EP0431448A1 - Procédé catalytique de préparation d'huiles lubrifiantes à bas point d'écoulement - Google Patents

Procédé catalytique de préparation d'huiles lubrifiantes à bas point d'écoulement Download PDF

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Publication number
EP0431448A1
EP0431448A1 EP90122676A EP90122676A EP0431448A1 EP 0431448 A1 EP0431448 A1 EP 0431448A1 EP 90122676 A EP90122676 A EP 90122676A EP 90122676 A EP90122676 A EP 90122676A EP 0431448 A1 EP0431448 A1 EP 0431448A1
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EP
European Patent Office
Prior art keywords
process according
catalyst
composite
dewaxing
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EP90122676A
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German (de)
English (en)
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EP0431448B1 (fr
Inventor
Robert Peter Leonard Absil
Philip Jay Angevine
Thomas Francis Degnan, Jr.
George Harry Hatzikos
Rene Bernard Lapierre
John Paul Mcwilliams
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ExxonMobil Oil Corp
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Mobil Oil Corp
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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
    • C10G45/60—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 characterised by the catalyst used
    • C10G45/64—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 characterised by the catalyst used containing crystalline alumino-silicates, e.g. molecular sieves
    • 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
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/10—Lubricating oil

Definitions

  • This invention relates to the processing of higher molecular weight vacuum distillates such as bright stock raffinates to lower their pour point.
  • a suitable feedstock for lubricant refining contains a quantity of lubricant stock having a predetermined set of properties such as appropriate viscosity, oxidation stability, and maintenance of fluidity at low temperatures.
  • the process of refining to isolate that lubricant stock consists of a set of subtractive unit operations which removes the unwanted components.
  • the most important of these unit operations include distillation, solvent refining, and dewaxing, which basically are physical separation processes in that if all the separated functions were recombined one would reconstitute the crude oil.
  • the complexity of the molecular makeup of the desired components is reflected by the first step in the lube refining process, vacuum distillation.
  • vacuum distillation the feed is separated into four boiling fractions, each of which has a different viscosity and a different mix of aromatics, naphthenes, paraffins, resins and asphaltenes. Separation must be exact because the resulting viscosity and composition cannot be adjusted later in subsequent refining steps.
  • the lightest fraction of the vacuum distillation step vacuum tower overhead, has a boiling range up to approximately 700°F (370°C) and is usually consigned to a fuel refinery to be made into light products.
  • the remaining three fractions can be used in preparing lube stock.
  • the second fraction, light neutral distillate has a boiling range between approximately 700 and 850°F (371 and 454°C), and is used to make low viscosity oils.
  • the fourth fraction, vacuum resid will not boil even under vacuum and will result in a lube base called "bright stock". This vacuum resid contains most of the resins and metals in the crude and all of the asphaltines.
  • Hydrotreating has been proposed to accomplish such upgrading.
  • a suitable fraction of a poor grade crude such as a California crude
  • the process is complex in that some of the oil is reduced in molecular weight and made unsuitable for lubes, but concurrently a substantial fraction of the polynuclear aromatics is hydrogenated to form naphthenes and paraffins.
  • Process conditions and choice of catalyst are selected to provide an optimal conversion of the polynuclear aromatic content of the stock, since this component degrades the viscosity index and stability of the stock.
  • hydrocracking is employed for processes such as the foregoing; by contrast the purpose of “hydrotreating” is to stabilize the lube base stock produced by hydrocracking. Hydrocracking and hydrotreating steps may be distinguished also by the amount of hydrogen consumed, the hydrocracking step typically consuming about 178 to 356 m3/m3 (1000-2000 SCF/bbl) while the hydrotreating step consumes only about a tenth as much.
  • hydrocracking process for increasing the availability of lube oils has an attractive feature that is not immediately apparent.
  • composition and properties of hydrocracked stocks are generally not particularly affected by the source and nature of the crude, i.e., they tend to be much more alike than fractions prepared from different crudes by conventional means.
  • the process therefore promises to free the refiner from dependence on a particular crude, with all of the advantages that this freedom implies.
  • Hydrocracked lube stocks tend to be unstable in the presence of air when exposed to sunlight. On such exposure, an unacceptable sludge is formed, sometimes very rapidly and in fairly substantial amount. Additionally, some hydrocracked lube oils tend to darken or to form a haze. Several methods have been proposed to correct this instability, such as those described in US-A-4,031,016, 3,666,657, 3,530,061, 4,162,962, 3,530,061 and 3,852,207.
  • Hydrocracked lubricating oils generally have an unacceptably high pour point and require dewaxing.
  • Catalytic methods for dewaxing have been proposed, for instance in US-A-3,700,585. Hydrotreating after catalytic dewaxing is disclosed in US-A-4,137,148.
  • US-A-4,283,271, 4,283,272, and 4,414,097 disclose processes for producing dewaxed lubricating oil base including hydrocracking a hydrocarbon feedstock, catalytically dewaxing the hydrocrackate and hydrotreating the dewaxed hydrocrackate, and employ catalyst compositions comprising zeolite ZSM-5, ZSM-11 and ZSM-23 for the dewaxing phase.
  • This invention provides an energy-efficient continuous process for producing dewaxed hydrocracked lubricating oil stock from a hydrocarbon feedstock effluent boiling over about 288°C (550°F), by passing such an effluent through a catalytic hydrodewaxing process in which the supported catalyst composition comprises a zeolite and matrix and, optionally, a Group VIII metal.
  • a cyclic catalytic dewaxing process for improving the pour point of a demetallized petroleum fraction free of components boiling below 371°C, comprises contacting a bright stock raffinate with a dewaxing catalyst at a temperature of 260 to 482°C, a pressure of 14.8 to 242.4 bar, a liquid hourly space velocity of 0.2 to 20 and a hydrogen circulation rate of 89 to 3560 m3/m3, said catalyst comprising a porous composite of a zeolite having a constraint index of 1 to 12 and a matrix whereof the zeolite constitutes 35 to 75 weight percent, at least 60 volume percent of the pores of said composite having a diameter less than 20 nm, the composite having a particle density of at least 1.0 g/cc.
  • Figure 1 is a plot of pore volume (cc/gm) vs. pore diameter
  • Figure 2 is a plot of reaction temperature vs. days on stream
  • Figure 3 is a plot of reaction temperature vs. days on stream.
  • Figure 4 is a plot of reactor temperature vs. days on stream.
  • the aging rate of dewaxing catalysts in dewaxing has been reduced. Accordingly, the start-of-cycle temperature in the second cycle, and subsequent cycles, of a multicycle dewaxing operation is reduced.
  • the capacity to reduce the aging rate of the dewaxing catalyst allows for longer periods between oxygen regeneration and hydrogen reactivation cycles and thus increases overall catalyst lifetime. It is noted that aging rate can be expressed by the daily increase in operating temperature necessary to maintain a product of constant pour point.
  • the benefits of the invention apply particularly to bright stock raffinate feedstocks, which induce among the fastest catalyst aging rates.
  • pore volume, pore size distribution and particle density can significantly affect catalytic performance.
  • a good example of this is in the design of demetallation catalysts, where a majority of the pores must be in the greater than 10 nm range to prevent pore plugging by deposited metals and to allow for diffusion of Ni- and V-containing porphyrins.
  • the design of the demetallation catalysts involves a critical balance between the required pore size distribution and the high surface area needed to produce the requisite activity.
  • the catalyst is a porous mixture, at least 60 percent of the pores of which, as measured by mercury porosimetry, have diameters less than 20 nm.
  • the average pore size of the mixture is preferably lower than 15 nm, more preferably lower than 10 nm, and in certain embodiments is less than 7 nm, and even less than 4 nm.
  • the particle density of the porous composite is at least 1.0 g/cc.
  • the zeolite component of the catalyst has a constraint index of 1 to 12.
  • the method by which constraint index is determined is described fully in US-A-4,016,218.
  • Constraint index (CI) values for some typical materials are:
  • test conditions e.g. temperature
  • constraint index of a particular zeolite e.g. ZSM-5, ZSM-11 and Beta.
  • the crystal size of the zeolite ranges from 0.02 to 0.05 micrometers.
  • the catalyst composition will generally, although not necessarily, contain a Group VIII metal, which when present may be exchanged into the composition, impregnated therein or physically and intimately admixed therewith by well known techniques.
  • the amount of Group VIII metal in the catalyst composition can range from 0.10 to 10 weight percent, preferably from about 0.1 to about 3 weight percent, most preferably from about 0.2 to about 1 weight percent, based on the total weight of the catalyst composition.
  • the Group VIII metal component can be platinum, palladium, iridium, ruthenium, cobalt, nickel, copper, molybdenum and mixtures thereof.
  • the preferred metal is nickel.
  • the Group VIII metal may be present alone or together with a metal from Group VI, such as chromium, molybdenum, tungsten and mixtures thereof.
  • the particle size (effective or hydraulic diameter) of preferred forms of the catalyst ranges from 0.75 to 3.2 mm.
  • the binder or matrix is suitably an alumina other than alpha alumina, preferably gammaalumina. Generally it is a small particle alumina with a packing density of 0.5 to 0.6 g/cc.
  • the matrix is characterized by a particle density of 0.95 to 1.50 g/cc.
  • Alumina monohydrate (pseudoboehmite) is converted into a desirably dense analogue during catalyst formation.
  • An alumina source for the matrix used for catalyst preparation preferably has a water content of 20 to 30 weight percent.
  • the alumina monohydrate used as the source of matrix material in the Examples has a water content of 28 percent.
  • the alumina source is convertible to gamma-alumina.
  • Gamma-alumina is a phase of alumina which occurs as a result of calcination at a temperature of no greater than about 538°C (1000°F).
  • deltaalumina is a result of calcination at a temperature of about 927°C (1700°F).
  • the zeolite, a Group VIII metal and a source of binder or matrix are mulled together to form a homogeneous mixture.
  • the important feature of the mulling step is the water content of the mixture.
  • the water content can be expressed as ash content of the mixture: the ash content can range from 40 to 60 wt%.
  • Water content can also be expressed as solid content, which can range from 45 to 60, preferably from 42 to 55 weight percent.
  • Mulling is undertaken at a temperature ranging from 10 to 37.7°C (50 to 100°F).
  • the mixture may contain 0.05 to 5 wt% of an extrusion aid such as polyvinyl alcohol.
  • Extrusion is undertaken in conventional apparatus to produce a particle with a length to diameter ratio of at least 2.
  • the matrix precursor can be alumina monohydrate (.e., pseudoboehmite), which during catalyst formation is converted to a more dense analogue.
  • alumina monohydrate .e., pseudoboehmite
  • the feed to the dewaxing unit is a fraction produced by vacuum distillation of crude oil which has been demetallized and is free of boiling range components having a boiling range up to about 700°F, in particular one based on the vacuum resid which as noted above will produce a lube base called bright stock.
  • a lube dewaxing catalyst was produced by preparing a mixture of 65 percent ZSM-5, 35 percent of a coarse, high-chemical purity, low density, high-surface-area alpha alumina monohydrate (pseudoboehmite), nickel nitrate hexahydrate, and enough water to form a paste-like mixture, mulling this mixture, and extruding it into 1.6 mm (1/16 inch) cylindrical pellets by conventional means.
  • the catalyst was pre-calcined in nitrogen for 3 hours at 482°C (900°F) (2.8°C/min heat-up) and then in air at 538°C (1000°F) for 3 hours. This procedure converts the alpha alumina monohydrate into gamma-alumina.
  • the physical properties and pore size distribution are shown in Table 1.
  • the catalyst in this example will be referred to as a medium pore diameter catalyst. This catalyst has 60 percent of its pore with diameters less than 20 nm (as measured by mercury porosimetry).
  • a lube dewaxing catalyst was produced by preparing a mixture of 65 percent ZSM-5, 21 percent of the same alpha alumina monohydrate (pseudoboehmite) used in Example 1, 14 percent delta alumina, nickel nitrate hexahydrate, and enough water to form a paste-like mixture, mulling this mixture, and extruding it into 1.6 mm (1/16 inch) cylindrical pellets by conventional means.
  • the delta alumina was prepared by calcining the alpha alumina monohydrate in air at 927°C (1700°F) for 4 hours.
  • the catalyst was pre-calcined in nitrogen for 3 hours at 482°C (900°F) (2.8°C/min heat-up) and then in air at 538°C (1000°F) for 3 hours.
  • the physical properties and pore size distribution are shown in Table 1.
  • the catalyst in this example will be referred to as a large pore diameter catalyst.
  • This catalyst has 44 volume percent of its pores (as measured by mercury porosimetry) with diameters less than 20 nm.
  • a lube dewaxing catalyst was produced by preparing a mixture of 65% ZSM-5, 35% of a finely divided, dense, high chemical purity alpha alumina monohydrate, Keith alumina (pseudoboehmite from Keith Corporation), nickel nitrate hexahydrate, and enough water to form a paste-like mixture, mulling this mixture, and extruding it into 1.6 mm (1/16 inch) cylindrical pellets by conventional means.
  • the catalyst was precalcined in nitrogen for 3 hours at 482°C (900°F) (2.8°C/min heat-up) and then in air at 5.38°C (1000°F) for 3 hours. This procedure converts the alpha alumina monohydrate into gamma alumina.
  • the physical properties and pore size distribution are shown in the following Table.
  • the catalyst in this example will be referred to as a small pore diameter catalyst. It has an average pore diameter of 4 nm, 92 volume percent of its pores (as measured by mercury porosimetry) being of diameter less than 20 nm.
  • the catalysts of Examples 1 and 2 were examined for dewaxing of paraffinic North Sea Heavy Neutral and Bright Stock raffinates. Properties of the feedstocks are given in Table 2. Both catalysts were able to produce -6.6°C (20°F) pour point products. The aging rates of the catalysts were tracked by adjusting the reaction temperature to compensate for activity loss so as to maintain a target -6.6°C (20°F) pour point while maintaining all other conditions constant.

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  • Chemical & Material Sciences (AREA)
  • Crystallography & Structural Chemistry (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)
  • Catalysts (AREA)
EP19900122676 1989-12-04 1990-11-27 Procédé catalytique de préparation d'huiles lubrifiantes à bas point d'écoulement Expired - Lifetime EP0431448B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US44520489A 1989-12-04 1989-12-04
US445204 1989-12-04

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EP0431448A1 true EP0431448A1 (fr) 1991-06-12
EP0431448B1 EP0431448B1 (fr) 1993-11-18

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EP (1) EP0431448B1 (fr)
JP (1) JPH03212493A (fr)
AU (1) AU629425B2 (fr)
CA (1) CA2029999A1 (fr)
DE (1) DE69004670T2 (fr)
ES (1) ES2045729T3 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2765207A1 (fr) * 1997-06-25 1998-12-31 Inst Francais Du Petrole Zeolithe nu-85, catalyseur et procede pour l'amelioration du point d'ecoulement de charges contenant des paraffines
FR2765209A1 (fr) * 1997-06-25 1998-12-31 Inst Francais Du Petrole Zeolithe eu-1, catalyseur et procede pour l'amelioration du point d'ecoulement de charges contenant des paraffines
FR2765208A1 (fr) * 1997-06-25 1998-12-31 Inst Francais Du Petrole Zeolithe nu-85, catalyseur et procede et pour l'amelioration du point d'ecoulement de charges contenant des paraffines
FR2765206A1 (fr) * 1997-06-25 1998-12-31 Inst Francais Du Petrole Zeolithe eu-1, catalyseur et procede pour l'amelioration du point d'ecoulement de charges contenant des paraffines

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0043681A1 (fr) * 1980-07-07 1982-01-13 Mobil Oil Corporation Procédé catalytique pour la production d'une huile lubrifiante
US4508615A (en) * 1984-02-16 1985-04-02 Mobil Oil Corporation Multi-stage process for demetalation, desulfurization and dewaxing of petroleum oils

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4510044A (en) * 1982-02-08 1985-04-09 Mobil Oil Corporation Process for hydrotreating petroleum residua and catalyst therefor
US4440630A (en) * 1982-02-08 1984-04-03 Mobil Oil Corporation Process for simultaneous hydrodesulfurization and hydrodewaxing with a catalyst of controlled pore size and metals content
US4510043A (en) * 1984-02-16 1985-04-09 Mobil Oil Corporation Process for dewaxing of petroleum oils prior to demetalation and desulfurization

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0043681A1 (fr) * 1980-07-07 1982-01-13 Mobil Oil Corporation Procédé catalytique pour la production d'une huile lubrifiante
US4508615A (en) * 1984-02-16 1985-04-02 Mobil Oil Corporation Multi-stage process for demetalation, desulfurization and dewaxing of petroleum oils

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2765207A1 (fr) * 1997-06-25 1998-12-31 Inst Francais Du Petrole Zeolithe nu-85, catalyseur et procede pour l'amelioration du point d'ecoulement de charges contenant des paraffines
FR2765209A1 (fr) * 1997-06-25 1998-12-31 Inst Francais Du Petrole Zeolithe eu-1, catalyseur et procede pour l'amelioration du point d'ecoulement de charges contenant des paraffines
FR2765208A1 (fr) * 1997-06-25 1998-12-31 Inst Francais Du Petrole Zeolithe nu-85, catalyseur et procede et pour l'amelioration du point d'ecoulement de charges contenant des paraffines
FR2765206A1 (fr) * 1997-06-25 1998-12-31 Inst Francais Du Petrole Zeolithe eu-1, catalyseur et procede pour l'amelioration du point d'ecoulement de charges contenant des paraffines
US6153548A (en) * 1997-06-25 2000-11-28 Institut Francais Du Petrole NU-85 zeolite catalyst and a process for improving the pour point of feeds containing paraffins
US6350370B1 (en) 1997-06-25 2002-02-26 Institut Francais Du Petrole NU-85 zeolite catalyst and a process for improving the pour point of feeds containing paraffins
US6733658B2 (en) 1997-06-25 2004-05-11 Institut Francais Du Petrole EU-1 zeolite catalyst and a process for the reduction of the pour point of feeds containing paraffins

Also Published As

Publication number Publication date
DE69004670T2 (de) 1994-03-10
EP0431448B1 (fr) 1993-11-18
CA2029999A1 (fr) 1991-06-05
JPH03212493A (ja) 1991-09-18
AU629425B2 (en) 1992-10-01
ES2045729T3 (es) 1994-01-16
DE69004670D1 (de) 1993-12-23
AU6652990A (en) 1991-06-06

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