EP0237655B1 - Prozess zur katalytischen Entwachsung von mehr als einem aus einer Raffinerie stammenden Grundöl-Precursor - Google Patents
Prozess zur katalytischen Entwachsung von mehr als einem aus einer Raffinerie stammenden Grundöl-Precursor Download PDFInfo
- Publication number
- EP0237655B1 EP0237655B1 EP86202162A EP86202162A EP0237655B1 EP 0237655 B1 EP0237655 B1 EP 0237655B1 EP 86202162 A EP86202162 A EP 86202162A EP 86202162 A EP86202162 A EP 86202162A EP 0237655 B1 EP0237655 B1 EP 0237655B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- lubricating base
- hydrodewaxing
- dewaxing
- process according
- refinery
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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- 238000006243 chemical reaction Methods 0.000 claims description 17
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- 125000004122 cyclic group Chemical group 0.000 description 5
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- 229910052799 carbon Inorganic materials 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 239000000356 contaminant Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000001491 aromatic compounds Chemical class 0.000 description 3
- 238000005194 fractionation Methods 0.000 description 3
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- 239000012188 paraffin wax Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical class [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000005341 cation exchange Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
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- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 2
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- 239000011707 mineral Substances 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
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- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000003209 petroleum derivative Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
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- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- -1 alkyl ketones Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
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- 230000008901 benefit Effects 0.000 description 1
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- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000010725 compressor oil Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
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- 238000007429 general method Methods 0.000 description 1
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- 238000011065 in-situ storage Methods 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229910001510 metal chloride Inorganic materials 0.000 description 1
- 239000010705 motor oil Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
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- 229910052712 strontium Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
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Images
Classifications
-
- 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
- C10G73/00—Recovery or refining of mineral waxes, e.g. montan wax
- C10G73/02—Recovery of petroleum waxes from hydrocarbon oils; Dewaxing of hydrocarbon oils
-
- 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
- C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
-
- 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
-
- 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
- C10G65/14—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural parallel stages only
- C10G65/16—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural parallel stages only including only refining steps
Definitions
- the invention relates to a process for catalytic dewaxing of more than one refinery-derived lubricating base oil precursor.
- tectosilicate catalyst with a pore size such that the long chain paraffin materials along with other waxy materials have selective access to the interior of the tectosilicate sieve while prohibiting entry of the non-waxy materials, which, of course, do not necessitate hydrodewaxing.
- lubricating base oil precursors can be derived which are commonly classified as (Light) HVI 80 to 100 or 80 to 150, (Medium) HVI 250 to 300, (Heavy) HVI 500 to 600 and HVI Bright Stock raffinate (hereinafter referred to as Bright Stock), all of which necessitate dewaxing before they can be used as lubricating base oil (components).
- Patent 4,372,839 recognition is made that a ZSM-35 catalyst alone is incapable of reducing the pour point to the most desired lowest level, however, this deficiency is resolved by a series flow technique of a common charge stream with both types of zeolites, i.e. a first contact with a ZSM-35 aluminosilicate and then a second with a ZSM-5 aluminosilicate.
- EP 161833 discloses a dewaxing process in which process "heavy" and "light” charge stocks are contacted with different catalysts.
- the "light” charge stock is defined by a 50% boiling-point of 454 °C and a kinematic viscosity at 100 °C of less than 9 cSt.
- this document fails to acknowledge the need to obtain and separately process two raffinate lubricating base oil precursors, where the separation is on the basis of the chemical nature of the waxy material present in the different lubricating base oil precursors.
- the HVI 250-300 lubricating oils cannot be adequately dewaxed in the process disclosed in EP 161833.
- An object of the invention is to provide a viable refinery dewaxing process flow scheme to selectively treat more than one refinery-derived lubricating base oil precursor in parallel flow in contrast to providing different catalysts in admixture in a single reactor which are respectively insufficient to treat one type of lubricating base oil precursor but highly efficient to treat another type of lubricating base oil precursor. Accordingly, a multiple number of dewaxed lubricating base oils having excellent pour points and viscosity indices can be obtained.
- the invention therefore related to a process for catalytic dewaxing of more than one refinery-derived lubricating base oil precursor which comprises contacting in a first reaction zone in the presence of a hydrogen-containing gas at hydrodewaxing conditions a first feed stream comprising a first refinery-derived raffinate lubricating base oil precursor which contains a first wax comprising straight-chain paraffins, said first wax containing less than 55% by weight of branched and cyclic hydrocarbons, with a first hydrodewaxing catalyst selective for conversion of said first wax and contacting in the presence of a hydrogen-containing gas at hydrodewaxing conditions in a parallelsituated second reaction zone a second refinery-derived raffinate lubricating base oil precursor which contains a second wax containing more than 55% by weight of branched and cyclic hydrocarbons with a second hydrodewaxing catalyst selective for conversion of said second wax, and optionally contacting in one or more further reaction zones further refinery-derived waxy r
- the process according to the invention suitably comprises three or more parallel operated catalytic hydrodewaxing zones.
- One embodiment of the invention resides in a process for the preparation of four or more dewaxed lubricating base oils from a crude oil feed stream which comprises: charging said crude oil feed stream to an atmospheric distillation column maintained at a pressure between 1.7 and 6.7 bar abs., at a bottoms temperature between 232 °C and 399 °C, and an overhead temperature of 204 °C to 316 °C to separate said crude oil feed stream into at least a light overhead stream, which is withdrawn from said atmospheric distillation unit, comprising heavy gas oil and lighter hydrocarbons and a bottoms stream, which is removed from said distillation unit, comprising heavier than heavy gas oil hydrocarbons; withdrawing said heavy gas oil and lighter hydrocarbons and passing the same to another refinery unit for further processing; charging the bottoms effluent from said atmospheric distillation column containing heavier than heavy gas oil to a vacuum distillation column maintained at an overhead pressure between 0.02 and 0.09 bar abs.
- All of the aforementioned four respective lubricating base oil precursor streams contain different waxy contaminants, i.e. waxy components which elevate the pour point to a degree such that the oils are less attractive for their intended use. These streams differ in their molecular character and viscosity. It is also possible that but two streams are attained that necessitate dewaxing, usually (1) a light stream HVI 80 to 100 or 80 to 150 and (2) a heavy Bright Stock stream. It is also possible that three or more streams of different viscosities are derivable from such separatory systems. This invention pertains to treating in order to substantially dewax any two or more such streams in parallel flow arrangement.
- tectosilicate catalysts In treating any of these streams various tectosilicate catalysts have been employed.
- One family of these tectosilicates are nomenclated as ZSM-5 aluminosilicate compositions which have been characterized by their X-ray diffraction pattern as set forth in Table 1 of U.S. Patent 3,852,189, Chen et al.
- mordenites crystalline borosilicates and silicalites may also be used.
- the mordenite may be modified by cation exchange including but not restricted to mordenites modified by cation exchange with H, Be, Mg, Tl, Ce, Nd, Pb, Th, Nb, Rh, Ba, Sr, La, and Ca. It also includes but is not restricted to mordenite modified by vapour deposition techniques employing compounds such as metal chlorides.
- the second family of tectosilicate catalysts are those which selectively dewax relatively light lubricating oils such as an HVI 80 to 100 or 80 to 150 waxy raffinate in contrast to the above aluminosilicates which selectively dewax the heavier lubricating oils.
- One example of such catalyst is exemplified by the disclosure of Winquist U.S. Patent 4,343,692.
- Other such catalysts are ZSM-35, ZSM-23, ZSM-38, ZSM-21 and natural ferrierite, treated or untreated, with or without the presence of catalytic metals thereon.
- both such catalysts are disposed on the same support and vary by the metals incorporated thereon, the strength of the acid sites, or by the cations incorporated into the support such that one catalyst will selectively react with the wax species characteristic of light lube stocks while the other catalyst selectively reacts with the wax species characteristic of heavier lube stocks.
- the dewaxing step or steps of this invention are undertaken in the presence of hydrogen, preferably at a hydrogen circulation rate of between 350 and 2670 l(S.T.P.) H2/l oil feed.
- S.T.P. indicates Standard Temperature (of 0 °C) and Pressure (of 1 bar abs.).
- the reaction conditions are usually maintained at a temperature of between 150 °C and 500 °C and a pressure between 2 and 200 bar abs., preferably between 2 and 20 bar abs.
- the liquid hourly space velocity (LHSV) preferably will be from 0.1 to 10 and more preferably between 0.5 and 5.0.
- the raw lubricating oils contemplated herein to be treated in parallel flow generally contain in the range of from 0.1 to 50% by weight of waxy hydrocarbons (by this latter term it is meant normally solid hydrocarbons at 3 °C below pour point temperatures). Pour point is defined on the basis of the ASTM D-97 Test Method. Example pour points for finished oils are -18 °C for HVI 80 to 100 or 80 to 150 and -7 °C for HVI Brights Stock. It is critical to the operation of this invention to properly select the particular feed material for the particular dewaxing catalyst.
- HVI 80 to 100 or 80 to 150 lubricating oil have an average carbon number of 23 although the individual constituents of this stream are known to encompass a range of hydrocarbon components including minute quantities with 18 carbon atoms and 31 carbon atoms. It is believed that waxy materials present in HVI 250 to 300 have an average carbon number of 29 or 31 depending on the crude source. HVI 250 to 300 is known to encompass a range of hydrocarbon components including quantities of hydrocarbons with 24 carbons to 37 carbons. It is believed that the waxy hydrocarbons in HVI Bright Stock have an average carbon number of 38. HVI Bright Stock is known to encompass a range of hydrocarbon components which include quantities of hydrocarbons with 22 carbon atoms to 52 carbon atoms.
- the wax content of the first waxy raffinate may have more than 45% by weight of normal paraffins in contrast to other waxy raffinate streams, such as HVI Bright Stock which may have less than 10% by weight of normal paraffin components.
- This concentration of normal paraffin wax structures is dependent on the crude oil feed charged to the unit. It was surprising to find such a large content of branched and cyclic components in the heavy oil i.e. more than 55% by weight while the light oil contained less than 55% by weight of branched and cyclic components.
- the overall dewaxing plant can have a smaller design, be constructed with less offsite tankage and be designed with less catalyst inventory for each reactor. If a plant error occurs and a contaminant like sodium, for example, is allowed into one reactor, the other may continue to function unimpeded. And if the crude oil feed of the refinery changes, the market target projections can still be maintained due to the flexibility of the complimentary catalysts.
- dewaxing In this parallel passage flow system a continuous operation of dewaxing is contemplated and preferred.
- a certain catalyst becomes deactivated due to occlusion by trapped hydrocarbons or weakly held catalyst poisons it is a simple procedure to cease the dewaxing step and begin a hydrogen reactivation of the catalyst.
- This hydrogen reactivation is performed in the presence of a hydrogen-containing gas at a temperature between 343 °C and 538 °C.
- One dewaxing catalyst can be reactivated or regenerated while other dewaxing catalysts continue to perform their respective catalytic function until they too become spent and thereby necessitate reactivation.
- An oxidative regeneration of the catalyst may be undertaken in situ or more preferably the regeneration may be performed at an offsite location in a separate regeneration vessel by passage of an oxygen-containing gas thereover at a temperature form 371 °C to 566 °C for a period of time sufficient to remove coke deposits and thereby regenerate the dewaxing catalyst. Thereafter the regenerated catalyst is passed back to its respective dewaxing reactor vessel.
- the oxygen-containing gas can be air, pure oxygen or mixtures of oxygen with any other inert gas such as nitrogen or argon.
- normal blending techniques can be utilized to prepare any type of lubricating base oil or industrial oil, such as an automotive engine oil, transformer oil, compressor oil, railroad oil, refrigerator oil, hydraulic oil, gear oil, or any other lubricant necessitating specific qualities of pour point at a certain temperature.
- the invention also relates to catalytically dewaxed lubricating base oils whenever prepared by a process as described hereinbefore.
- An HVI 80 to 100 or 80 to 150 distillate stream is withdrawn via conduit 13
- an HVI 250 to 300 distillate stream is withdrawn via conduit 15
- an HVI 500 to 600 distillate stream is withdrawn via conduit 17.
- a fifth stream, withdrawn from the bottom of vacuum distillation unit 9 via conduit 19, contains heavy materials, such as asphalt and residua.
- This stream is passed to deasphalting unit 21 wherein an asphalt-rich product is withdrawn in conduit 23 concomitant with the deasphalted oil withdrawn in conduit 25.
- This stream commonly nomenclated as (DAO) also has indigenous undesirable waxy material which raises the pour point of the lubricating oil to a degree to render same unsuitable for most commercial use.
- the solvent is any conventional extraction solvent such as phenol, N-methyl-2-pyrrolidone, furfural, etc.
- solvent streams are added to respective batch extraction units 27, 29, 31 and 33 through conduits 35, 37, 39, and 41.
- a slip stream or bottom contaminant stream is withdrawn containing extracted aromatics, nitrogen and sulphur compounds in streams 43, 45, 47 and 49, which may likewise be treated in a distillation column (not shown herein) for return of the solvent to the solvent extraction system(s). This is also true for a portion or the entirety of streams 51, 53, 55 and 57.
- this solvent extraction system can be performed in a batch type method in a multitude of zones or the same can be performed in one zone, one-at-a-time, with only one respective particular waxy raffinate stream derived from the vacuum distillation column being solvent extracted at one time.
- the respective effluent streams from the solvent extraction zone in conduits 51, 53, 55 and 57 are passed into optional hydrotreating systems 59, 61, 63 and 65 which have ingress of hydrogen through conduits 67, 69, 71 and 73. While these hydrotreaters are shown as different units, they may physically be one integrated vessel useful for treating a multitude of streams. It is also contemplated that the hydrotreating be performed before the solvent extraction.
- the pre-dewaxing hydrotreating zone is purely optional and its presence or placement does not form an integral process parameter of the instant flow scheme contemplating the dual bed parallel passage flow of lubricating base oil precursors to different hydrodewaxing catalysts.
- the function of the hydrotreater is to excise additional aromatic compounds, sulphur compounds, nitrogen compounds and convert complex aromatic compounds to simpler aromatic compounds which renders the catalytic dewaxing processing more feasible.
- Hydrotreating is performed at mild hydrotreating conditions, which include a temperature of from 260 °C to 454 °C and a pressure from 74 bar abs. to 107 bar abs.
- the hydrogen may be present concomitant with an inert gas or the same may be present in its pure form. It is also contemplated that a refinery stream such as a reformer gas stream may be utilized as the source of hydrogen.
- the solvent extracted, or if desired, hydrotreated effluent streams are withdrawn from respective (or one single hydrotreater operating in blocked out mode) from hydrotreaters 59, 61, 63 and 65 through conduits 75, 77, 79 and 81. They are passed directly to the respective appropriate catalytic dewaxing steps 83, 85, 87 and 89, which are provided with hydrogen entry ports 91, 93, 95 and 97.
- the respective dewaxed lube oils are withdrawn from respective catalytic dewaxing units (or as few as two units) 83, 85, 87 and 89 through conduits 99, 101, 103 and 105 for further blending.
- One salient advantage of this invention is that use of ferrierite catalyst in dewaxing zone 83 totally vitiates the need to hydrotreat the product in conduit 99 after blending with other feed streams. Rendering this expensive and potentially troublesome extra process step superfluous surprisingly produces an overall process much more efficient and less expensive than any other type process which requires that the dewaxed light oils are to be hydrotreated. If desired, the light oil dewaxed effluent steam may be hydrotreated within the scope of this invention although, to do so is a processing of the dewaxed oil in a non-economically rewarding sequence of steps.
- this process produces a light HVI 80 to 100 or 80 to 150 lubricating base oil using a more efficient catalyst without the necessity for hydrotreating, in the presence of hydrogen, the dewaxed oil concomitant with other heavy dewaxed oils which may necessitate dewaxing.
- Another embodiment of this invention comprises the passage of the DAO stream directly from deasphalting unit 21 to hydrotreater 65 without need for the solvent extraction step, said pre-dewaxing hydrotreating being carried out at mild to severe hydrotreating conditions, i.e. over 74 bar abs. pressure and over 260 °C. Hydrotreated effluent is passed via conduit 81 to catalytic dewaxing unit 89 for aforementioned treatment.
- the solvent is any conventional dewaxing solvent such as propane, or alkyl ketones in admixture with an aromatic component, i.e. methylethyl ketone and toluene. These streams may be added in a batch processing manner.
- the solvent may be recovered by distillation and reused in the solvent dewaxing process.
- This preliminary solvent dewaxing can be performed in a multitude of zones or the same can be performed in one zone using a batch-type method one-at-a-time with each such particular waxy raffinate derived from the vacuum distillation column.
- the preferred catalyst in hydrogen dewaxing unit 83 is one with a pore size similar to the pore size of synthetic ferrierite.
- the preferred catalyst of hydrogen dewaxing unit 89 (for the Bright Stock waxy raffinate) is a catalyst with a pore size similar or larger than the pore size of the ZSM-5 catalyst taught in U.S. Patent 3,702,886.
- the latter can also be used in hydrogen dewaxing units 85 and 87 with or without accompaniment of a smaller pore zeolite.
- the use of the preferred ferrierite-containing catalyst obviates post-dewaxing hydrotreatment.
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- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Catalysts (AREA)
Claims (10)
- Ein Verfahren zum katalytischen Entwachsen von mehr als einem aus einer Raffinerieanlage stammenden Vorläufer für ein Basisschmieröl, welches das Kontaktieren in einer ersten Reaktionszone in Gegenwart eines Wasserstoff enthaltenden Gases bei Entwachsungsbedingungen eines ersten Zuspeisungsstroms, enthaltend einen ersten aus einer Raffinerieanlage stammenden Basisschmieröl-Vorläufer in Form eines Raffinats, welcher ein erstes Wachs, umfassend geradkettige Paraffine, enthält, wobei das erste Wachs weniger als 55 Gewichtsprozent an verzweigten und zyklischen Kohlenwasserstoffen enthält, mit einem ersten Entwachsungskatalysator, welcher für die Umwandlung des genannten ersten Wachses geeignet ist, und das Kontaktieren in Gegenwart eines Wasserstoff enthaltenden Gases bei Hydroentwachsungsbedingungen in einer parallel angeordneten zweite Reaktionszone eines zweiten aus einer Raffinerieanlage stammenden Basisschmieröl-Vorläufers in Form eines Raffinats, welcher ein zweites Wachs, enthaltend mehr als 55 Gewichtsprozent an verzweigten und zyklischen Kohlenwasserstoffen enthält, mit einem zweiten Hydroentwachsungskatalysator, welcher für die Umwandlung des genannten zweiten Wachses geeignet ist, und gegebenenfalls das Kontaktieren von weiteren aus Raffinerieanlagen stammenden wachshaltigen Basisschmieröl-Vorläuferzuspeisungsströmen in Form von Raffinaten in einer oder mehreren Reaktionsstufe(n) in Gegenwart eines Wasserstoff enthaltenden Gases bei Hydroentwachsungsbedingungen mit einem Hydroentwachsungskatalysator, und das Abziehen mindestens zwei paralleler Abflußströme in Form von Raffinerie- entwachsten Basisschmierölen aus den genannten Reaktionszonen umfaßt.
- Ein Verfahren nach Anspruch 1 , in welchem die Basisschmieröl-Vorläuferzuspeisungsströme durch Fraktionieren eines Bodenstroms aus einer atmosphärischen Destillation eines Kohlenwasserstoffölzuspeisungsstroms erhalten werden.
- Ein Verfahren nach Anspruch 1 oder 2, in welchem die Hydroentwachsungsbedingungen eine Temperatur zwischen 150°C und 500°C, einen Druck zwischen 2 und 200 bar abs. und ein Wasserstoff/Öl-Zuspeisungsverhältnis zwischen 350 und 2670 l(S.T.P) H2/l Ölzuspeisung umfassen.
- Ein Verfahren nach einem der vorstehenden Ansprüche, in welchem der erste Hydroentwachsungskatalysator einen synthetischen Ferrierit umfaßt, in welchem mindestens ein Metall, ausgewählt aus Metallen der Gruppe, bestehend aus Gruppe VIB, Gruppe VIIB und Gruppe VIII des Periodischen Systems der Elemente, integriert ist.
- Ein Verfahren nach Anspruch 4, in welchem ein erster Zuspeisungsstrom, umfassend einen wachshaltigen HVI 80 bis 150 oder 80 bis 100 Schmierölvorläufer , in der ersten Reaktionszone hydroentwachst wird, aus welcher ohne anschließende Hydrobehandlung ein Basisschmieröl erhalten wird.
- Ein Verfahren nach einem der vorstehenden Ansprüche, in welchem der zweite Hydroentwachsungskatalysator ein kristallines Aluminosilikat mit einer Porengröße von 0,5 bis 0,9 nm und einer Zusammensetzung, ausgedrückt in Molverhältnissen, wie folgt, umfaßt:
0,9 + 0,2 M2/nO: Al₂O₃:5-100 SiO₂:0-40 H₂O,
wobei M ein Kation ist und n die Wertigkeit dieses Kations bedeutet. - Ein Verfahren nach einem der vorstehenden Ansprüche, welches mindestens 3 und vorzugsweise 4 oder mehr parallel angeordnete Zonen zum katalytischen Hydroentwachsen umfaßt.
- Ein Verfahren nach einem der vorstehenden Ansprüche, in welchem jeder Hydroentwachsungskatalysator unabhängig von dem(den) Entwachsungsvorgang(bzw.-Vorgängen) in der(den) anderen Entwachsungszone(n) in Gegenwart eines sauerstoffhaltigen Gases bei einer Temperatur von 371°C bis 566°C regeneriert wird.
- Ein Verfahren nach Anspruch 8, in welchem auf die genannte Regenerierung eine Spülung des regenerierten Katalysators mit Inertgas und eine anschließende Reaktivierung in Gegenwart eines wasserstoffhaltigen Gases bei einer Temperatur von 343°C bis 538°C folgt.
- Ein Verfahren nach einem der vorstehenden Ansprüche, in welchem mindestens zwei entwachste Basisschmieröle vermischt werden, um schließlich ein Schmierölprodukt zu erhalten.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US81321485A | 1985-12-24 | 1985-12-24 | |
US813214 | 1985-12-24 |
Publications (2)
Publication Number | Publication Date |
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EP0237655A1 EP0237655A1 (de) | 1987-09-23 |
EP0237655B1 true EP0237655B1 (de) | 1992-06-03 |
Family
ID=25211785
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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EP86202162A Expired - Lifetime EP0237655B1 (de) | 1985-12-24 | 1986-12-03 | Prozess zur katalytischen Entwachsung von mehr als einem aus einer Raffinerie stammenden Grundöl-Precursor |
Country Status (11)
Country | Link |
---|---|
EP (1) | EP0237655B1 (de) |
JP (1) | JPS62190286A (de) |
KR (1) | KR940008389B1 (de) |
CN (1) | CN1016249B (de) |
AU (1) | AU592137B2 (de) |
BR (1) | BR8606234A (de) |
CA (1) | CA1282363C (de) |
DE (1) | DE3685578T2 (de) |
ES (1) | ES2031820T3 (de) |
IN (1) | IN168775B (de) |
SG (1) | SG44393G (de) |
Families Citing this family (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0161833B1 (de) * | 1984-05-03 | 1994-08-03 | Mobil Oil Corporation | Katalytische Entwachsung von leichten und schweren Ölen in zwei Parallelreaktoren |
US5378348A (en) * | 1993-07-22 | 1995-01-03 | Exxon Research And Engineering Company | Distillate fuel production from Fischer-Tropsch wax |
US5833837A (en) * | 1995-09-29 | 1998-11-10 | Chevron U.S.A. Inc. | Process for dewaxing heavy and light fractions of lube base oil with zeolite and sapo containing catalysts |
KR970074901A (ko) * | 1996-05-14 | 1997-12-10 | 조규향 | 미전환유를 이용하여 연료유 및 윤활기유를 제조하는 방법 |
DE60205596T2 (de) | 2001-02-13 | 2006-05-24 | Shell Internationale Research Maatschappij B.V. | Schmierölzusammensetzung |
AR032932A1 (es) | 2001-03-05 | 2003-12-03 | Shell Int Research | Procedimiento para preparar un aceite de base lubricante y un gas oil |
AR032930A1 (es) | 2001-03-05 | 2003-12-03 | Shell Int Research | Procedimiento para preparar un aceite de base lubricante y gas oil |
AR032941A1 (es) * | 2001-03-05 | 2003-12-03 | Shell Int Research | Un procedimiento para preparar un aceite base lubricante y aceite base obtenido, con sus diversas utilizaciones |
AU2003242766A1 (en) | 2002-07-12 | 2004-02-02 | Shell Internationale Research Maatschappij B.V. | Process to prepare a heavy and a light lubricating base oil |
AU2003255058A1 (en) | 2002-07-18 | 2004-02-09 | Shell Internationale Research Maatschappij B.V. | Process to prepare a microcrystalline wax and a middle distillate fuel |
JP5221999B2 (ja) * | 2008-03-31 | 2013-06-26 | Jx日鉱日石エネルギー株式会社 | 潤滑油基油の製造方法 |
WO2015007691A1 (en) * | 2013-07-15 | 2015-01-22 | Shell Internationale Research Maatschappij B.V. | Process to prepare two or more base oils |
US20160168490A1 (en) * | 2013-07-15 | 2016-06-16 | Shell Oil Company | Process to prepare two or more base oils |
US9796936B2 (en) | 2015-09-09 | 2017-10-24 | Chevron U.S.A. Inc. | Production of heavy API group II base oil |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0161833A2 (de) * | 1984-05-03 | 1985-11-21 | Mobil Oil Corporation | Katalytische Entwachsung von leichten und schweren Ölen in zwei Parallelreaktoren |
Family Cites Families (4)
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US4211635A (en) * | 1979-04-23 | 1980-07-08 | Mobil Oil Corporation | Catalytic conversion of hydrocarbons |
JPS57100190A (en) * | 1980-12-09 | 1982-06-22 | Mobil Oil Corp | Lube base stock and manufacture of slate thereof |
CA1188247A (en) * | 1981-04-02 | 1985-06-04 | Nai Y. Chen | Process for making naphthenic lubestocks from raw distillate by combination hydrodewaxing/hydrogenation |
US4400265A (en) * | 1982-04-01 | 1983-08-23 | Mobil Oil Corporation | Cascade catalytic dewaxing/hydrodewaxing process |
-
1986
- 1986-11-25 IN IN906/MAS/86A patent/IN168775B/en unknown
- 1986-11-25 CA CA000523708A patent/CA1282363C/en not_active Expired - Fee Related
- 1986-12-03 ES ES198686202162T patent/ES2031820T3/es not_active Expired - Lifetime
- 1986-12-03 DE DE8686202162T patent/DE3685578T2/de not_active Revoked
- 1986-12-03 EP EP86202162A patent/EP0237655B1/de not_active Expired - Lifetime
- 1986-12-17 CN CN86108258A patent/CN1016249B/zh not_active Expired
- 1986-12-17 KR KR1019860010844A patent/KR940008389B1/ko active IP Right Grant
- 1986-12-17 JP JP61299087A patent/JPS62190286A/ja active Pending
- 1986-12-17 AU AU66639/86A patent/AU592137B2/en not_active Ceased
- 1986-12-17 BR BR8606234A patent/BR8606234A/pt active Search and Examination
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- 1993-04-14 SG SG44393A patent/SG44393G/en unknown
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0161833A2 (de) * | 1984-05-03 | 1985-11-21 | Mobil Oil Corporation | Katalytische Entwachsung von leichten und schweren Ölen in zwei Parallelreaktoren |
Also Published As
Publication number | Publication date |
---|---|
DE3685578D1 (de) | 1992-07-09 |
CN86108258A (zh) | 1987-10-28 |
CN1016249B (zh) | 1992-04-15 |
CA1282363C (en) | 1991-04-02 |
IN168775B (de) | 1991-06-01 |
JPS62190286A (ja) | 1987-08-20 |
AU592137B2 (en) | 1990-01-04 |
BR8606234A (pt) | 1987-09-29 |
EP0237655A1 (de) | 1987-09-23 |
AU6663986A (en) | 1987-06-25 |
DE3685578T2 (de) | 1993-01-21 |
KR940008389B1 (ko) | 1994-09-14 |
KR870006168A (ko) | 1987-07-09 |
SG44393G (en) | 1993-06-25 |
ES2031820T3 (es) | 1993-01-01 |
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