EP0188898B1 - Procédé de déparaffinage en cascade - Google Patents

Procédé de déparaffinage en cascade Download PDF

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Publication number
EP0188898B1
EP0188898B1 EP19850309273 EP85309273A EP0188898B1 EP 0188898 B1 EP0188898 B1 EP 0188898B1 EP 19850309273 EP19850309273 EP 19850309273 EP 85309273 A EP85309273 A EP 85309273A EP 0188898 B1 EP0188898 B1 EP 0188898B1
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Prior art keywords
process according
zsm
zeolite
contacting
catalyst
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EP0188898A3 (en
EP0188898A2 (fr
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Nai Yuen Chen
Jeffrey Hsing-Gan Yen
Tracy Jau-Hau Huang
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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
    • 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

  • This invention relates to a cascade dewaxing process using a large pore crystalline zeolite as catalyst in a first contacting with a feedstock and a medium pore crystalline zeolite catalyst in a subsequent contacting.
  • lubricating oil or lube oil is that part of a hydrocarbon feedstock having a boiling point of 650°F (343°C) or higher as determined by ASTM D-97 test method.
  • a suitable crude oil contains a quantity of lubricant stock having a predetermined set of properties, such as, for example, 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 the sense that if all the separated fractions were recombined, one would reconstitute the crude oil.
  • a refined lubricant stock may be used by itself, or it may be blended with another refined lubricant stock having different properties. Prior to use it may be compounded with one or more additives which function, for example, as antioxidants, extreme pressure additives, V.I. improvers.
  • a high grade distillate lubricating oil stock it is known to vacuum distill an atmospheric tower residuum from an appropriate crude oil as the first step.
  • This step provides one or more raw stocks within the boiling range of about 450°F to 1050°F (232-566°C).
  • a solvent e.g., furfural, phenol, sulfolane, or chlorex, which is selective for aromatic hydrocarbons, and which removes undesirable components.
  • the raffinate from solvent refining is then dewaxed, for example, by admixing with a solvent, such as a blend of methylethyl ketone and toluene.
  • the mixture is chilled to induce crystallization of the paraffin waxes, which are then separated from the raffinate. Sufficient quantities of wax are removed to provide the desired pour point for the raffinate.
  • Viscosity index is a quality parameter of considerable importance for distillate lubricating oils to be used in automotive engines and aircraft engines subject to wide variations in temperature. This index indicates the degree of change of viscosity with temperature. A high V.I. of 100 indicates an oil that does not tend to become viscous at low temperature or become thin at high temperatures. Measurement of the Saybolt Universal Viscosity of an oil at 100°F (38°C) and 210°F (99°C), and referral to correlations, provides a measure of the V.I. of the oil. For purposes of the present invention, whenever W.I. is referred to, it is meant the V.I. as noted in the Viscosity Index tabulations of the ASTM (D567), published by ASTM, 1916 Race Street, Philadelphia, PA, or equivalent.
  • US ⁇ A ⁇ 3,700,585 describes a process for catalytic dewaxing with a catalyst comprising zeolite ZSM-5. Such a process combined with catalytic hydrofinishing is described in US-A-3,894,936.
  • US ⁇ A ⁇ 3,956,102 discloses a particular method for dewaxing a petroleum distillate with a ZSM-5 catalyst.
  • US ⁇ A ⁇ 3,769,202 teaches catalytic conversion of hydrocarbons using as a catalyst two different crystalline silicate zeolites, one having a pore size greater than 8 Angstroms and the other having a pore size less than 7 Angstroms, and that a conventional hydrogenation/dehydrogenation component may be added, in an amount from about 0.01 to about 30 wt. %.
  • a process for dewaxing a hydrocarbon feedstock comprises, first, contacting said feedstock at elevated temperature with a catalyst comprising a crystalline zeolite having a constraint index less than 2, possessing acidic sites and associated with a catalytically effective quantity of a component possessing hydrogenation/dehydrogenation activity, and, second, contacting at least the majority of the effluent from said first contacting, at elevated temperature, with a catalyst comprising a crystalline zeolite having a constraint index greater than 2, possessing acidic sites and associated with a catalytically effective quantity of a component possessing hydrogenation/dehydrogenation activity, and recovering a normally liquid hydrocarbon product of reduced wax content relative to said feedstock.
  • the first and/or second contacting is preferably carried out in the presence of added hydrogen, each hydrogenation/dehydrogenation component comprising a metal of Group VI, VII and/or VIII of the Periodic Table.
  • a metal is a Group VIII noble metal it usually constitutes 0.1 to 5, suitably 0.3 to 3, wt. % of the catalyst with which it is associated.
  • a non-noble metal it usually constitutes 0.3 to 25 wt % of the catalyst with which it is associated.
  • the process is typically conducted at an overall liquid hourly space velocity between 0.1 and 5, preferably between 0.2 and 3.0.
  • Each contacting may be carried out at a temperature in the range 232 to 371°C (450 to 700°F), a liquid hourly space velocity of 0.1 to 10 and a pressure no greater than 70 bar (1000 psig), advantageously below 42.5 bar (600 psig), even more advantageously below 28.5 bar (400 psig).
  • the preferred individual stage liquid hourly space velocity is 0.2 to 6.0.
  • the usual form of reactor for the first and/or second contacting is a fixed slurry or moving bed unit.
  • Large pore zeolites for use in the first contacting embrace zeolite Y, ultrastable zeolite Y, dealuminised zeolite Y, ZSM-3, ZSM-18 or ZSM-20, medium pore zeolites for use in the second contacting, zeolite ZSM-12, ZSM-23, ZSM-35, ZSM-38, ZSM-48 or TMA Offretite.
  • the large pore zeolite of choice is zeolite beta, and in such cases the hydrogenation/dehydrogenation component associated with the zeolite will usually be platinum.
  • the zeolite of choice for the second contacting will in many applications be ZSM-5, or on occasion ZSM-11, usually associated with nickel.
  • the feedstock contains waxy components which are normal and/or slightly branched paraffins, and the majority of it may be expected to have a boiling point above 250°C.
  • the process may advantageously be controlled so that the normally liquid effluent from the first contacting has a pour point less than that of said feedstock but no less than 50°F (10°C), optionally no less than 70°F (21°C).
  • the activity of the zeolite employed in the first contacting may advantageously be reduced prior to the contacting, and optionally a 650°F- (343°C-) fraction may be removed from the effluent of the first contacting before the second contacting is performed.
  • the invention concerns a dewaxing process which comprises:
  • This embodiment may be regarded as directed to a cascade catalytic dewaxing process wherein a solvent-refined raffinate feedstock is sequentially passed over a first reaction zone containing a zeolite from the group having the structure of TEA Mordenite, Zeolite Y, Deal Y, USY, REY, Zeolite Beta, ZSM-4, ZSM-20, H-Zeolon and amorphous alumina, and having a silica/alumina ratio greater than 10, and having associated therewith acidic sites and 0.1 to 25 wt.
  • a zeolite from the group having the structure of TEA Mordenite, Zeolite Y, Deal Y, USY, REY, Zeolite Beta, ZSM-4, ZSM-20, H-Zeolon and amorphous alumina, and having a silica/alumina ratio greater than 10, and having associated therewith acidic sites and 0.1 to 25 wt.
  • % of a hydrogenation/dehydrogenation component selected from the metals of Groups VI, VII, and VIII passing the entire effluent from the first reaction zone into a second reaction zone containing a medium pore zeolite having the structure of ZSM-5, ZSM-11, ZSM-12, ZSM-23, ZSM-34, ZSM-35, ZSM-38, ZSM-48, TMA Offretite and Erionite, and containing from 0.1 to 25 wt. % of a hydrogenation/dehydrogenation component selected from the group of Group VI, VII and VIII and mixtures thereof, to produce a hydrocarbon liquid product with a reduced wax content.
  • Zeolite Beta is place in the first stage reactor, it is optional, and in fact preferred in the embodiment, to discard the reaction product of the first stage for the first 1 or 2 days after fresh catalyst has been added to the first reactor. It is believed that the product of the chargestock as it passes through the highly active fresh catalyst of the first reactor, will contain poisons which will damage the shape-selective catalyst in the second reactor. After a period of 1 or 2 days onstream, the fresh catalyst will have had a chance to age and stabilize in order to produce a chargestock product which will be suitable for feeding to the second stage catalyst. Other methods of aging the catalyst of the first reactor are known to the art, such as, for example, steaming the catalyst.
  • the interstage separation step offers a variety of advantages over and above those disclosed by a cascade reaction system without interstage separation. It is speculated that the interstage separation process rids a variety of poisons from the chargestock.
  • the 650 0- F (343°C) stock is not considered a lube stock, and contains such components as alkyl aromatics, nitrogen components, and other "poisons". Some of these products are useful for the production of naphthas, gasoline and distillates. However, they may damage the effectiveness of the second and subsequent stages of a cascade reactor process.
  • the interstage separation step is that it lowers the start of cycle (SOC) and line out (LO) temperatures.
  • SOC temperature is the temperature at which catalysis is initiated.
  • LO temperature is that temperature where the activity of the catalyst begins to level out. It is well known in the field of catalytic conversion that a fresh catalyst exhibits high activity and aging during the first part of the catalytic conversion process. After a certain amount of time, generally about 2 to 12 days, the activity and the aging process of the catalyst begin to settle or line out. By ridding the chargestock of the 650 0- F (343°C) component, the SOC and LO temperatures are much lower. This will be considered more directly with respect to the examples.
  • this embodiment will frequently take the form of a cascade catalytic dewaxing process wherein a hydrocarbon feedstock with a boiling point in excess of 482°F (250°C) and containing normal paraffins and slightly branched chain paraffins is sequentially passed over a first reaction zone containing a zeolite from the group having the structure of Mordenite, Zeolite Y, Zeolite Beta, ZSM-4 and ZSM-20, and having a silica/alumina ratio greater than 10, and having associated therewith acidic sites and 0.1 to 25 wt.
  • the feedstock is hydroisomerized over the high silica, large pore zeolite catalyst, followed by shape selective dewaxing in the second stage over ZSM-11.
  • ZSM-11 has a Constraint Index between 6 and 8.7 and an effective pore size of generally not greater than about 7 Angstroms, so as freely to sorb normal hexane. In many process applications it has shown little or no difference from ZSM-5. However, as reported in Faraday Disc. Chem. Soc., 72, p. 353 (1982), ZSM-11 has shown high hydroisomerization activity where ZSM-5 exhibits only shape-selective cracking. Additionally, the structure of ZSM-11 has intersecting linear channels, rather than the intersecting linear and tortuous channels of ZSM-5. Although conventional dewaxing catalysts generally utilize a zeolite having the structure of ZSM-5, it will be seen in the Examples which follow that the ZSM-11 can be more active and selective for dewaxing than ZSM-5.
  • the acidity of the ZSM-11 zeolite will usually be very similar to the acidity of the large pore zeolite. If it is desired, for reasons of economy or otherwise, to use a noble metal promoter in association with a large pore zeolite, and a base metal promoter in association with ZSM-11, it may be beneficial to operate with different acidities or silica/alumina ratios in the large pore zeolite and ZSM-11. Best results will be obtained when the acidity of the ZSM-11 zeolite is matched to the strength and amount of the hydrogenation/dehydrogenation component incorporated in the ZSM-11 zeolite.
  • a cascade operation in this embodiment may be achieved by using a large down flow reactor, wherein the lower portion contains the catalyst comprising the ZSM-11 zeolite and the upper portion contains the catalyst comprising the large pore zeolite.
  • Two or more reactors in series may also be used, e.g., a three-reactor system may be used.
  • the first one or two reactors in series would contain the relatively large pore zeolite, while the last, and optionally all or a portion of the second reactor would contain the ZSM-11 zeolite.
  • Both stages, i.e., the large pore zeolite reactor and the ZSM-11 zeolite reactor are operated in the presence of hydrogen and under the same pressure.
  • This embodiment may also be regarded as directed to a cascade catalytic dewaxing process wherein a hydrocarbon feedstock with a boiling point in excess of 482°F (250°C) and containing normal paraffins and slightly branched chain paraffins is sequentially passed over a first reaction zone containing a zeolite from the group having the structure of Mordenite, Zeolite Y, Zeolite Beta, ZSM-4 and ZSM-20, and having a silica/alumina ratio greater than 10, and having associated therewith acidic sites and 0.1 to 25 wt.
  • % of a hydrogenation/dehydrogenation component selected from the metals of Groups VI, VII and VIII passing the entire effluent from the first reaction zone into a second reaction zone containing a medium pore zeolite selected from the group having the structure of ZSM-5 and ZSM-11, having a silica to alumina ratio greater than 10 and containing from 0.1 to 25 wt. % of a hydrogenation/dehydrogenation component selected from the group of Groups VI, VII and VIII and mixtures thereof, to produce a hydrocarbon liquid product with a reduced wax content.
  • the present invention is preferably arranged in a two-stage cascading relationship whereby, in the first stage, the feedstock is hydroisomerized over a high silica large pore zeolite catalyst, followed by shape selective dewaxing in the second stage over a medium pore zeolite catalyst. It is believed that a cascade relationship of the large pore zeolite and the medium pore zeolite, in the right proportion, will offer superior dewaxing activities and lube yield, higher V.I., improved catalyst stability in the second stage and flexibility in catalyst regeneration than the lube dewaxing catalysts of the prior art.
  • the present process may be used to dewax a variety of feedstocks ranging from relatively light distillate fractions up to high boiling stocks, such as whole crude petroleum, reduced crudes, vacuum tower residua, propane deasphalted residua, e.g., brightstock, cycle oils, FCC tower bottoms, gas oils, vacuum gas oils, deasphalted residua and other heavy oils.
  • feedstock will normally be a C10 feedstock since lighter oils will usually be free of significant quantities of waxy components.
  • the process is also particularly useful with waxy distillate stocks, such as gas oils, kerosenes, jet fuels, lubricating oil stocks, heating oils, hydrotreated oil stock, solvent-refined raffinate, furfural-extracted lubricating oil stock, and other distillate fractions whose pour point and viscosity need to be maintained within certain specification limits.
  • Lubricating oil stocks for example, will generally boil above 450°F (230°C), and more easily above 600°F (313°C).
  • the process is also useful for solvent refined neutral oil and hydrocracked oil produced by the catalytic hydrocracking or hydrotreating of hydrocarbon feedstocks boiling about 650°F (343°C).
  • the catalysts used according to the invention are zeolites, a term employed herein to designate not only aluminosilicates having a crystal lattice made up of Si0 4 and AI0 4 tetrahedra cross-linked by the sharing of oxygen atoms but also such structures from which aluminum is absent, and which may thus be termed crystalline silicates, or is replaced by a different lattice component.
  • Such other components may be present in minor amounts, usually less than 14 mole %, and preferably less than 4 mole %, and include gallium, iron, boron and the like.
  • the silica-to-alumina mole ratio of an aluminosilicate zeolite may be determined by conventional analysis. This ratio is meant to represent, as closely as possible, the ratio in the zeolite crystal lattice and to exclude aluminum in the binder or in cationic or other forms within the channels. Although zeolites with a silica-to-alumina mole ratio of at least 10 are useful, it is preferred to use zeolites having much higher silica-to-alumina mole ratios, i.e., ratios of at least 50:1.
  • zeolites which are substantially free of aluminum, i.e., having silica-to-alumina mole ratios of the order of 500, and up to and including infinity, are found to be useful and even preferable in some instances. Such zeolites, after activation, acquire an intracrystalline sorption affinity for normal hexane which is greater than that for water, i.e., they exhibit "hydrophobic" properties.
  • Constraint Index A convenient measure of the extent to which a zeolite impedes access by molecules of varying sizes to its internal structure is the Constraint Index of the zeolite. Zeolites which provide a highly restricted access to and egress from their internal structure have a high Constraint Index, and zeolites of this kind usually have pores of small size. On the other hand, zeolites which provide relatively free access to the internal zeolite structure have a low Constraint Index. The method by which Constraint Index is determined is described fully in US-A-4,016,218, to which reference is made for details of the method.
  • Constraint Index Cl Constraint Index
  • Constraint Index is a critical factor in the definition of those zeolites which are useful in the invention. The very nature of this parameter and the technique by which it is determined, however, admit of the possibility that a given zeolite can be tested under somewhat different conditions and thereby exhibit different Constraint Indices. Constraint Index seems to vary somewhat with severity of operation (conversion) and the presence or absence of binders. Likewise, other variables, such as crystal size of the zeolite, the presence of occluded contaminants, etc., may affect the Constraint Index. Therefore, it will be appreciated that it may be possible to so select test conditions as to establish more than one value for the Constraint Index of a particular zeolite. This explains the range of Constraint Indices provided for some zeolites, such as ZSM-5, ZSM-11, ZSM-34 and Zeolite Beta.
  • Zeolites ZSM-3, -4, -5, -11, -12, -18, -20, -23, -34, -35, -38, -48 and beta are defined by the x-ray data set forth in US ⁇ A ⁇ 3,415,736; 3,923,639; 3,702,886; 3,709,979; 3,832,449; 3,950,496; 3,972,983; 4,076,342; 4,086,186; 4,016,245; 4,046,859; 4,397,827; and 3,308,069, respectively.
  • Large pore zeolites i.e., those zeolites having a Constraint Index less than 2 and used in the first contacting hereof, are well known to the art and have a pore size sufficiently large to admit the vast majority of components normally found in a feed charge stock. They are generally considered to have a pore size in excess of 7 Angstroms and are represented by, e.g., Zeolite Beta, Zeolite Y, Mordenite, ZSM-3, ZSM-4, ZSM-18 and ZSM-20. An exceptionally suitable large pore material is zeolite beta, although all of these zeolites provide hydroisomerization activity.
  • the preferred hydrogenation components to be associated with the large pore zeolite are the noble metals of Group VIIIA, especially platinum, but other noble metals, such as palladium, rhenium or rhodium, may also be used.
  • noble metals such as platinum-rhenium, platinum-palladium, platinum-iridium or platinum-iridium-rhenium, with combinations with non-noble metals, particularly of Groups VIA and VIIIA are of interest, particularly with metals such as cobalt, nickel, vanadium, tungsten, titanium and molybdenum, for example, platinum-tungsten, platinum-nickel or platinum-nickel-tungsten.
  • Base metal hydrogenation components may also be used, especially nickel, cobalt, molybdenum, tungsten, copper or zinc.
  • Combinations of base metals such as cobalt-nickel, cobalt-molybdenum, nickel-tungsten, cobalt-nickel-tungsten or cobalt-nickel-titanium, may also be used.
  • the metal may be incorporated into the catalyst by any suitable method, such as impregnation or exchange.
  • the metal may be incorporated in the form of a cationic, anionic or neutral complex.
  • the large-pore-catalysed (isomerization) reaction is one which requires a relatively small degree of acidic functionality in the catalyst.
  • the zeolite may have a very high silica:alumina ratio, since this ratio is inversely related to the acid site density of the catalyst.
  • structural silica:alumina ratios of 50:1 or higher are preferred and, in fact, the ratio may be much higher, e.g., 100:1, 200:1, 500:1, 1000:1, or even higher. Since zeolites are known to retain their acidic functionality even at very high silica:alumina ratios of the order of 25,000:1, ratios of this magnitude or even higher are contemplated.
  • the original cations associated with the zeolites utilized herein may be replaced by a wide variety of other cations, according to techniques well known in the art.
  • Replacing cations include hydrogen and metal cations, including mixtures of the same.
  • metallic cations particular reference is made to cations of metals such as rare earth metals, manganese, as well as metals of Group II A and B of the Periodic Table, e.g., zinc, and Group VIII of the Periodic Table, e.g. nickel, platinum and palladium.
  • the intermediate or medium pore size zeolites used in the second contacting hereof have a Constraint Index between 2 and 12 and an effective pore size of generally not greater than about 7 Angstroms, and freely sorb normal hexane.
  • the structure provides constrained access to larger molecules. It is sometimes possible to judge from a known crystal structure whether such constrained access exists. For example, if the only pore windows in a crystal are formed by 8-membered rings of silicon and aluminum atoms, then access by molecules of larger cross-section than normal hexane is excluded and the zeolite is not of the desired type. Windows of 10-membered rings are preferred, although in some instances excessive puckering of the rings or pore blockage may render these zeolites ineffective.
  • the preferred medium pore zeolites in this invention include those having the structure of ZSM-5, ZSM-11, ZSM-12, ZSM-23, ZSM-35, ZSM-38, ZSM-48 and TMA Offretite.
  • the medium pore zeolite is associated with a hydrogenation/dehydrogenation component, just as disclosed in relation to the large pore zeolites. It is not essential, but may be beneficial, to use different hydrogenation/dehydrogenation components for the medium pore and large pore zeolites.
  • the acidity of the medium pore zeolite will usually be very similar to the acidity of the large pore zeolite. If it is desired, for reasons of economy or otherwise, to use a noble metal promoter in association with a large pore zeolite, and a base metal promoter in association with a medium pore zeolite, it may be beneficial to operate with different acidities, or silica/alumina ratios, in the large pore and medium pore zeolites. Best results will be obtained when the acidity of the medium pore zeolite is matched to the strength and amount of the hydrogenation/dehydrogenation component incorporated in the medium pore zeolite.
  • medium pore zeolite into a conventional matrix, as discussed previously with regard to the use of matrix encapsulating agents for the large pore zeolites. It is possible, and preferable, to operate with the same matrix material for both the medium pore zeolite and the large pore zeolite.
  • hydrodewaxing conditions include a temperature of between about 450°F (230°C) and about 750°F (400°C), and a pressure between 0 (1 bar) and 1000 psig (70 bar), preferably below 600 psig (42.5 bar).
  • the liquid hourly space velocity (LHSV), i.e., volume of feedstock per volume of catalyst per hour, is generally in the range of 0.1 to 5.0, and preferably in the range of 0.2 to 2.0.
  • Both stages of the cascade process are operated in the presence of hydrogen at a hydrogen-to-feedstock ratio of generally between about 400 and about 8000 (71 to 1424 m 3 /m 3 ) and preferably between about 800 and 4000 standard cubic feet (SCF) (142.5 to 712 m 3 /m 3 ) of hydrogen per barrel of feed.
  • a hydrogen-to-feedstock ratio of generally between about 400 and about 8000 (71 to 1424 m 3 /m 3 ) and preferably between about 800 and 4000 standard cubic feet (SCF) (142.5 to 712 m 3 /m 3 ) of hydrogen per barrel of feed.
  • At least 90%, and preferably all, of the material passed over the large pore zeolite is also passed over the medium pore zeolite. In some embodiments there is no intermediate separation or cooling of fluid passing from one reaction zone to the next.
  • a cascade operation may be realised by using a large down flow reactor wherein the lower portion contains the catalyst comprising the medium pore zeolite and the upper portion contains the catalyst comprising the large pore zeolite.
  • Two or more reactors in series may also be used, e.g., a three-reactor system, the first one or two reactors in series containing the relatively large pore zeolite, the last, and optionally all or a portion of the second reactor, containing the medium pore zeolite.
  • Another criticality in this process is that the pressure must be no greater than 1000 psig (70 bar), preferably below 600 psig (42.5 bar).
  • both reactors are confined to the same temperature range of 450° to 750°F ( 230° - 4 00°C), and preferably 500 to 700°F (276-371°C), they can be operated under the same or different temperatures as desired.
  • hydrotreating It is frequently advantageous to conduct hydrotreating either immediately before or after catalytic dewaxing. Hydrotreating will usually be practised when necessary to remove sulfur or nitrogen or to meet some other product specification. Hydrotreating the feed before subjecting it to catalytic dewaxing advantageously converts many of the catalyst poisons in the hydrotreater or deposits them on the hydrotreating catalyst. Any convenient hydrotreating catalyst and processing conditions may be used.
  • the charge stock was a severely hydrotreated waxy heavy neutral base stock having the following properties:
  • a fixed-bed, down-flow operation was employed for both the cascade two-stage scheme and the single-stage processing.
  • 10 cc of 0.6% Pt/Zeolite Beta/A1 2 0 3 extrudate catalyst was mixed with an equal volume of sand and placed in the first reactor.
  • the platinum catalyst was steamed at 1000°F (538°C) for 72 hours prior to platinum exchange.
  • 10 cc of a steamed 1.1 % NiIZSM-5 extrudate catalyst was mixed with an equal volume of sand and placed in the second reactor. Both catalysts were presulfided prior to catalytic lube processing after the cascade operation.
  • the first catalyst was by-passed and the feedstock was directly charged into the second reactor.
  • Table 1 The results and process conditions are given in Table 1.
  • Example 2 The same experimental procedures as in Example 1 were employed except that a Ni/ZSM ⁇ 5 catalyst was used for the single-stage processing. The results and the processing conditions are presented in Table 2:
  • Example 3 was designed to show the effective differences of pressure on the lube yield obtained from the first stage (hydroisomerization) reactor using hydrotreated waxy bright stock as a charge stock. The same catalyst and experimental procedures as in Example 1 forthe first reactor were employed. The results and the processing conditions are given in Table 3:
  • Table 3 shows the effect of pressure on the lube yield obtained from the first stage (hydroisomerization) process using the hydrotreated waxy bright stock as a charge stock. At a given pour point of lube product, it can be seen that the lower pressure gave a higher lube yield. Table 3 also shows that the lube yield from the first stage reactor at 400 psig was decreased from 88.5 wt. % to 50.3 wt. % when the pour point of the lube fraction was reduced from +75° to +30°F. This indicates that severe conditions in the first stage reactor would significantly reduce the overall yield in the cascade two-stage operation. It should be noted that the 50.3 wt. % lube yield is already below the 59 wt.
  • % lube yield which can be achieved from single-stage shape selective dewaxing alone, as illustrated in Table 2. Therefore, it is not desirable in this context to operate the first stage in such a way that the pour point of the lube fraction is reduced to below approximately +50°F, and preferably +70°F.
  • This Example employs a solvent-refined raffinate oil chargestock having the following properties:
  • Examples 5-23 illustrate a dual catalyst cascade operation employing steamed 0.6% Pt/Zeolite Beta in the first zone and steamed 1.0% Ni/ZSM ⁇ 5 in the second zone of a two-tone reactor.
  • a fixed-bed, down-flow operation was employed for the cascade two-zone scheme. Both catalysts were reduced in situ of 400 psig of hydrogen and 900°F (480°C) for 1 hour. The results and process conditions are given in Table 5.
  • the cascade reactor system of Examples 5-23 improved viscosity index by up to 4 numbers.
  • Fig. 1 shows the effect of pour point on viscosity index for both a cascade and a single zone reactor
  • the viscosity index of solvent-refined raffinate is higher in the cascade reactor system than in the single zone reactor system at the designated pour point.
  • Fig. 2 illustrates the effect of the number of days a catalyst is on-stream for both a single zone and cascade reactor with regard to the temperature of the catalyst. It can be seen that after approximately 20 days on-stream, the temperature of the single zone reactor must operate in excess of 675°F (357°C) for efficient reaction to occur. In contrast, the cascade reactor system may operate in excess of 27 days below a reactor temperature of 675°F (357°C). Thus, the cascade reactor system operates more efficiently, for a larger period of time and produces a superior product for a solvent-refined raffinate chargestock, when compared to the single zone reactor.
  • Figure 3 illustrates the effect of the presence of interstage separation on the second stage reactor temperature with regard to days onstream. It can be seen that in the first few days onstream, the dewaxing catalyst aged at approximately 5°F (2.8°C) per day with an SOC temperature of 542°F (283°C). After 20 days onstream, the dewaxing catalyst lined out at about 585°F (307°C). In contrast, the cascade dewaxing process without interstage separation had an SOC temperature of 575°F (302°C) and lined out at 650°F. The aging rate after line-out was 0.5°F (0.28°C) per day.
  • the SOC temperature was 550°F (288°C) and aged at a rate of approximately 5°F/day until the end of cycle temperature (set at 675°F (357°C)).
  • the results indicate that the pretreatment of the chargestock over a large pore zeolite, preferably Zeolite Beta, and the removal of light ends, e.g., the 650°F- stock, can significantly reduce the severity level for the second reactor.
  • the chargestock was a light neutral lubricating oil chargestock having the following properties:
  • Examples 38 to 42 are comparative examples, showing the effects of three different catalysts on the chargestock as it was passed over the catalyst in a single reactor operation.
  • Example 38 illustrates the effect of a 0.5% Pt-ZSM-5 catalyst on the chargestock.
  • the platinum catalyst was reduced in situ at 900°F (482°C) and 400 psig of hydrogen for one hour before introducing the feed into the reactor.
  • the procedure of Example 38 was followed under conditions specified in Table 8, which also recites the results.
  • Example 39 illustrates the effect of a .44% Pt-Zeolite Beta on the chargestock.
  • the procedure of Example 39 was followed under conditions specified in Table 9, which also recites the results:
  • Example 39 illustrates the effect of .44% Pt-Zeolite Beta on the chargestock under reaction conditions different from those of Example 40 (reaction temperature 550°F vs. 800°F).
  • reaction temperature 550°F vs. 800°F reaction temperature 550°F vs. 800°F.
  • Example 39 illustrates the effect of .5% Pt/ZSM-11 on the chargestock.
  • the procedure of Example 39 was followed under conditions specified in Table 11, which also recites the results.
  • This Example illustrates the effect of 0.5% Pt/ZSM ⁇ 11/Zeolite Beta in admixture on the chargestock.
  • ZSM-11 was first calcined in a nitrogen atmosphere at 1000°F (538°C) for 3 hours to decompose tetrabutyl ammonium and other organics in its structure. The ZSM-11 was subsequently NH 4 NO 3 exchanged to reduce its Na content to less than 0.02%.
  • Zeolite Beta was pretreated similarly. 32.5 parts of NH 4 ZSM-11, 32.5 parts of NH 4 -Zeolite Beta and 35 parts of alpha alumina monohydrate were mulled together to form a uniform mixture which was then impregnated with H 2 PtCl 6 in a stream of C0 2 . The sample was finally sized to 30/60 mesh and activated with an air calcination for 3 hours at 1000°F (538°C). The sample was analyzed and found to contain 0.49 wt. % and 0.01 wt. % Na.
  • the runs were made in a 15/32" (1.19 cm) ID fixed-bed reactor with a spiral preheater and a three-zone furnace for good temperature control.
  • the platinum composite catalyst was reduced in situ at 900°F (482°C) and 400 psig of hydrogen for one hour before the reactor temperature was lowered to 500°F(260°C) and the feed was started pumping into the reactor.
  • the product stream leaving the reactor was passed through a heated trap, a cold water trap, and a gas-sampling bomb.
  • the gas samples were analyzed by mass spectrometry for C 1 ⁇ C 6 components. Liquid products were topped under less than 0.1 mm ⁇ Hg pressure, maximum pot temperature 400°F (204°C), to isolate the 650°F * part.
  • Light liquid products (the condensate in the cold trap and the overhead from topping) were sent for gas chromatography analysis. Overall material balances were made based on total liquid feed charge plus hydrogen.
  • Pt/ZSM-11 improved product yields by approximately 5% and 4%, respectively, and VI by about 2 and 4 numbers, respectively.
  • the cascade operation (Examples 44 and 45) enhanced catalyst activity by 25°-35°F (13.9-19.5°C) and improved product yields by 5% and VI by 3 numbers, respectively.
  • the cascade operation enhanced catalyst activity by at least 150°F (83.5°C), lube yield by 32% and VI by 16 numbers.
  • Pt-Zeolite Beta exhibits very little dewaxing activity at a temperature of 550°F; however, the dewaxing activity is greatly enhanced by the use of Zeolite Beta and ZSM-11 in a cascade relationship.
  • the cascade operation had a slightly lower catalyst activity, i.e., 5°-15°F (2.8-8.5°C), than Pt/ZSM-11 in the single reactor operation, but the cascade operation produced 3% more lube yield.
  • Equivalent lube yield and product VI were observed between the cascade operation and the single reactor operation utilizing the composite Pt-ZSM-5/Zeolite Beta catalyst.
  • the cascade operation offered a catalyst activity advantage of 25°-35°F.

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Claims (25)

1. Un procédé de déparaffinage d'une charge d'hydrocarbures comprenant les étapes suivantes: premièrement, mise de cette charge, à température élevée, au contact d'un catalyseur comprenant une zéolite cristalline dont l'indice de contrainte est inférieur à 2, qui possède des sites acides et qui est associée à une quantité catalytiquement efficace d'un composé possédant une activité d'hydrogénation/dés- hydrogénation et, deuxièmement, mise au moins de la majorité de l'effluent provenant de cette première étape de contact, à température élevée, au contact d'un catalyseur comprenant une zéolite cristalline dont l'indice de contrainte est supérieur à 2, qui possède des sites acides et qui est associée à une quantité catalytiquement efficace d'un composé possédant une activité d'hydrogénation/déshydrogénation, et récupération d'un hydrocarbure normalement liquide, à teneur en paraffines réduite par rapport à cette charge.
2. Un procédé selon la revendication 1, dans lequel la première et/ou la deuxième étape de mise en contact est effectuée en présence d'un supplément d'hydrogène.
3. Un procédé selon la revendication 1 ou la revendication 2, dans lequel chaque composé d'hydrogénation/déshydrogénation comprend un métal des groupes VI, VII et/ou VIII de la Classification Périodique des Eléments.
4. Un procédé selon la revendication 3, dans lequel ce métal est un métal noble du groupe VIII et représente de 0,1 à 5% en poids du catalyseur auquel il est associé.
5. Un procédé selon la revendication 4, dans lequel le métal représente de 0,3 à 3% en poids du catalyseur.
6. Un procédé selon l'une quelconque des revendications précédentes, dans lequel le composé d'hydrogénation/déshydrogénation est le platine.
7. Un procédé selon la revendication 3, dans lequel ce métal est un métal non noble et représente de 0,3 à 25% en poids du catalyseur auquel il est associé.
8. Un procédé selon l'une quelconque des revendications précédentes, dans lequel chaque étape de mise en contact est effectuée à une température comprise entre 232 et 371°C (450 et 700°F), une vitesse spatiale horaire liquide de 0,1 à 10 et une pression ne dépassant pas 70 bars (1 000 psig).
9. Un procédé selon l'une quelconque des revendications précédentes, dans lequel chaque mise en contact est effectuée à une pression inférieure à 42,5 bars.
10. Un procédé selon la revendication 9, dans lequel la pression est inférieure à 28,5 bars (400 psig).
11. Un procédé selon l'une quelconque des revendications précédentes, dans lequel chaque mise en contact est effectuée à une vitesse spatiale horaire liquide de 0,2 à 6,0.
12. Un procédé selon l'une quelconque des revendications précédentes, dans lequel la vitesse spatiale horaire liquide globale est comprise entre 0,1 et 5.
13. Un procédé selon la revendication 12, dans lequel la vitesse spatiale horaire liquide globale est comprise entre 0,2 et 3,0.
14. Un procédé selon l'une quelconque des revendications précédentes, dans lequel la première et/ou la seconde mise en contact est effectuée dans un lit fixe, un lit fluidisé ou un lit mobile.
15. Un procédé selon l'une quelconque des revendications précédentes, dans lequel la zéolite employée dans ladite première mise en contact est une zéolite Y, zéolite Y ultrastable, zéolite Y désaluminisée, ZSM-3, ZSM-18 ou ZSM-20.
16. Un procédé selon l'une quelconque des revendications précédentes, dans lequel la zéolite employée dans ladite deuxième mise en contact est une zéolite ZSM-5, ZSM-1 1, ZSM-12, ZSM-23, ZSM-35, ZSM-38, ZSM-48 ou une TMA Offretite.
17. Un procédé selon l'une quelconque des revendications 1 à 14, dans lequel la zéolite employée dans ladite première mise en contact est un zéolite bêta.
18. Un procédé selon l'une quelconque des revendications précédentes, dans lequel ladite charge contient des composants paraffiniques qui sont des paraffines normales et/ou des paraffines légèrement ramifiées.
19. Un procédé selon l'une quelconque des revendications précédentes, dans lequel l'effluent normalement liquide sortant de ladite première mise en contact présente un point d'écoulement inférieur à celui de ladite charge mais non inférieur à 10°C (50°F).
20. Un procédé selon la revendication 19, dans lequel ce point d'écoulement n'est pas inférieur à 21°C (70°F).
21. Un procédé selon l'une quelconque des revendications 7 à 20, dans lequel le composé d'hydrogénation/déshydrogénation qui est associé à la zéolite est le nickel.
22. Un composé selon l'une quelconque des revendications précédentes, dans lequel ladite charge est un raffinat raffiné au solvant.
23. Un procédé selon la revendication 22, dans lequel l'activité de la zéolite employée dans ladite première mise en contact est réduite avant la mise en contact.
24. Un procédé selon la revendication 22 ou la revendication 23, dans lequel une fraction 343°C-(650°F-) est retirée de l'effluent de ladite première mise en contact avant que l'on n'effectue cette seconde mise en contact.
25. Un procédé selon l'une quelconque des revendications 1 à 18, dans lequel le point d'ébullition d'au moins la majorité de ladite charge est supérieur à 250°C.
EP19850309273 1984-12-21 1985-12-19 Procédé de déparaffinage en cascade Expired EP0188898B1 (fr)

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US68500184A 1984-12-21 1984-12-21
US68500084A 1984-12-21 1984-12-21
US68508984A 1984-12-21 1984-12-21
US685089 1984-12-21
US685001 1984-12-21
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US73881885A 1985-05-29 1985-05-29
US738818 1985-05-29

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US4919788A (en) * 1984-12-21 1990-04-24 Mobil Oil Corporation Lubricant production process
AU603344B2 (en) * 1985-11-01 1990-11-15 Mobil Oil Corporation Two stage lubricant dewaxing process
CA1299131C (fr) * 1986-12-04 1992-04-21 Clinton R. Kennedy Procede pour le deparaffinage en continu d'huiles minerales
MY125670A (en) * 1995-06-13 2006-08-30 Shell Int Research Catalytic dewaxing process and catalyst composition
BR9710326A (pt) * 1996-07-15 1999-08-17 Chevron Usa Inc Processos para hidrocraqueamento de segundo est gio em um processo para processamento de hidrocarbonetos de Äleos lubrificantes para produ-Æo de um estoque de provisÆo de Äleo lubrificante para prepara-Æo e para produ-Æo de uma multiplicidade de mat-rias primas de Äleo lubrificante e para opera-Æo em uma refinaria para produzir um Äleo desengordurado
EP0989908A2 (fr) * 1997-06-18 2000-04-05 Exxon Chemical Patents Inc. Conversion d'un gaz de synthese en olefines de faible poids moleculaire a l'aide de tamis moleculaires modifies
US8182672B2 (en) * 2007-12-28 2012-05-22 Exxonmobil Research And Engineering Company Process for preparing lube basestocks having superior low temperature properties at high VI
US8303804B2 (en) 2008-10-06 2012-11-06 Exxonmobil Research And Engineering Company Process to improve jet fuels
LT3554693T (lt) * 2016-12-16 2022-12-12 Shell Internationale Research Maatschappij B.V. Katalizatoriaus sistema vaškui pašalinti
EP3781308A1 (fr) 2018-04-17 2021-02-24 Shell Internationale Research Maatschappij B.V. Système catalyseur pour le déparaffinage

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US4372839A (en) * 1981-01-13 1983-02-08 Mobil Oil Corporation Production of high viscosity index lubricating oil stock

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EP0188898A2 (fr) 1986-07-30
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