EP0707057A1 - Addition von Kohlendioxid in Hydrokrack/Hydroisomerizierungsverfahren zur Kontrolierung der Methanherstellung - Google Patents

Addition von Kohlendioxid in Hydrokrack/Hydroisomerizierungsverfahren zur Kontrolierung der Methanherstellung Download PDF

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Publication number
EP0707057A1
EP0707057A1 EP95305724A EP95305724A EP0707057A1 EP 0707057 A1 EP0707057 A1 EP 0707057A1 EP 95305724 A EP95305724 A EP 95305724A EP 95305724 A EP95305724 A EP 95305724A EP 0707057 A1 EP0707057 A1 EP 0707057A1
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Prior art keywords
carbon dioxide
catalyst
silica
feed
alumina
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French (fr)
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EP0707057B1 (de
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Daniel Francis Ryan
Robert Jay Wittenbrink
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ExxonMobil Technology and Engineering Co
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Exxon Research and Engineering Co
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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
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/58—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins

Definitions

  • This invention relates to hydroisomerization processes including hydrocracking wherein the reaction is conducted in the presence of carbon dioxide, and terminal cracking, i.e., methane formation, is substantially minimized without substantial effect on C2-C4 yields.
  • catalysts including noble metals, Pt, Pd, Rh supported on flourided alumina, and Group VIII non-noble metals with or without one or more Group VI metals supported on silica, alumina or silica-alumina. These catalysts are usually bifunctional; they contain a metal hydrogenation catalyst and an acidic cracking function.
  • Carbon oxides, carbon dioxide and particularly carbon monoxide have been disclosed in United States Patent No. 3,711,399 as inhibitors of hydrocracking in isomerization processes using highly acidic fluorine containing catalyst, the carbon oxide being added in relatively small amounts. Hydrocracking is virtually completely suppressed and C4- yields are virtually negligible.
  • Hydroisomerization processes produce diesel and jet fuels, and LPG and light hydrocarbon products if the fuels' pour-points are to be appropriate.
  • Methane is a particularly undesirable product since, for example, isomerized products can be made from Fischer-Tropsch waxes which, in turn, ultimately are derived from methane via synthesis gas production. Consequently, there is a requirement for isomerization processes that suppress or substantially eliminate methane formation without substantial effect on LPG and light liquid yields.
  • terminal cracking of C5+ hydrocarbons is substantially suppressed, e.g., to less than about 1.0 weight percent based on feed, by conducting a hydroisomerization process incorporating carbon dioxide in the reaction mixture in the presence of a catalyst comprising one or more Group VIII non-noble metals or one or more Group VI metals, or both, the metals being supported on an acidic support comprising alumina or silica alumina.
  • LPG yields e.g., C2-C4
  • light liquid yields e.g., C5-320°F (160°C), 320-500°F (160-260°C) are unaffected while C1 yields are suppressed to less than about 1 wt%, preferably less than about 0.5 wt%.
  • Figure 1 shows plots of various product yields when carbon monoxide is added to the feed. Time is always on the abscissa.
  • Figures 1a-1f are plots of 700°F+ (371°C+) wax conversion, methane yield, C2-C4 yield, C5-320°F (160°C) yield, 320-500°F (160-260°C) yield, and 500-700°F (260-371°C) yield, all v. time.
  • the first vertical dotted line shows CO in at 320 hours and the second dotted line shows CO out at about 650 hours.
  • Figure 2 shows plots of various product yields when carbon dioxide is added to the feed. Time is always on the abscissa.
  • Figures 2a-2f show yields for the same products as in Figures 1a-1f.
  • the dotted line shows CO2 in at about 320 hours.
  • the amount of carbon dioxide used in conjunction with feed is at least about 0.2 mole % based in feed, preferably at least about 0.3 mole %, preferably about 0.3 mole % to about 1.0 mole %.
  • carbon oxides are often lumped together as catalyst poisons, only carbon dioxide suppressed terminal cracking with the non-noble metal, functional catalyst of this invention; carbon monoxide had virtually no effect on the process.
  • Total conversion of feed during the process is 20-90%, preferably 30-70%, and more preferably 40-60%.
  • the active hydroisomerization metals are non-noble metals selected from Group VIII of the Periodic chart of the Elements.
  • Preferred metals are nickel and cobalt or mixtures thereof and mixtures thereof with molybdenum, a Group VI metal.
  • the Group VIII metals may be present on the catalyst in amounts sufficient to be catalytically active for hydroisomerization. Specifically, metal concentrations ranging from about 0.05 to about 20 wt%, preferably about 0.1 to 10 wt%, still more preferably 2.0 to 5.0 wt% may be used.
  • the cobalt loading may be 1-4 wt%, and the nickel loading may be 0.1-1.5 wt%.
  • a Group VI metal such as molybdenum also can be employed in amounts more or less than or equal to the non-noble Group VIII metal, e.g., 1.0 to 20 wt%, preferably 8-15 wt%, in all cases by total weight of catalyst.
  • the metals are impregnated onto or added to the support as suitable metal salts or acids, e.g., nickel or cobalt nitrate, etc.
  • suitable metal salts or acids e.g., nickel or cobalt nitrate, etc.
  • the catalyst is then dried and calcined in well known fashions.
  • tetraalkoxysilane tetraalkoxysilane
  • orthosilicic acid ester etc.
  • sulfates nitrates, or chlorides of aluminum alkali metal aluminates, or inorganic or organic salts of alkoxides or the like.
  • Precipitation and aging are carried out, with heating, by adding an acid or base under reflux to prevent evaporation of the treating liquid and change of pH.
  • the remainder of the support producing process is the same as those commonly employed, including filtering, drying and calcination of the support material.
  • the support may also contain small amounts, e.g., 1-30 wt% of materials such as magnesia, titania, zirconia, hafnia, or the like.
  • a preferred support is an amorphous silica-alumina carrier, containing less than about 35 wt% silica, preferably about 2-35 wt% silica, more preferably 5 to 30 wt% silica, and having the following pore-structural characteristics: Pore Radius (A) Pore Volume 0-300 >0.03 ml/g 100-75,000 ⁇ 0.35 ml/g 0-30 ⁇ 25% of the volume of the pores with 0-300 A radius 100-300 ⁇ 40% of the volume of the pores with 0-300 A radius
  • the materials have a surface area ranging from about 180-400 mg, preferably 230-375 m/g, a pore volume of 0.3 to 1.0 ml/g, preferably 0.5 to 0.95 ml/g, bulk density of about 0.5-1.0 g/ml, and a side crushing strength of about 0.8 to 3.5 kg/mm.
  • the feed materials that are isomerized with the catalyst of this invention are waxy feeds, i.e., C5+, preferably boiling above about 350°F (177°C) preferably above about 550°F (288°C) and may be obtained either from a Fischer-Tropsch process which produces substantially normal paraffins or from slack waxes.
  • Slack waxes are the by-products of dewaxing operations where a diluent such as propane or a ketone (e.g., methylethyl ketone, methyl isobutyl ketone) or other diluent is employed to promote wax crystal growth, the wax being removed from the lubricating oil base stock by filtration or other suitable means.
  • the slack waxes are generally paraffinic in nature, boil above about 600°F (316°C), preferably in the range of 600°F (316°C) to about 1050°F (566°C), and may contain from 1 to 35 wt% oil. Waxes with low oil contents, e.g., 5-20 wt% are preferred; however, waxy distillates or raffinates containing 5-45% wax may also be used as feeds.
  • Slack waxes are usually freed of polynuclear aromatics and heteroatom compounds by techniques known in the art, e.g., mild hydrotreating as described in U.S. Patent No. 4,900,707, which also reduces sulfur and nitrogen levels preferably to less than 5 ppm and less than 2 ppm, respectively. Fischer-Tropsch waxes are preferred feed materials, having negligible amounts of aromatics, sulfur and nitrogen compounds.
  • Isomerization conditions usually include temperatures of 300-400°C, 500-3000 psig hydrogen, 1000-10,000 SCF/bbl hydrogen treat and space velocity of 0.1-10.0 LHSV.
  • Preferred conditions include 320-385°C, 750-1500 psig hydrogen, 0.5-2 v/v/hr.
  • the catalyst is generally employed in a particulate form, e.g., cylindrical extrudates, trilobes, quadrilobes, and ranging in size from about 1-5 mm.
  • the hydroisomerization can be carried out in a fixed bed reactor and the products may be recovered by distillation.
  • the catalyst was evaluated at 750 psig, 0.50 LHSV, 690-700°F (366-377°C), and with a nominal H2 treat rate of 2500 SCF/B. A 10 cc charge of catalyst crushed and sized to 14/35 mesh was employed in each case.
  • the catalyst comprised 15.2 wt% MoO3 and 3.2 wt% CoO on a silica-alumina Co gel with 20-30 wt% bulk silica. Balances were typically collected at 24-72 hour intervals. The reaction temperature was set to meet a target of 50% 700°F+ wax conversion and was not adjusted during the run.
  • the Fischer-Tropsch wax employed in these studies had a nominal composition of 0.70% IBP-500°F (260°C), 20.48% 500-700°F (260-371°C), 78.82% 700°F+ (371°C). Typical run lengths were 800-1000 hours. Boiling range distributions for gas, naphtha, distillate range products, and lubes were obtained by a combination of simulated gas chromatography distillation and gas chromatography-mass spectroscopy.
  • methane yield actually increased when the CO was introduced. This occurred even though the conversion level was decreasing.
  • methane yield tracks reasonably well with conversion (i.e., an increase in conversion usually leads to an increase in methane).
  • the slight increase in methane yield may be due to CO hydrogenation, particularly since the methane level drops significantly when pure hydrogen is reintroduced and corresponds almost exactly with the amount of methane which would be produced if the CO was quantitatively converted to methane.
  • the methane yield shows the most dramatic change as a result of the CO2.
  • the activation procedure used in this run caused an extremely high methane yield of about 2 wt%.
  • Introduction of CO2 caused this level to drop to less than 0.30 wt% where it remained for the duration of the run.
  • a small reduction in the methane yield would be expected due to the decrease in the conversion; however, the effect is too great to account for the total reduction.
  • C1 methane
  • C2 was suppressed somewhat
  • C3 and C4 were virtually unaffected and as a result C2-C4 was substantially unaffected.
  • total conversion was suppressed at the outset of CO2 addition, and recovered somewhat as the reaction proceeded.
  • C2-C4 cracked products can range from about 1 wt% to about 3 wt%.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
EP19950305724 1994-10-13 1995-08-16 Addition von Kohlendioxid in Hydrokrack/Hydroisomerizierungsverfahren zur Kontrolierung der Methanherstellung Revoked EP0707057B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US29336294A 1994-10-13 1994-10-13
US293362 1994-10-13

Publications (2)

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EP0707057A1 true EP0707057A1 (de) 1996-04-17
EP0707057B1 EP0707057B1 (de) 2000-01-12

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EP19950305724 Revoked EP0707057B1 (de) 1994-10-13 1995-08-16 Addition von Kohlendioxid in Hydrokrack/Hydroisomerizierungsverfahren zur Kontrolierung der Methanherstellung

Country Status (6)

Country Link
EP (1) EP0707057B1 (de)
JP (1) JP3671246B2 (de)
AU (1) AU689286B2 (de)
CA (1) CA2156212C (de)
DE (1) DE69514476T2 (de)
NO (1) NO311178B1 (de)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6951605B2 (en) 2002-10-08 2005-10-04 Exxonmobil Research And Engineering Company Method for making lube basestocks
US7077947B2 (en) 2002-10-08 2006-07-18 Exxonmobil Research And Engineering Company Process for preparing basestocks having high VI using oxygenated dewaxing catalyst
US7087152B2 (en) 2002-10-08 2006-08-08 Exxonmobil Research And Engineering Company Wax isomerate yield enhancement by oxygenate pretreatment of feed
US7125818B2 (en) 2002-10-08 2006-10-24 Exxonmobil Research & Engineering Co. Catalyst for wax isomerate yield enhancement by oxygenate pretreatment
US7220350B2 (en) 2002-10-08 2007-05-22 Exxonmobil Research And Engineering Company Wax isomerate yield enhancement by oxygenate pretreatment of catalyst
US7282137B2 (en) 2002-10-08 2007-10-16 Exxonmobil Research And Engineering Company Process for preparing basestocks having high VI
US7670983B2 (en) 2002-10-08 2010-03-02 Exxonmobil Research And Engineering Company Oxygenate treatment of dewaxing catalyst for greater yield of dewaxed product
US7704379B2 (en) 2002-10-08 2010-04-27 Exxonmobil Research And Engineering Company Dual catalyst system for hydroisomerization of Fischer-Tropsch wax and waxy raffinate

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB772478A (en) * 1952-03-18 1957-04-17 Gulf Research Development Co Improved process of hydroisomerization of hydrocarbons
US3711399A (en) 1970-12-24 1973-01-16 Texaco Inc Selective hydrocracking and isomerization of paraffin hydrocarbons
US4900707A (en) 1987-12-18 1990-02-13 Exxon Research And Engineering Company Method for producing a wax isomerization catalyst

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB772478A (en) * 1952-03-18 1957-04-17 Gulf Research Development Co Improved process of hydroisomerization of hydrocarbons
US3711399A (en) 1970-12-24 1973-01-16 Texaco Inc Selective hydrocracking and isomerization of paraffin hydrocarbons
US4900707A (en) 1987-12-18 1990-02-13 Exxon Research And Engineering Company Method for producing a wax isomerization catalyst

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6951605B2 (en) 2002-10-08 2005-10-04 Exxonmobil Research And Engineering Company Method for making lube basestocks
US7077947B2 (en) 2002-10-08 2006-07-18 Exxonmobil Research And Engineering Company Process for preparing basestocks having high VI using oxygenated dewaxing catalyst
US7087152B2 (en) 2002-10-08 2006-08-08 Exxonmobil Research And Engineering Company Wax isomerate yield enhancement by oxygenate pretreatment of feed
US7125818B2 (en) 2002-10-08 2006-10-24 Exxonmobil Research & Engineering Co. Catalyst for wax isomerate yield enhancement by oxygenate pretreatment
US7220350B2 (en) 2002-10-08 2007-05-22 Exxonmobil Research And Engineering Company Wax isomerate yield enhancement by oxygenate pretreatment of catalyst
US7282137B2 (en) 2002-10-08 2007-10-16 Exxonmobil Research And Engineering Company Process for preparing basestocks having high VI
US7429318B2 (en) 2002-10-08 2008-09-30 Exxonmobil Research And Engineering Company Process for preparing basestocks having high VI using oxygenated dewaxing catalyst
US7670983B2 (en) 2002-10-08 2010-03-02 Exxonmobil Research And Engineering Company Oxygenate treatment of dewaxing catalyst for greater yield of dewaxed product
US7704379B2 (en) 2002-10-08 2010-04-27 Exxonmobil Research And Engineering Company Dual catalyst system for hydroisomerization of Fischer-Tropsch wax and waxy raffinate

Also Published As

Publication number Publication date
DE69514476T2 (de) 2000-08-24
AU689286B2 (en) 1998-03-26
NO953255L (no) 1996-02-20
AU3010795A (en) 1996-02-29
JP3671246B2 (ja) 2005-07-13
DE69514476D1 (de) 2000-02-17
CA2156212A1 (en) 1996-04-14
CA2156212C (en) 2004-01-06
EP0707057B1 (de) 2000-01-12
JPH08176561A (ja) 1996-07-09
NO311178B1 (no) 2001-10-22
NO953255D0 (no) 1995-08-18

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