than starting up with presulfided catalyst, it is also better than starting up with unsulfided catalyst and not sulfiding it at as rapid a rate as proposed or only at the rate possible when processing normally hydrogen refined feeds.
  • the catalysts employed in this example had the same nickel and tungsten content and were deposited on the same carrier as that described in Example 1.
  • EXAMPLE III In this example the feed stock described in Example I in connection with the unpresulfided catalyst was treated in the same manner as described in Example I in con nection with the unpresulfided catalyst, excepting that no sulfur was added to the feed stock until the operation had been continued for about 12 days. Thereafter sulfur addition to the fresh feed was started, and the reactor sulfur level counting hydrogen sulfide returned in the hydrogen rich recycle quickly lined-out at about 0.70 percent based on total liquid reactor feed. Prior to the sulfur addition, the aging rate of the catalyst was such as to require a temperature increase of 1.2 F. per day in order to maintain conversion. After the addition of sulfur was started, the daily temperature increase in order to maintain conversion amounted only to- 0.4 or 0.5 F.
  • EXAMPLE IV In this example, start-up was at 450 F. with pelleted unpresulfided 6 percent nickel-19 percent tungsten-2 percent fluorine Triple A silica-alumina supported catalyst. Operation for the first three days was with the sulfur-free severely hydrogen refined FCC furnace oil described in Table I, Column D, and operation for the next day was with the essentially sulfur-free hydrogen refined FCC furnace oil described in Table I, Column B. During this period the temperature was increased to and maintained at 500 F. with other processing conditions being 1.0 LHSV, 1000 p.s.i.g. and 10,000 s.c.f. of 100 percent hydrogen/bbl. in single-pass operation.
  • Example II This may be compared with the run in Example I, with the catalyst presulfided to the maximum lined-out sulfur content of about 5.5 percent and maintained at that sulfur content by processing the same feed fortified to 1.38 percent sulfur content by t-butyl mercaptan addition, where the conversion of stock to gasoline after 2 days was only 57 percent and after 4% days was only 51 percent. Furthermore, the catalyst contained 13.39 percent carbon at the end of the 4% days.
  • an advantageous modification of our operation as compared with the prior art can be to operate for a period of time under sulfur-free conditions during which time the catalyst is subjected to reducing conditions and then to cause sulfiding of the catalyst by addi- 8 tion of sulfur to the feed and prior to expiration of the major portion of the conversion period.
  • a start-up procedure for use in a hydrocracking process which process comprises hydrocracking a hydrocarbon feed which is substantially composed of hydrocarbons having a boiling point below about 800 R, which has a nitrogen content below about 25 ppm. and which is substantially free of asphaltic materials utilizing a catalyst comprising essentially nickel-tungsten sulfide composited with a siliceous carrier having a high activity index, the nickel-tungsten components being substantially in sulfided form during the major conversion portion of the hydrocracking process, said start-up procedure comprising initially contacting the hydrocarbon feed with hydnogen in the presence of a catalyst consisting of nickel-tungsten composited with a siliceous carrier while the nickel and tungsten components are substantially unsulfided, at a hydrogen partial pressure of between about 400 and 3000 p.s.i., at an initial temperature below about 500 F.
  • a start-up procedure for use in a hydrocracking process which process comprises hydrocracking a hydrocarbon feed which is substantially composed of hydrocarbons boiling between about 350 and 800 E, which has a nitrogen content below about 25 ppm. and which is substantially free of asphaltic materials utilizing a cata lyst comprising essentially a nickel-tungsten sulfide corn posited with a silica-alumina carrier having an activity index of at least 45, the nickel-tungsten components being substantially in sulfided form during the major conversion portion of the hydrocracking process, said startup procedure comprising initially contacting the hydrocarbon feed with hydrogen in the presence of a catalyst consisting of nickel-tungsten composited with a silicaalumina carrier while the nickel and tungsten components are substantially unsulfided, at a hydrogen partial pressure of between about 400 and 1500 p.s.i., at an initial temperature below about 500 F.
  • a start-up procedure for use in a hydrocracking process which process comprises hydrocracking a hydrocarbon feed 'which is substantially composed of hydrocarbons boiling between about 350 and 550 R, which has a nitrogen content below about ppm. and which is substantially free of asphaltic materials utilizing a catalyst comprising essentially a nickel-tungsten sulfide composited with a silicaaalumina carrier having an activity index of at least and a surface area of at least 500 square meters per gram, the catalyst containing at least about 0.1 percent by weight combined halogen and the nickel-tungsten components being substantially in sulfided form during the major conversion portion of the hydrocracking process, said start-up procedure comprising initially contacting the hydrocarbon feed with hydrogen in the presence of a catalyst consisting of nickeltungsten composited with a silica-alumina carrier while the nickel and tungsten component are substantially unsulfided, at a hydrogen partial pressure of between about 400 and 600 p.s.i., at an initial temperature below about 500 F.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
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US226090A 1962-09-25 1962-09-25 Starting up procedure in the hydrocaracking of hydrocarbons Expired - Lifetime US3213012A (en)

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Application Number Priority Date Filing Date Title
GB1050968D GB1050968A (enrdf_load_stackoverflow) 1962-09-25
NL298382D NL298382A (enrdf_load_stackoverflow) 1962-09-25
US226090A US3213012A (en) 1962-09-25 1962-09-25 Starting up procedure in the hydrocaracking of hydrocarbons
FR948103A FR1374581A (fr) 1962-09-25 1963-09-20 Procédé d'hydrocraquage utilisant un catalyseur
NL129111D NL129111C (enrdf_load_stackoverflow) 1962-09-25 1963-09-25
DEP1267A DE1267772B (de) 1962-09-25 1963-09-25 Verfahren zum Anfahren der hydrierenden Spaltung von Kohlenwasserstoffdestillaten

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DE (1) DE1267772B (enrdf_load_stackoverflow)
FR (1) FR1374581A (enrdf_load_stackoverflow)
GB (1) GB1050968A (enrdf_load_stackoverflow)
NL (2) NL129111C (enrdf_load_stackoverflow)

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3294674A (en) * 1964-12-28 1966-12-27 Gulf Research Development Co Hydrocracking of hydrocarbons with a sulfided tungsten oxide catalyst on a silica-alumina cracking support
US3305477A (en) * 1964-07-17 1967-02-21 Texaco Inc Hydrocracking nitrogen-containing feed in the presence of halides
US3306842A (en) * 1963-06-07 1967-02-28 British Petroleum Co Hydrocatalytic treatment of wax containing hydrocarbon distillates
US3316169A (en) * 1964-10-16 1967-04-25 Texaco Inc Catalytic hydrocracking of hydrocarbons with the use of halogen and sulfur activators
US3336216A (en) * 1966-03-18 1967-08-15 Chevron Res Catalytic hydrocracking process with a silica-magnesia cracking base promoted with nickel and tungsten
US3347780A (en) * 1966-02-04 1967-10-17 Chevron Res Naphtha hydroconversion to produce lower boiling hydrocarbon products
US3349025A (en) * 1965-07-15 1967-10-24 Gulf Research Development Co Hydrocracking with a presulfided tungsten oxide composite catalyst from the group comprising of silver, zinc or thorium on a siliceous carrier
US3354076A (en) * 1965-10-22 1967-11-21 Gulf Research Development Co Process for the hydrocracking of hydrocarbon oils under reaction conditions so as toretain substantial amounts of aromatics in the naphtha product
US3395095A (en) * 1965-07-01 1968-07-30 Texaco Inc Hydrocracking of hydrocarbons with the constant addition of sulfur to the reaction zone
US3505205A (en) * 1968-04-23 1970-04-07 Gulf Research Development Co Production of lpg by low temperature hydrocracking
US3673108A (en) * 1969-12-31 1972-06-27 Shell Oil Co Hydrocracking catalyst activation treatment
US3852372A (en) * 1970-06-25 1974-12-03 Texaco Inc Isomerization with fluorided composite alumina catalysts
US3963601A (en) * 1973-08-20 1976-06-15 Universal Oil Products Company Hydrocracking of hydrocarbons with a catalyst comprising an alumina-silica support, a group VIII metallic component, a group VI-B metallic component and a fluoride
US3965253A (en) * 1972-05-01 1976-06-22 Shell Oil Company Process for producing hydrogen

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4040979A (en) * 1976-02-23 1977-08-09 Uop Inc. Hydrocarbon conversion catalytic composite

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2934492A (en) * 1956-12-03 1960-04-26 Exxon Research Engineering Co Hydrogenation of heavy oils
US2944005A (en) * 1958-08-13 1960-07-05 California Research Corp Catalytic conversion of hydrocarbon distillates
US3099617A (en) * 1960-08-04 1963-07-30 Union Oil Co Pretreatment of catalyst employed in the hydrocracking of hydrocarbons

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB780263A (en) * 1954-07-30 1957-07-31 Gulf Research Development Co Process for the destructive hydrogenation of hydrocarbon mixtures containing difficultly vaporizable components
FR1287661A (fr) * 1960-03-16 1962-03-16 Universal Oil Prod Co Procédé pour l'hydrocraquage des huiles hydrocarbonées

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2934492A (en) * 1956-12-03 1960-04-26 Exxon Research Engineering Co Hydrogenation of heavy oils
US2944005A (en) * 1958-08-13 1960-07-05 California Research Corp Catalytic conversion of hydrocarbon distillates
US3099617A (en) * 1960-08-04 1963-07-30 Union Oil Co Pretreatment of catalyst employed in the hydrocracking of hydrocarbons

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3306842A (en) * 1963-06-07 1967-02-28 British Petroleum Co Hydrocatalytic treatment of wax containing hydrocarbon distillates
US3305477A (en) * 1964-07-17 1967-02-21 Texaco Inc Hydrocracking nitrogen-containing feed in the presence of halides
US3316169A (en) * 1964-10-16 1967-04-25 Texaco Inc Catalytic hydrocracking of hydrocarbons with the use of halogen and sulfur activators
US3294674A (en) * 1964-12-28 1966-12-27 Gulf Research Development Co Hydrocracking of hydrocarbons with a sulfided tungsten oxide catalyst on a silica-alumina cracking support
US3395095A (en) * 1965-07-01 1968-07-30 Texaco Inc Hydrocracking of hydrocarbons with the constant addition of sulfur to the reaction zone
US3349025A (en) * 1965-07-15 1967-10-24 Gulf Research Development Co Hydrocracking with a presulfided tungsten oxide composite catalyst from the group comprising of silver, zinc or thorium on a siliceous carrier
US3354076A (en) * 1965-10-22 1967-11-21 Gulf Research Development Co Process for the hydrocracking of hydrocarbon oils under reaction conditions so as toretain substantial amounts of aromatics in the naphtha product
US3347780A (en) * 1966-02-04 1967-10-17 Chevron Res Naphtha hydroconversion to produce lower boiling hydrocarbon products
US3336216A (en) * 1966-03-18 1967-08-15 Chevron Res Catalytic hydrocracking process with a silica-magnesia cracking base promoted with nickel and tungsten
US3505205A (en) * 1968-04-23 1970-04-07 Gulf Research Development Co Production of lpg by low temperature hydrocracking
US3673108A (en) * 1969-12-31 1972-06-27 Shell Oil Co Hydrocracking catalyst activation treatment
US3852372A (en) * 1970-06-25 1974-12-03 Texaco Inc Isomerization with fluorided composite alumina catalysts
US3965253A (en) * 1972-05-01 1976-06-22 Shell Oil Company Process for producing hydrogen
US3963601A (en) * 1973-08-20 1976-06-15 Universal Oil Products Company Hydrocracking of hydrocarbons with a catalyst comprising an alumina-silica support, a group VIII metallic component, a group VI-B metallic component and a fluoride

Also Published As

Publication number Publication date
NL129111C (enrdf_load_stackoverflow) 1965-11-25
GB1050968A (enrdf_load_stackoverflow) 1900-01-01
FR1374581A (fr) 1964-10-09
DE1267772B (de) 1968-05-09
NL298382A (enrdf_load_stackoverflow)

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