EP0300103B1 - Wachskristallveränderung durch die Verwendung von entwachsenden Hilfsmitteln unter besonderen Rührverhältnissen - Google Patents
Wachskristallveränderung durch die Verwendung von entwachsenden Hilfsmitteln unter besonderen Rührverhältnissen Download PDFInfo
- Publication number
- EP0300103B1 EP0300103B1 EP19870306510 EP87306510A EP0300103B1 EP 0300103 B1 EP0300103 B1 EP 0300103B1 EP 19870306510 EP19870306510 EP 19870306510 EP 87306510 A EP87306510 A EP 87306510A EP 0300103 B1 EP0300103 B1 EP 0300103B1
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- EP
- European Patent Office
- Prior art keywords
- dewaxing
- chilling
- solvent
- oil
- wax
- 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
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Classifications
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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
- 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
- C10G73/04—Recovery of petroleum waxes from hydrocarbon oils; Dewaxing of hydrocarbon oils with the use of filter aids
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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
- 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
- C10G73/32—Methods of cooling during dewaxing
Definitions
- the filter feed rate and liquid/solid ratio of solvent dewaxed oil are improved by conducting the lube oil solvent dewaxing process under conditions of agitation in indirect chilling means while employing dewaxing aids.
- dewaxing aid assisted indirect chilling lube oil solvent dewaxing under agitated conditions, the quantity of dewaxing aid employed can be minimal, on the order of 0.01 to 1.0 weight percent active ingredient, based on waxy oil feed.
- the indirect chiller apparatus makes use of paddles, which preferably extend substantially the length of the chiller apparatus, to produce agitation in the chiller. These paddles must not touch the interior wall of the chiller since to do so results in scraping, which is detrimental to filter rate and liquid/solid performance.
- the paddles are at least 0.05 inch to 5 inches (0.127 to 12.7 cm) away from the internal wall of the chiller, i.e., a gap of 0.05 to 5 inches (0.127 to 12.7 cm) exists between the tip of the paddle and the internal chiller wall.
- This gap is preferably 0.1 to 2 inches (0.254 to 5.08 cm), most preferably 0.25 to 1 inch (0.635 to 2.54 cm).
- the larger gaps can exist only in those units which have a correspondingly larger internal diameter. This gap, therefore, ranges from between 0.5 to 40% of the chiller internal diameter, preferably 1 to 40% of the chiller internal diameter, most preferably 2 to 20% of the chiller internal diameter.
- These paddles are rotated so as to exhibit a tip velocity of between 25 to 400 ft./min. (7.62 to 121.92 m/minute), preferably between 50 to 250 ft./min. (15.24 to 76.2 m/minute), most preferably 50 to 100 ft./min. (15.24 to 30.48 m/minute), which for the purposes of the specification is deemed to be tangential fluid velocity in the region of crystallization.
- a tip velocity of between 25 to 400 ft./min. (7.62 to 121.92 m/minute), preferably between 50 to 250 ft./min. (15.24 to 76.2 m/minute), most preferably 50 to 100 ft./min. (15.24 to 30.48 m/minute), which for the purposes of the specification is deemed to be tangential fluid velocity in the region of crystallization.
- a chiller having a 5.25 inch (13.335 cm) internal diameter paddles which exhibit a paddle to chiller wall gap of about 0.5 inch
- paddle speeds of about 100 rpm are employed, as operation in this agitation region produces the best results when one considers both feed filter rate and liquid/solid ratio as a total entity.
- These rotational speeds correspond to fluid velocities of between about 50 to 250 feet/minute (15.24 to 76.20 m/minute) in the crystallization region near the chilling surface, where the flow generated by a rotating paddle is mainly tangential.
- This additional agitation component when added to the longitudinal flow due to fluid velocity through the vessel will produce an excellent environment for good heat transfer, optimum dewaxing aid-wax interaction and the formation of dense, spherical crystal structures.
- the paddle rotational speed needed to achieve a tangential fluid velocity of between 25 to 400 feet/minute (7.62 to 121.92 m/minute, preferably between 50 to 250 feet/minute (15.24 to 76.2 m/minute), by means of a rotating agitator means in an indirect chiller with the agitator not touching the walls of the chiller can be easily determined by practitioners for any size apparatus.
- the waxy oil feeds which may be effectively dewaxed employing the process of the present invention include any waxy hydrocarbon lube oil feedstream, preferably a waxy petroleum lubricating oil, speciality oil, turbine oil, white oils, refrigerator oils, etc.
- waxy hydrocarbon oil feedstocks can come from any natural or synthetic source, including coal oils, tar sands oils, shale oils, etc.
- the natural petroleum oil stocks can be any naphthenic or paraffinic oil, such as oils obtained from Aramco, Kuwait, the Panhandle, North Louisiana, Western Canada, South Texas, Tia Juana, North Sea, North Slope, etc.
- the waxy hydrocarbon lube oil feedstock will have a boiling range within the broad range of 500°F (260°C) to 1,300°F (704.4°C).
- the preferred oil stocks are the lubricating oil and specialty oil fractions boiling within the range of 550°F to 1,200°F (287.8 to 648.9°C) (atmospheric).
- Solvent dewaxing employs a solvent to both dilute the oil and as an aid in wax precipitation.
- This solvent can be selected from any of the known, readily available solvents.
- Representative of such solvents are the aliphatic ketones having from 3 to 6 carbon atoms, such as acetone, methylethyl ketone (MEK) , methylisobutyl ketone (MIBK) , and mixtures thereof; the lower molecular weight, normally gaseous, liquefied hydrocarbons, such as methane, ethane, propane, butane, propylene, butylene, etc.
- halogenated hydrocarbons of lower molecular weight such as C1-C4 halogenated hydrocarbons
- C1-C4 chlorinated hydrocarbons i.e., dichloromethane, dichloroethane, tetrachloropropane, etc.
- Ethers may also be employed as dewaxing solvents, such as methyl tertbutyl ether (MTBE).
- the preferred solvents are mixtures of MEK/MIBK, MEK/toluene, propylene/acetone.
- the process will be conducted under typical solvent dewaxing conditions, including chilling to a wax filtration temperature in whatever range satisfies the requirements of the practitioner and is compatible with the oil being employed.
- waxy oils are chilled to a temperature 10 to 30°F (5.6 to 16.7°C) below the finally desired oil cloud point temperature. Consequently, if an oil with a cloud point of about -10°F (-23.3°C) is desired, the oil will be chilled to a temperature, called the wax filtration temperature, of between -20°F to -40°F(-28.9 to -40°C), depending on the oil and solvent employed. Chilling will be at a relatively uniform rate so as to minimize the effects of shock chilling. Consequently, chilling rates on the order of 1 to 20°F/minute (0.56 to 11.1°C/minute) will be employed.
- the waxy lube oil feed is introduced at a temperature above its cloud point into an indirect chilling apparatus, such as a double tube chiller.
- the space between the inner and outer pipes is the space through which a chilling medium is passed.
- the oil, with or without solvent predilution, preferably with solvent predilution is introduced into the central pipe in which an agitated environment is maintained by means of a centrally rotating shaft upon which are located paddles, blades, turbine plates, propellers, etc., in other words, means suited for establishing a level of agitation in the central pipe.
- agitation can be achieved by the use of propellers, blades or paddles which effectively sweep the cold exchanger wall surfaces and which are uniformly distributed to sweep at least 10% of the wall, preferably about 50% of the wall surface, and most preferably at least 90% of the wall surface.
- a typical design would be similar to a conventional scraped surface exchanger where the scraper blades are moved away from the wall providing greater than 90% sweeping of the cold exchanger surfaces.
- These agitator means i.e., paddles, blades, propellers, etc., are sized so as not to touch the interior wall of the chiller.
- the waxy feed is pre-diluted with from 1 to 10 volumes of solvent prior to being introduced into the central pipe, more preferably 2 to 5 volumes.
- This predilution alternative is the preferred mode of operation.
- the agitation means within scraped surface chiller devices must not be in its "as designed" configuration, that is, the scraper blades must not be touching the interior walls of the chiller pipe, but must be adjusted so as not to be in contact with the wall, but just sweep past the interior wall at some specific distance from the wall.
- This configuration is necessary as it eliminates the possibility of the precipitated wax being physically crushed by the blades as the blades sweep past the interior wall, as compared to the configuration in which the blades are in physical contact with the interior chiller walls. It is also advantageous to move the blades away from the interior wall as this facilitates increasing the rotational speed of the sweeper blade assembly without the need to overcome blade/wall friction or drag.
- Figure 1 shows the improvement in dewaxing aid performance (at similar dose levels) when a gapped agitator operates at a high agitation tip speed, as compared to a standard scraper also operating at high rotational speeds.
- Figure 2 shows that increasing agitator speed along which, produces some benefit, is not as significant as when agitator speed is increased when a dewaxing aid is used.
- wax precipitation was conducted under conditions of low or no agitation. This procedure was followed since it was believed that precipitation under conditions of high agitation would result in the formation of fine wax particles which could clog the liquid-solid separators.
- the typical wax precipitation technique employed scraped surface chillers. In such a unit, a waxy oil and a dewaxing solvent are premixed at a temperature sufficient to effect complete solution of the oil and wax. If necessary, the waxy oil is heated (either prior to or after addition of solvent) to insure complete solution of the wax contained therein.
- the solution is then indirectly cooled at a uniformly slow cooling rate, e.g. , 1°F to 5°F (0.56 to 2.78°C) per minute, under conditions which avoid substantial agitation of the solution during precipitation of the wax.
- a uniformly slow cooling rate e.g. 1°F to 5°F (0.56 to 2.78°C) per minute.
- the DILCHILL R (DILCHILL is a registered service mark of Exxon Research and Engineering Company) process was developed so as to overcome the inherent limitations and disadvantages of scraped surface chilling dewaxing.
- cooling is accomplished in a staged tower.
- the waxy oil is removed through the tower, while cold solvent is injected along the tower directly into a plurality of the stages (either some or all of the stages have cold solvent injected into them).
- the cold solvent injection is accompanied by a high degree of agitation in at least a portion of the stages containing waxy oil and solvent so as to insure substantially instantaneous mixing of the cold solvent and waxy oil.
- This oil-solvent-wax slurry is then withdrawn from the DILCHILL chilling zone and introduced into a second chilling zone wherein it is cooled to the wax separation temperature, thereby precipitating a further portion of the wax from the waxy oil Cooling rates in this zone are in the range of 5°F-20°F (2.78 to 11.11°C) per minute.
- the second chilling zone may incorporate any conventional cooling process, such as scraped surface chilling, autorefrigeration and the like; however, scraped surface chilling is preferred.
- scraped surface chillers the partially cooled oil-solvent-wax slurry is indirectly cooled to the wax separation temperature without the addition of more solvent.
- the scrapers are used to remove any wax which adheres to the walls of the chillers.
- a disadvantage of the scraped surface chiller in this embodiment is the same as that encountered when employing scraped surface chillers as the sole cooling unit. The scrapers physically crush the wax crystals formed on the chiller wall, thereby reducing the wax filtration rates and increasing the amounts of occluded oil in the wax.
- U. S. Patent No. 4,140,620 to Paulett described an incremental dilution dewaxing process wherein a lubricating oil stock, at a temperature above its cloud point, is cooled in a cooling zone with vigorous agitation to a temperature below its cloud point and then further cooled with minimum agitation and incremental solvent addition to its final temperature, followed by filtration for the removal of wax. Rapid stirring is provided during the early part of the cooling period.
- the cooling zone is described as being a conventional, double wall heat exchanger provided with means for agitating the oil during cooling by more rapid rotation of the scrapers.
- the base oil stock is diluted with solvent during the initial period of agitated chilling.
- the cooling zone comprises a double wall chiller wherein the waxy oil feed is introduced into the inner zone with cold filtrate supplied to the outer jacket of the chiller, with increased agitation being provided by increased rotational speed of the scrapers.
- U. S. Patent No. 4,354,003 and U. S. Patent No. 4,422,924 teach a dewaxing aid and that solvent dewaxing is improved by using said dewaxing aid, which dewaxing aid comprises a mixture of (a) an alpha-olefin polymer having an average molecular weight of from about 10,000 to 1,000,000 and a wide molecular weight distribution exceeding the range of from about 10,000 to 1,000,000, but falling within the range of from about 2,000 to 3,000,000 wherein the alpha-olefin polymer is a homo-polymer made up of a C10 to C25 alpha olefin monomer or is a copolymer made up of a monomer mixture comprising more than 50 weight percent of at least two C10 to C25 alpha olefin monomers, having a melt index greater than 1.8 g/10 min.; and (b) an olefin vinyl acetate copolymer having a vinyl acetate content of from about 15 to 40
- solvent dewaxing is improved by using a polymeric dewaxing aid which comprises a condensation product of naphthalene and chlorinated wax, having an average molecular weight ranging from about 20,000 to 500,000 and a molecular weight distribution exceeding the range of from about 10,000 to 1,000,000.
- a polymeric dewaxing aid which comprises a condensation product of naphthalene and chlorinated wax, having an average molecular weight ranging from about 20,000 to 500,000 and a molecular weight distribution exceeding the range of from about 10,000 to 1,000,000.
- a dewaxing aid which comprises a mixture of (a) polyalkyl acrylate having alkyl group side chain lengths of from 10-26 carbons (excluding branching); and (b) an n-alkyl methacrylate polymer having alkyl group side chain lengths of from 10-20 carbons, excluding branching.
- Component (a) typically has a number average molecular weight of from 3,000 to 500,000, while component (b) has a number average molecular weight of from 5,000 to 200,000.
- the combination (a) plus (b) may be employed in a weight ratio within the range from about 1/100 to 100/1 at an aid dose level ranging from about 0.01 to 1.0 weight percent active ingredient.
- a dewaxing aid comprising (a) a poly di-alkyl fumarate/vinyl acetate copolymer in combination with (b) poly alkyl (meth-) acrylate polymers.
- Component (a) has a number average molecular weight of about 1,000 to 100,000 and possesses alkyl side chains of from C16-C24+ in length excluding branching with a pendant side chain length of predominantly (>50%) C20.
- the polyalkyl (meth-) acrylate is the polymeric ester of aliphatic alcohols having groups 10 to 20 carbons in length, excluding branching (pendant side chain length predominantly (>50%) C14 and lower) and acrylic or (meth-) acrylic acid (preferably methacrylic acid) and possesses a number average molecular weight of at least 5,000.
- the solvent dewaxing processes benefited by the use of the present combination are those using standard, normally liquid solvents, such as C3 to C6 ketones, aromatic hydrocarbons, halogenated hydrocarbons and mixtures thereof.
- the waxy hydrocarbon oil dewaxed is a bright stock.
- the dewaxing aid combination may be used at a dose level of from about 0.005 to 5 weight percent active ingredient at a component A/B ratio of about 4/1 to 1/100.
- U. S. Patent No. 4,439,308 teaches solvent dewaxing Bright stock waxy raffinate oil employing a dewaxing aid, which dewaxing aid is a mixture of (a) poly-di-alkyl fumarate/vinyl acetate copolymers; and (b) a wax-naphthalene condensate.
- the dewaxing aid mixture is a mixture of (a) poly-di-alkyl fumarate/vinyl acetate copolymer, having a number average molecular weight of about 1,000 to 100,000, preferably 5,000 to greater, possessing alkyl side chains of from C16-C24+ in length (excluding branching) with an average pendant side chain length of predominantly (>50%) C20; and (b) a wax-naphthalene condensation product having a number average molecular weight of about 1,000 and greater.
- the combination (a) plus (b) may be employed in a weight ratio within the range from about 45/55 to 1/100, preferably about 1/3, and an aid dose level ranging from about 0.005 to 2.0 weight percent, preferably 0.01 to 0.2 weight percent active ingredient.
- U. S. Patent No. 4,461,698 teaches solvent dewaxing processes for dewaxing waxy hydrocarbon oil distillates employing a dewaxing aid, which dewaxing aid is a mixture of (a) a poly-dialkylfumarate/vinyl acetate copolymer; and (b) a wax-naphthalene condensation product.
- Component (a) has pendant alkyl side chain groups of from 16 to 30 carbon atoms in length (excluding branching) with an average pendant side chain carbon length of predominantly (>50%) C22.
- Component (a9) has a number average molecular weight of from about 1,000 to 100,000, preferably greater than about 5,000.
- Component (b) has a number average molecular weight of at least about 1,000.
- the combination (a) and (b) may be employed in a weight ratio A/B within the range of from about 1/10 to 20/1 and at an aid dose level ranging from about 0.005 to 2.0 weight percent.
- U. S. Patent No. 3,393,144 describes a dewaxing process which is benefited by using an added dewaxing aid in a high agitation, indirect chilling environment for fuels dewaxing. Agitation is on the order of 250 to 1,000 rpm and is recited in the Examples. In the Examples feed filter rate improves on going to higher impeller speeds (rpm). The agitated indirect chilling is not performed in a scraped-surface heat exhanger.
- feed filter rate is maximized in a solvent dewaxing environment by practicing the dewaxing in the presence of a dewaxing aid in indirect chilling means under conditions of agitation.
- a dewaxing aid in indirect chilling means under conditions of agitation.
- From between about 0.01 to 1.0 weight percent dewaxing aid active ingredient may be employed, preferably between about 0.01 to 0.5 weight percent dewaxing aid active ingredient based on waxy oil feed.
- Any of the dewaxing aids common in the trade may be employed, such as those listed in the above-identified patents, as well as in U. S. Patent No. 3,475,321 and U. S. Patent No. 3,479,278 to Henselman, et al.
- V/V dilution solvent From 1 to 10 V/V dilution solvent are employed, preferably with at least part of the solvent being added to the waxy feed prior to the feed being introduced to the dewaxing zone. From .2 to 2 volumes of solvent per volume of waxy feed is preferably used as the predilution solvent. Total solvent employed (predilution plus dilution) is preferably in the 1 to 8 V/V range.
- the dewaxing environment is an agitated environment. Agitation can be achieved, for example, by employing indirect chillers within which is a rotating shaft upon which are affixed paddles or blades extending substantially the entire internal length of the chiller unit, rotating at a paddle tip velocity of 25 to 400 ft.(7.62 to 60.96 m)/min.
- the system for practicing this invention uses rotating paddles having a diameter only slightly smaller than the chilling vessel, the gap between the paddle tip and the chiller internal wall being from 0.5 to 40% of the chiller internal diameter, preferably 1 to 15% of the chiller internal diameter, most preferably 2% to 20% of the chiller internal diameter.
- This configuration imparts additional agitation, which is mainly radial and tangential close to the chiller wall in the critical region where crystallization is initiated.
- the data indicate a sensitivity and critical agitation limitation of 50 to 250 feet (15.24 to 76.2 m) per minute fluid velocity near the chilling surface.
- the practitioner can easily determine how to achieve such levels of fluid velocity for any size apparatus. For example, in a 12" (30.48 cm) vessel with an 11" (27.94 cm) agitator a tip speed of 100 ft. (30.48 m)/min. would require an agitator speed of 35 rpm.
- Indirect chilling devices are benefited most by the practice of the present invention. Practicing the present invention with direct chilling dewaxing procedures does not result in the same, if any, benefit.
- Typical activity parameters are summarized below in Table II for a 600 neutral feedstock dewaxed under lab-simulated surface chilling (comparing scraped surface chilling and agitated surface [blades not touching the walls] conditions and DILCHILL conditions.
- a dialkylfumarate vinyl acetate copolymer made from a mixture of 70% C22, 15% C20 and 15% C18 alcohols.
- Acryloid 144 (Rohm and Haas Company) A polyalkyl methacrylate polymer made from a mixture of 4% ⁇ C12, 7% C14, 39% C16, 45% C16, 45% C18, 5% >C20 alcohols.
- Figure 1 demonstrates the significant improvements in activity parameters for the paddle over the scraper operating at similar rpm in identical systems employing the data from Tables III and IV.
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- 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)
Claims (5)
- Verfahren zum Entparaffinieren von paraffinhaltigen Kohlenwasserstoffölen, bei dem eine Mischung aus paraffinhaltigem Öl/Entparaffinierungslösungsmittel und Entparaffinierungshilfsmittel in indirekten Kühlmitteln auf eine Paraffinfiltrationstemperatur gekühlt wird, wobei in den indirekten Kühlmitteln mit Hilfe von in den Kühlmitteln angeordneten Rührflügeln, die sich entlang der Kühlmittel erstrecken, Durchmischungsbedingungen aufrechterhalten werden, die Rührflügel nicht die inneren Wände der Kühlmittel berühren, was zu einem Spalt zwischen der Rührflügelspitze und der inneren Wand der Kühlmittel führt, der im Bereich von 0,5 bis 20% des inneren Durchmessers der Kühlmittel liegt, und der Rührflügel so rotiert, daß die Spitze eine Geschwindigkeit im Bereich von 7,62 bis 121,92 m/min (25 bis 400 Fuß/Minute) aufweist.
- Verfahren nach Anspruch 1, bei dem das Entparaffinierungshilfsmittel in einer Dosierung von 0,01 bis 1,0 Gew.% Wirkstoff verwendet wird.
- Verfahren nach Anspruch 1 oder Anspruch 2, bei dem die Geschwindigkeit der Rührflügelspitze 15,24 bis 76,2 m/min (50 bis 250 Fuß/Minute) beträgt.
- Verfahren nach einem der Ansprüche 1 bis 3, bei dem die Geschwindigkeit der Rührflügelspitze 15,24 bis 30,48 m (50 bis 100 Fuß)/Minute beträgt.
- Verfahren nach einem der Ansprüche 1 bis 4, bei dem das Entparaffinierungshilfsmittel in einer Dosierung von 0,01 bis 0,5 Gew.-% Wirkstoff, bezogen auf ein paraffinhaltiges Öleinsatzmaterial, verwendet wird.
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US06/867,141 US4695363A (en) | 1986-05-27 | 1986-05-27 | Wax crystal modification using dewaxing aids under agitated conditions |
EP19870306510 EP0300103B1 (de) | 1987-07-23 | 1987-07-23 | Wachskristallveränderung durch die Verwendung von entwachsenden Hilfsmitteln unter besonderen Rührverhältnissen |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP19870306510 EP0300103B1 (de) | 1987-07-23 | 1987-07-23 | Wachskristallveränderung durch die Verwendung von entwachsenden Hilfsmitteln unter besonderen Rührverhältnissen |
Publications (2)
Publication Number | Publication Date |
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EP0300103A1 EP0300103A1 (de) | 1989-01-25 |
EP0300103B1 true EP0300103B1 (de) | 1991-11-06 |
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Application Number | Title | Priority Date | Filing Date |
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EP19870306510 Expired EP0300103B1 (de) | 1986-05-27 | 1987-07-23 | Wachskristallveränderung durch die Verwendung von entwachsenden Hilfsmitteln unter besonderen Rührverhältnissen |
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EP (1) | EP0300103B1 (de) |
Families Citing this family (2)
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US5187329A (en) * | 1991-06-28 | 1993-02-16 | At&T Bell Laboratories | Twisted pairs of insulated metallic conductors for transmitting high frequency signals |
CN110407365B (zh) * | 2019-08-19 | 2021-11-19 | 南通四建集团有限公司 | 一种商业广场给水蓄水池及其水净化结构 |
Family Cites Families (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
USRE19869E (en) * | 1936-02-25 | Method and apparatus fob avoiding | ||
US1871172A (en) * | 1926-08-20 | 1932-08-09 | Standard Oil Co | Recovery of wax from oils |
US1892283A (en) * | 1927-12-27 | 1932-12-27 | Texas Co | Treating hydrocarbon oil |
US1867580A (en) * | 1928-04-18 | 1932-07-19 | Texas Co | Dewaxing hydrocarbon oil |
US2036966A (en) * | 1930-12-20 | 1936-04-07 | Sharples Specialty Co | Dewaxing oil |
US2903411A (en) * | 1957-01-02 | 1959-09-08 | Sun Oil Co | Wax crystallization process |
US3393144A (en) * | 1965-05-14 | 1968-07-16 | Mobil Oil Corp | Dewaxing process using a low boiling fraction of fuel oil to reduce the viscosity of a high boiling fraction of fuel oil |
US4203824A (en) * | 1978-12-22 | 1980-05-20 | Exxon Research & Engineering Co. | Polyvinylpyrrolidone dewaxing aid for bright stocks |
US4406771A (en) * | 1982-09-29 | 1983-09-27 | Exxon Research And Engineering Co. | Solvent dewaxing waxy hydrocarbon oil distillates using a combination poly di-alkyl fumarate-vinyl acetate copolymer having pendent carbon side chain length of predominantly C22 and polyalkyl(meth-)acrylate polymer dewaxing aid |
GB2152527B (en) * | 1984-01-12 | 1988-10-19 | Exxon Research Engineering Co | Process for dewaxing hydrocarbon oils using agitated indirect heat exchanger |
US4728413A (en) * | 1984-09-24 | 1988-03-01 | Exxon Research And Engineering Company | Agitated dewaxing employing modified agitator means |
US4695363A (en) * | 1986-05-27 | 1987-09-22 | Exxon Research And Engineering Company | Wax crystal modification using dewaxing aids under agitated conditions |
-
1987
- 1987-07-23 EP EP19870306510 patent/EP0300103B1/de not_active Expired
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Publication number | Publication date |
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EP0300103A1 (de) | 1989-01-25 |
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