EP0304251A1 - Katalytisches Entwachsungsverfahren - Google Patents

Katalytisches Entwachsungsverfahren Download PDF

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Publication number
EP0304251A1
EP0304251A1 EP88307526A EP88307526A EP0304251A1 EP 0304251 A1 EP0304251 A1 EP 0304251A1 EP 88307526 A EP88307526 A EP 88307526A EP 88307526 A EP88307526 A EP 88307526A EP 0304251 A1 EP0304251 A1 EP 0304251A1
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European Patent Office
Prior art keywords
dewaxing
feed
catalyst
process according
cycle
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EP88307526A
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English (en)
French (fr)
Inventor
Emmerson Bowes
Fritz Arthur Smith
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Mobil Oil AS
ExxonMobil Oil Corp
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Mobil Oil AS
Mobil Oil Corp
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Priority claimed from US07/087,198 external-priority patent/US4921593A/en
Priority claimed from US07/087,199 external-priority patent/US4908120A/en
Application filed by Mobil Oil AS, Mobil Oil Corp filed Critical Mobil Oil AS
Publication of EP0304251A1 publication Critical patent/EP0304251A1/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
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
    • 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
    • C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
    • C10G65/02—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
    • C10G65/04—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only refining steps
    • C10G65/043—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only refining steps at least one step being a change in the structural skeleton

Definitions

  • the present invention relates to a catalytic dewaxing process for the production of low pour point lubricants.
  • Mineral oil lubricants are derived from various crude oil stocks by a variety of refining processes. Generally, these refining processes are directed towards obtaining a lubricant base stock of suitable boiling point, viscosity, viscosity index (VI) and other characteristics. Generally, the base stock will be produced from the crude oil by distillation of the crude in atmospheric and vacuum distillation towers, followed by the separation of undesirable aromatic components and finally, by dewaxing and various finishing steps.
  • the use of asphaltic type crudes is not preferred as the yield of acceptable lube stocks will be extremely low after the large quantities of aromatic components contained in such crudes have been separated out; paraffinic and naphthenic crude stocks will therefore be preferred but aromatic separation procedures will still be necessary in order to remove undesirable aromatic components.
  • the neutrals e.g. heavy neutral, light neutral, etc.
  • the aromatics will be extracted by solvent extraction using a solvent such as furfural, N-methyl-2-pyrrolidone phenol or another material which is selective for the extraction of the aromatic components.
  • the asphaltenes will first be removed in a propane deasphalting step followed by solvent extraction of residual aromatics to produce a lube generally referred to as bright stock.
  • a dewaxing step is normally necessary in order for the lubricant to have a satisfactorily low pour point and cloud point, so that it will not solidify or precipitate the less soluble paraffinic components under the influence of low temperatures.
  • the catalytic dewaxing processes which have been proposed are generally similar to those which have been proposed for dewaxing the middle distillate fractions such as heating oils, jet fuels and kerosenes, of which a number have been disclosed in the literature, for example, in Oil and Gas Journal , January 6, 1975, pp. 69-73 and U.S. Patents Nos. RE 28,398, 3,956,102 and 4,100, 056.
  • these processes operate by selectively cracking the normal and slightly branched paraffins to produce lower molecular weight products which may then be removed by distillation from the higher boiling lube stock.
  • the catalysts which have been proposed for this purpose have usually been zeolites which have a pore size which admits the straight chain, waxy n-paraffins either alone or with only slightly branched chain paraffins but which exclude more highly branched materials and cycloaliphatics.
  • Zeolites such as ZSM-5, ZSM-11, ZSM-12, ZSM-22, ZSM-23, ZSM-35, ZSM-38 and the synthetic ferrierites have been proposed for this purpose in dewaxing processes, as described in U.S. Patent Nos.
  • catalytic dewaxing processes of this type operate by selective cracking of the waxy components in the feed.
  • the increasing severity of operation may lead to unaceptably short cycle times between successive catalyst reactivations because the high level of paraffin cracking which takes place under these conditions tends to deposit coke on the catalyst more rapidly than usual so that the catalyst quickly becomes deactivated and the operating temperature required to achieve the target pour point may increase excessively.
  • cycle life may become extremely short and may even become as short as a matter of a few hours which is quite unacceptable for commercial operation.
  • the preliminary dewaxing steps are carried out under conditions of relatively low and relatively constant reactor inlet temperature.
  • the final dewaxing step is carried out under conditions which provide the required degree of dewaxing to achieve the target pour point. In the final dewaxing reactor, no attempt is made to keep to a constant temperature during the dewaxing cycle but rather, the temperature is progressively increased in the conventional manner to achieve the target pour point as the catalyst becomes deactivated during the course of the dewaxing cycle.
  • a single preliminary dewaxing step will be sufficient but with some highly waxy feeds it may be necessary to employ two or more preliminary dewaxing reactors, each of which is operated at a low temperature with relatively constant inlet temperature conditions during each dewaxing cycle.
  • This mode of operation is distinct from the normal catalytic dewaxing procedure where the dewaxing steps are conventionally operated so as to maintain constant yield or constant pour poiint.
  • This conventional type of operation requires the inlet temperature and, therefore, the average catalyst bed temperature of the reactor to be progressively increased over a relatively wide range of inlet temperatures, typically greater than 40°F (about 22° C) during each dewaxing cycle as the catalyst becomes deactivated by coke deposition and contamination from heteroatom containing impurities in the feed.
  • the present dewaxing process is generally applicable to the production of low pour point products from hydrocarbon feeds.
  • the feed will boil above the naphtha boiling range so that the initial boiling point will be at least about 330°F (about 165°C) or higher, e.g. 385°F+ (about 195°C+).
  • the present process may be used with distillates such as jet fuel, diesel fuel, heating oil and fuel oil to produce corresponding products of improved fluidity. It is, however, particularly useful for the production of low pour point lubricating products from lube boiling range hydrocarbon feeds.
  • lubricants generally have an initial boiling point of at least 650°F (about 345°C) in order to prevent excessive volatilisation during use.
  • the feed will necessarily be comprised of components which boil about 343°C (650°F) or higher but the presence of components boiling below 343°C (650°F) is not to be excluded although it should be understood that these components will be removed during subsequent separation steps so that they do not form part of the final dewaxed lubricant. It is, however, desirable to separate such components prior to the initial dewaxing since they only serve to load up the reactor and prevent it being used effectively for the dewaxing of the high boiling range materials.
  • the end point of a particular feed will be in the range of 750°F (about 400°C) to over about 1050°F (about 565°C) depending upon whether the feed is a distillate (neutral) feed or a deasphalted resid feed (bright stock).
  • the end point of the feed is not in itself significant although the presence of large amounts of high boiling, unextracted residual type materials will generally be undesirable because they are generally rich in coke precursors which lead to shortened cycle life for the dewaxing catalyst.
  • the present process may be used with neutral lube feeds ranging from light neutrals, e.g. from 21mm2s ⁇ 1 (100 SUS) at 40°C to 150mm2s ⁇ 1 (700 SUS) at 40°C, to bright stock.
  • Typical light to medium neutral stocks may have an IBP below 650°F (about 345°C) (ASTM D-2887) and the end point may be below 1000°F (about 540°C).
  • Heavier neutrals will generally boil in the range 650° - 1050°F (about 345° - 565°C, ASTM D-1160, 10 mm. Hg), typically from 650° to 1050°F (about 400° - 565°C, ASTM D-1160).
  • Residual feeds usually boil above 750°F (about 400°C) and have a 50% point above 850°F (about 455°C) (ASTM D 1160-1, 1 mm. Hg).
  • the lube feeds which are treated in the present process are highly waxy feeds which contain at least 25 and usually at least 35 weight percent waxy components.
  • the waxy components are n-paraffins and slightly branched chain paraffins, mainly mono methyl paraffins. The presence of such large quantities of waxy components implies that the feeds will be generally waxy in nature and characterized by high pour points and in many cases may be solid at ambient temperatures. Feeds of this type are typically obtained from highly paraffinic crude sources such as the southeast Asian crudes.
  • the 343°C+ (650°F+) distillates may be used for production of the distillate or neutral lubes and the vacuum tower residuum may be used after deasphalting for the production of bright stock lubes.
  • Aromatics may be removed from the distillate (neutral) feeds by solvent extraction using solvents such as phenol, furfural, N-methyl-pyrrolidone or other materials which are selective for the removal of aromatics.
  • the vacuum tower residuum may be deasphalted by conventional deasphalting techniques, preferably propane deasphalting.
  • the deasphalted resid may then be subjected to aromatics extraction by a conventional solvent extraction process as with the neutral stocks or used as such.
  • the solvent extraction steps may, however, be replaced by hydrotreating in order to effect aromatic saturation as well as to remove heteroatom contaminants such as nitrogen and sulfur.
  • Hydrotreating for this purpose is generally carried out at high pressure in order to increase aromatic saturation as much as possible and in most cases, pressures of at least 1000 psig (7000 kPa) and more typically at least 2000 psig (14,000 kPa) e.g. 2500 psig (17,340 kPa) will be used.
  • the hydrogen:oil ratio will be selected according to the aromatics concentration in the feed and the design degree of aromatics removal. It will generally be in excess of about 2000 SCF/bbl (356 n.l.l. ⁇ 1), usually in excess of 4000 SCF/bbl (712 3n.l.l. ⁇ 4) e.g. typically about 4500 SCF/bbl (800 n.l.l. ⁇ 1). Space velocities for the hydrotreating typically are in the range 0.25 to 5 and more commonly from 0.5 to 1 LHSV (hour ⁇ 1).
  • hydrotreating catalysts comprising a hydrogenation component or components on a solid, porous carrier.
  • the metal (hydrogenation) component is typically a metal of Group VIA or VIIIA of the Periodic Table, usually nickel, cobalt, molybdenum, tungsten or vanadium although noble metals such as platinum and palladium may be used if the feed is of sufficiently low hetero atom content.
  • the support is usually of low acidic activity in order to minimize the degree of cracking since the objective of the hydrotreating step is to convert aromatics to naphthenes and paraffins by saturation rather than by cracking to lower molecular weight components.
  • a small degree of acidic functionality is desired for hetero atom removal since this requires a limited degree of ring opening to be effective.
  • a typical example of a highly paraffinic feed which may treated by the present invention is a hydrotreated 343° - 454°C (650° - 850°F) (nominal) vacuum gas oil obtained from a North Sea crude of the composition shown in Table 1 below: Table 1 HDT North Sea Feed Nominal boiling range, °C 345-455 (650-850) API Gravity 31.0 H, wt.pct 13.76 S, wt.pct 0.012 N,ppmw 34 Pour point,°C (°F) 32 (90) KV at 100°C, mm2s ⁇ 1 4.139 P/N/A wt.% Paraffins 30 Naphthenes 42 Aromatics 28
  • a more highly paraffinic feed which is highly suitable for processing by the present procedure is the 343° - 540°C (650° - 1000°F) (nominal) vacuum gas oil obtained from a Minas (Indonesian) crude oil, having the composition set out in Table 2 below.
  • Table 2 Minas Gas Oil Nominal boiling range, °C (°F) 345°-540° (650°-1000°) API Gravity 33.0 Hydrogen, wt pct 13.6 Sulfur, wt pct 0.07 Nitrogen, ppmw 320 Basic Nitrogen, ppmw 160 CCR 0.04 Composition, wt pct Paraffins 60 Naphthenes 23 Aromatics 17 Bromine No. 0.8 KV, 100°C, cSt 4.18 Pour Point, °C (°F) 46 (115) 95% TBP, °C (°F) 510 (950)
  • Table 2 is the composition of a hydrotreated Minas VGO (hydrotreating over Ni-Mo/Al2O3 hydrotreating catalyst, 5620kPa (800 psig) H2, 377° - 390°C (710° - 735°F), 1 LHSV, 712 n.l.l. ⁇ 1 hydrogen: feed ratio).
  • Table 3 HDT Minas Feed Nominal boiling range, °C (°F) 345-510 (650-950) API Gravity 38.2 H, wt. pct 14.65 S, wt.
  • feeds which may suitably be treated by the present process include the difficult Kirkuk (Iraq) lube feeds such as the light (100 SUS) and medium (400 SUS) neutrals and the bright stock shown in Table 4 below.
  • the feed is subjected to catalytic dewaxing in the characteristic dewaxing steps of the present invention.
  • the catalytic dewaxing is carried out by contacting the feed under dewaxing conditions of elevated temperature and pressure with a catalyst which selectively removes the waxy components (n-paraffins and slightly branched chain paraffins, especially monomethyl paraffins) from the feed. Dewaxing is usually carried out in the presence of hydrogen.
  • Removal of the waxy components may be by shape selective cracking as is the case when the dewaxing catalyst comprises an intermediate pore size zeolite such as, for example, ZSM-5, ZSM-11, ZSM-22, ZSM-23 or a synthetic ferrierite such as ZSM-35 or ZSM-38 or by isomerisation when the dewaxing catalyst comprises zeolite beta.
  • ZSM-5 for the dewaxing of oils by shape selective cracking is disclosed, for example, in U.S. Patent No.
  • Catalyst aging is expected to be best when the dewaxing catalyst either employs either a silica binder or, preferably, is a binder-free zeolite catalyst. It has been found that when the zeolite is extruded without binder, unexpectedly low aging rates are achieved. These rates are five to ten times less than rates achieved with alumina-bound catalysts and significantly better than those obtained with silica-bound catalysts. Besides the advantage of a reduced aging rate, the absence of binder enables the amount of zeolite-the component actually effective for the dewaxing-to be increased in a reactor of given size.
  • alumina binder used for the catalysts is non-acidic in character and therefore would not be expected to participate in non-shape-selective catalytic cracking reactions, it does nevertheless have a deleterious effect which is overcome by the use of the present unbound zeolite catalysts.
  • silica is known to be superior to alumina in certain respects, as described in U.S. Patent No. 4,013,732, the present unbound catalysts are even better, for reasons that are not readily explicable.
  • the unbound (or, alternatively, self-bound) dewaxing catalysts used in the present process are suitably produced by the extrusion method described in U.S. Patent No. 4,582,815, to which reference is made for a description of the method and of the extruded products obtained by its use.
  • the method described there enables extrudates having high constraining strength to be produced on conventional extrusion equipment and accordingly, the method is eminently suitable for producing the present catalysts which are silica-rich (by reason of the silica content of the zeolite and the binder).
  • the catalysts are produced by mulling the zeolite, as described in U.S.
  • the catalysts are used in the form of extruded shaped particles.
  • the particles may be cylindrical or polygonal, e.g., square, rectangular, hexagonal, in cross section or any other shape which lends itself to formation by extrusion. Lobed shapes are particularly useful, e.g. tri-lobe (cloverleaf) or quadrulobe.
  • extrudates which have a minimum diffusion distance of not more than 0.025 inch (0.63mm), preferably not more than 0.02 inch (0.51 mm).
  • Catalysts of this type are particularly useful for dewaxing residual foods, for example, feeds with an IBP of at least 700°F (370°C) and a 50 vol.
  • a direct comparison between the bound and self-bound catalysts with typically heavy neutral feeds indicates that the self-bound catalyst achieves a reduction of about 65 to 75 percent in the initial aging rate with the same zeolitic dewaxing component.
  • the difference in the zeolite content of the catalysts accounts for roughly one-third to one-half of the directly observed benefit.
  • the benefit is reduced by a factor reflecting the greater packing density of the self-bound catalyst as compared to the bound catalyst. Typically, this factor is about 10 percent with densities of about 0.65 g/cc (self-bound) and 0.56 g/cc (bound).
  • Example 2 illustrates the improvement above and beyond the attributable to the change in space velocity relative to the zeolite upon changing from the bound to the unbound catalyst.
  • the aging mechanism is one which involves random plugging of the pores of the zeolite.
  • a very large amount of coke can be accomodated before shape selectivity changes occur and even more before activity decreases rapidly (a condition not reached at the high end of cycle temperature but probably inevitable eventually).
  • the random plugging is not "random" and there will be a tendency for contiguous plugging probably nearer the surface than deeper into the crystal.
  • the plugging materials or their precursors redistribute throughout the zeolite crystal.
  • the dewaxing is effected either by shape selective cracking as with the intermediate pore size zeolite such as ZSM-5 or by isomerisation, possibly accompanied by some cracking, as with zeolite beta, coke becomes deposited on the active catalyst sites during the dewaxing reactions and this progressively deactivates the catalyst.
  • the progressive deactivation of the catalyst is generally compensated for by a progressive increase in the temperature of the dewaxing operation as the dewaxing cycle proceeds.
  • the cycle requires to be terminated and the catalyst treated to restore its dewaxing activity and selectivity, either by a reactivation treatment with hydrogen at elevated temperature or other conventional technique for restoring the dewaxing capabilities of the catalyst.
  • Hydrogen treatment to activate the catalyst is useful between successive oxidative regenerations in which the coke deposits are burned off the catalyst in the presence of an oxygen containing gas.
  • oxidative regeneration tends to cause agglomeration of metal components (expecially noble metal components) on the dewaxing catalyst which reduces catalyst activity. Since oxidative regeneration effects a reactivation of the catalyst i.e. a reversal of the deactivation process which takes place during use, it is regarded as a "reactivation" for the purposes of this disclosure.
  • the dewaxing is carried out in at least two reactors with different conditions prevailing in each reactor.
  • a preliminary dewaxing is carried out in one of more reactors under relatively mild conditions so that coke deposition on the catalyst is maintained at a low level.
  • one preliminary dewaxing reactor will be sufficient but with extremely waxy feeds, it may be desirable to use two or more preliminary dewaxing reactors each of which is operated under relatively mild conditions so as to obtain an extended cycle life with the catalyst.
  • the preliminary dewaxing is operated so as to obtain an extended cycle life and because the pour point of the product of the preliminary dewaxing is of no moment, the temperature of the preliminary dewaxing is not raised as the catalyst becomes deactivated during the course of the cycle.
  • the preliminary dewaxing step is carried out at substantially constant reactor inlet temperature during the dewaxing cycle between catalyst reactivations and is maintained at a relatively low level. Minor variations in the inlet temperature and hence, to the average bed temperature in the reactor, may take place and may be desirable, for example, to compensate for changes in feed composition or to make some compensation for catalyst aging.
  • the inlet temperature may therefore be varied with a controlled and narrow range, for example, increasing not more than 40°F (about 22°C) or less, e.g. 25°F (about 14°C) during the cycle.
  • the exact temperature selected will depend upon the wax content of the feed, the target pour point and the acceptable duration of each cycle.
  • the temperature should be lower with the more highly waxy feeds e.g. with paraffin contents of at least 50 wt percent such as the hydrotreated Minas VGO described above.
  • the temperature of the first stage will not exceed about 400°C and in most cases will be below 380°C.
  • a temperature of 370°C was found to give a cycle life in excess of one month which is regarded as satisfactory.
  • the pour point of the oil was reduced from 60°C for the feed to 25°C at a line out temperature of 370°C with stable operation under these conditions indicating that cycle life could be extended even further.
  • the temperature in the first stage will usually be from 625° from 725°F with typical dewaxing catalysts and once a line out temperature has been achieved in each cycle, it will be maintained constant at that value during the cycle.
  • Hydrogen pressures will be typical of those used to afford catalytic dewaxing: because the dewaxing does not require hydrogen for stoichiometric balance regardless of whether it proceeds by shape selective cracking or by isomerisation, only low hydrogen pressures are needed, typically below 1000 psig (7000 kPa) and pressures below 500 psig (3550 kPa) are typical. Space Velocities are typically between 0.25 and 5 LHSV (hour ⁇ 1) more commonly from 0.5 to 2 LHSV.
  • hydrogen:oil ratios may be relatively low, typically below 4000 SCF/bbl (about 770 n.l.l. ⁇ 1) but normally in the range 1000 to 3000 SCF/bbl (about 180 - 535 n.l.l. ⁇ 1).
  • the function of the preliminary dewaxing step or step is to achieve a partial dewaxing under conditions of mild but constant severity and to obtain an extended cycle time for the catalyst used in this step or steps.
  • a final dewaxing is therefore carried out to bring the pour poiint within specification limits and this step is carried out under conditions which achieve the requisite degree of dewaxing.
  • extended cycle life for the catalyst in the secondary dewaxing step may be achieved even under the conditions of higher severity necessary to reduce the pour point to the desired level.
  • the secondary dewaxing step is characterized by being carried out under conditions of progressively increasing temperature between catalyst reactivations.
  • the inlet temperature to the final reactor will generally be between 250° and 425°C with start-of-cycle (SOC) temperature typically about 275°C and end of cycle (EOC) temperature typically going up to 400°C, depending upon the degree of dewaxing effected in the preliminary dewaxing step and the target pour point.
  • the temperature in the secondary dewaxing step is progressively raised to compensate for catalyst aging so that the dewaxed product conforms to pour point specifications.
  • the inlet temperature to the secondary step will therefore be raised over a relatively wide range greater than that over which the inlet temperature to the first reactor is varied.
  • the inlet temperature to the secondary dewaxing reactor will be increased by at least 25° (about 14°C) and typically more than 40°F (about 22°C). In most cases, a significantly greater increase will be necessary in the course of the cycle, for example, from 500°F (about 260°C) to about 670°F (about 355°C) i.e.
  • Interstage separation of light ends may take place between the dewaxing stages and is desirable since it will not only contribute to removal of inorganic heteroatoms but also avoid loading up the secondary reactors.
  • the dewaxed product may be subject to hydrotreating in order to saturate olefins in the lube boiling range produced by cracking so as to stabilize the product and also to remove any residual color bodies and to saturate aromatics.
  • the hydrotreating may be carried out under relatively mild conditions using relatively low temperature and hydrogen pressures. Temperatures below 300°C and hydrogen pressures below 100 psig (7000 kPa) are generally suitable since at this poiint it is not desired to carry out any extensive cracking neither is extensive aromatics saturation necessary. Space velocities are typically from 0.25 to 5, more commonly from 0.5 to 2 LHSV (hour ⁇ 1).
  • hydrogen circulation rates of 500 to 3000 SCF/bbl (about 90 - 535 n.l.l. ⁇ 1) are generally suitable.
  • the hydrotreating catalyst is generally chosen to have a relatively low acidity in view of the need to minimize cracking and because a significant degree of hetero atom removal has been accomplished at this stage, noble metal hydrogenation components may be employed such as platinum or palladium but base metals such as nickel, cobalt, tungsten, etc. or other metals from Groups VIA and VIIIA of the Periodic Table may also be used.
  • the support may be a low acidity intermediate pore size zeolite such as ZSM-5 which has been steamed to a low acidity level (alpha value) or subjected to alkali metal exchange to obtain the requisite level of acidity.
  • a zeolite of high silica:alumina ratio with low inherent acidity may be used or conventional hydrotreating catalyst support of the amorphous type such as alumina, silica or silica-alumina, again of low acidity may be employed.
  • a waxy feed comprised a furfural refined heavy neutral from a mainland Chinese crude source having the properties set out below in Table 5.
  • the product was hydrotreated (Cyanamid HDN-30, NiMo/Al2O3 catalyst, 268°C, 400 psig H2, 0.5 LHSV, 2500 SCF/bbl H2:oil) to saturate olefins.
  • the temperature was raised from the lowest to the highest value shown as the catalyst aged in an attempt to obtain a dewaxed lube oil product with a pour point of 16°F (-9°C).
  • the catalyst aging rate was so rapid that the target pour point could not be met after only one day on stream.
  • a pour point of 60°F (15°C) was attainable at the maximum temperature shown in the above Table for each case.
  • the runs in Examples 1,2,and 3 were terminated after about 4,2, and 6 days on stream, respectively, as the target pour point could not be attained at acceptable reactor temperatures.
  • This Example illustrates dewaxing using a preliminary dewaxing under low severity, constant temperature conditions coupled with a secondary dewaxing to target pour point.
  • the reactor configuration used is shown in the Figure. For simplicity and clarity the hydrogen circuit is not shown.
  • the feed passes into the preliminary (first stage) reactor to where it is partly dewaxed under conditions of substantially constant temperature during the dewaxing cycle.
  • the partly dewaxed product is fractionated in interstage separator 11 and the higher boiling fraction passed to the secondary reactor 12 in which it is dewaxed to target pour point with the reactor temperature being raised during the cycle to compensate for catalyst aging.
  • the dewaxed product then passes the hydrotreater 13 to saturate lube boiling range olefins to stabilize the product.
  • the hydrotreated, dewaxed product then passes the product separator 14 to remove products boiling below the lube boiling range. Cut points on separators 11 and 14 may be set as desired.
  • Cut point on separator 14 will be set according to product specification, e.g. to remove 650°F- (about 345°C-) fractions from the lube product. For demonstration purposes only, it was set at 330°F (165°C) in the Example, although obviously different values would be appropriate in normal operation.
  • the feed was the same solvent-refined heavy neutral raffinate used in Examples 1-3. It was subjected to dewaxing over the same 1% NiZSM-5 dewaxing catalyst used in Examples 1-3 at 400 psig (2860 kPa abs.) H2 pressure, 0.5 LHSV and a hydrogen:oil ratio of 2500 SCF/Bbl (445 n.l.l. ⁇ 1). Reactor inlet temperature was lined out at 370°C which produced a pour point of 26 up to 29°C for the partly dewaxed product consistently from 6 to 53 days on stream. An analysis of the partly dewaxed 330°F+ (165°C+) product is given below in Table 7. Table 7 Single Stage Dewaxed Product Sp.
  • the partly dewaxed 330°F+ (165°C+) product was fed to a secondary dewaxing stage at 400 psig (2860 kPa abs) H2 pressure, 0.5 LHSV, 2500 SCF/Bbl (445 n.l.l. ⁇ 1) H2:oil.
  • the reactor inlet temperature was raised from 290°C (SOC) to 380°C at eight days on stream and then maintained at this value until 11 days on stream (temperatures normalized to -9°C product pour point by 1°C/1°C pour), to activate a normalized aging rate of 11°C/day.
  • the product was cascaded to a hydrotreater to saturate lube boiling range olefins(Cyanamid HDN-30, NiMo/Al2O3 catalyst, 268°C 400 psig H2, 0.5 LHSV, 2500 SCF/Bbl H2O:oil). This did not affect the dewaxing results.

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EP88307526A 1987-08-20 1988-08-12 Katalytisches Entwachsungsverfahren Withdrawn EP0304251A1 (de)

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US87199 1979-10-22
US87198 1987-08-20
US07/087,198 US4921593A (en) 1987-08-20 1987-08-20 Catalytic dewaxing process
US07/087,199 US4908120A (en) 1987-08-20 1987-08-20 Catalytic dewaxing process using binder-free zeolite

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EP0304251A1 true EP0304251A1 (de) 1989-02-22

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JP (1) JPS6470594A (de)
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KR100483356B1 (ko) * 1995-11-21 2005-08-05 피나 테크놀러지, 인코포레이티드 니켈-실리카라이트촉매로디왁싱하는방법
KR100487044B1 (ko) * 2002-04-17 2005-05-06 주식회사 하슬라 전이금속의 수용성 염 용액의 코팅에 의한 채색 도자기의 제조방법
KR100476114B1 (ko) * 2003-12-04 2005-03-14 서찬기 하얀 도자기 표면에 사쿠라 꽃, 단풍잎 같은 다양한 붉은 반점을 갖는 도자기의 제조 방법
US7195706B2 (en) * 2003-12-23 2007-03-27 Chevron U.S.A. Inc. Finished lubricating comprising lubricating base oil with high monocycloparaffins and low multicycloparaffins
CN1966620B (zh) * 2005-11-16 2011-11-30 中国石油化工股份有限公司 一种催化脱蜡催化剂
JP5737981B2 (ja) * 2011-02-04 2015-06-17 独立行政法人石油天然ガス・金属鉱物資源機構 炭化水素油の製造方法
KR102884483B1 (ko) * 2023-09-14 2025-11-10 하태훈 아연결정유의 소성 조건에 따른 도자기 결정체 무늬 형성방법

Citations (2)

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US4446007A (en) * 1982-06-08 1984-05-01 Mobil Oil Corporation Hydrodewaxing
EP0181066A2 (de) * 1984-10-29 1986-05-14 Mobil Oil Corporation Verfahren zur Entwachsung von schweren Destillaten und residualen Flüssigkeiten

Patent Citations (2)

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Publication number Priority date Publication date Assignee Title
US4446007A (en) * 1982-06-08 1984-05-01 Mobil Oil Corporation Hydrodewaxing
EP0181066A2 (de) * 1984-10-29 1986-05-14 Mobil Oil Corporation Verfahren zur Entwachsung von schweren Destillaten und residualen Flüssigkeiten

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CN1031558A (zh) 1989-03-08
JPS6470594A (en) 1989-03-16
AU2013488A (en) 1989-02-23
KR890003926A (ko) 1989-04-18

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