CN1140199A - Process for producing lubricating base oils - Google Patents

Process for producing lubricating base oils Download PDF

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Publication number
CN1140199A
CN1140199A CN96106271A CN96106271A CN1140199A CN 1140199 A CN1140199 A CN 1140199A CN 96106271 A CN96106271 A CN 96106271A CN 96106271 A CN96106271 A CN 96106271A CN 1140199 A CN1140199 A CN 1140199A
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weight
oil
preferred
dewaxing
hydrogenation
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CN96106271A
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CN1102641C (en
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P·M·里诺莱恩
B·施佛尔
P·J·沃德尔
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Shell Internationale Research Maatschappij BV
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Shell Internationale Research Maatschappij BV
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    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING 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
    • C10G65/00Treatment of hydrocarbon oils by two or more hydrotreatment processes only
    • C10G65/02Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
    • C10G65/10Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only cracking steps
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2400/00Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/10Lubricating oil

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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)
  • Lubricants (AREA)

Abstract

Process for producing lubricating base oils, which process comprises the steps of: (a) contacting a hydrowax obtained as the bottom fraction of a hydrocracked effluent with a catalyst comprising platinum and/or palladium on a refractory oxide carrier in the presence of hydrogen under such conditions that at least 10% by weight, preferably at least 25% by weight, of the hydrocarbons having a boiling point of 370 degree C or higher, which are present in the hydrogen, is converted into hydrocarbons having a lower boiling point, (b) separating the product obtained in step (a) in at least one lighter distillate fraction and a heavy distillate fraction having a VI of 125 or higher, preferably of 135 or higher, and a kinematic viscosity at 100 degree C of a least 3.5 centiStokes, and (c) dewaxing the heavy distillate fraction obtained in step (b).

Description

Produce the method for lubricating base oil
The present invention relates to a kind of method of producing lubricating base oil.More particularly, the present invention relates to the method that a kind of hydrogenation wax oil that makes with the residual oil fraction of hydrocracked, treated is made raw material production high viscosity index (HVI) (VI) lubricating base oil.
The known lubricating base oil that very high VI (being that VI is more than 125 or 125) can be arranged by the raw material production that contains quite a large amount of wax molecules (being straight chain and slight branched alkanes and chain alkyl aromatic hydrocarbons and chain alkyl naphthenic hydrocarbon).In other words, such wax molecule itself has very high VI, so they have good influence to the VI of the product that contains these molecules.The object lesson of high wax content raw material is gatch and the synthetic wax of being produced by expense-holder building-up reactions.Gatch contains 50% (weight) or more wax usually, and synthetic wax even contain 80% (weight) or the wax more than 80% (weight).Purpose of the present invention aims to provide a kind of like this method, and the lubricating base oil that high VI wherein arranged is by the raw material production that low wax content is arranged, promptly in the raw material wax content less than 50% (weight), even less than 30% (weight).More particularly, the present invention aims to provide a kind of with hydroeracking unit residual oil fraction or the hydrogenation wax oil method as the such lubricating base oil of raw material production.Therefore, method of the present invention is particularly suitable for being combined in the refinery of hydrocracking throughput.
The whole bag of tricks of being produced lubricating base oil by the hydrogenation wax oil is that everybody is familiar with in this specialty.For example, disclose a kind of like this method in EP-A-0272729, the hydrocarbon raw material that wherein contains the flash distillation distillate of producing in residuum conversion process is by hydrocracking, subsequently that cracked stream is fuel-displaced residual oil fraction, is that the hydrogenation wax oil dewaxes.Before or after dewaxing treatment, can carry out hydrotreatment, with all unsaturated component hydrogenation.Preferred order is at first to dewax, the oily hydrotreatment that will dewax then.Last hydrogenation step increases the amount of the saturated component that contains, and hydrogenation of olefins becomes paraffinic hydrocarbon and isomery paraffinic hydrocarbon component to help increasing the VI of the base oil that finally makes.But contained aromatic component is also by hydrogenation, and it does not have the VI of final base oil or almost without any influence, therefore is helpless to improve VI.Therefore, can not make VI with the method for EP-A-0272729 is 125 or higher base oil.
The present invention aims to provide so a kind of method, and it is 125 or higher lubricating base oil that the hydrogenation wax oil that wherein available efficient manner is obtained by the residual oil fraction of hydrocracking effluent oil makes VI.
Therefore, the present invention relates to a kind of method of producing lubricating base oil, this method may further comprise the steps:
(a) the hydrogenation wax oil that the residual oil fraction of hydrocracking effluent oil is obtained contacts under such condition with the catalyzer that contains platinum and/or palladium/refractory oxide, so that the boiling point in the hydroeracking unit residual oil fraction is at least 1 0% (weight) of the hydro carbons more than 370 ℃ or 370 ℃, preferably at least 25% (weight) has been converted to more lower boiling hydro carbons
(b) product that obtains in the step (a) is separated at least a lighter oil distillate and heavy oil fraction, the latter's VI is more than 125 or 125, more than preferred 135 or 135, is at least 3.5 centistokes under 100 ℃ of its kinetic viscosities, and
The heavy oil fraction dewaxing that (c) will in step (b), obtain.
The used raw material of the inventive method is the residual oil fraction of hydrocracking effluent oil, and this effluent oil is obtained by the hydrocracking operation.The cut that term " residual oil fraction " refers to from the effluent oil that hydrocracking operation obtains, reclaim in the separation unit bottoms of separating this effluent oil.Therefore, described residual oil fraction (being commonly referred to the hydrogenation wax oil) is the hydrocracking effluent oil cut that contains heavy constituent.As the hydrogenation wax oil of the raw material of the inventive method should be that 300~450 ℃, the hydrocracking effluent oil of preferred 310~380 ℃ of scopes make by effective cut point (cutpoint).Effectively cut point is such temperature, and at least 85% (weight) in the hydrogenation wax oil of recovery, preferably the boiling point of at least 90% (weight) hydro carbons is higher than this temperature.
Hydrocracking is the known a kind of method for transformation of this specialty, and it relates in the presence of hydrogen hydrocarbon molecules is catalytically converted into less hydrocarbon molecules in essence.Various raw materials all can be used for the hydrocracking operation, comprising the oil distillate that obtains by other hydrocarbon conversion process, vacuum flashing distillate, and long residuum.Hydrocracking condition generally includes 250~500 ℃ of temperature, hydrogen dividing potential drop 1~300 crust, 0.1~10 kilogram of charging of weight space-time speed/rise catalyzer hour, and gas/charge ratio 100~5000 marks rise gas/kilogram charging.Hydrocracking catalyst also is that this specialty is known, and it comprises amorphous catalyst and based on the catalyzer of zeolite.Usually, hydrocracking catalyst contains the hydrogenation component of at least a VI family metal and/or hydrogenation component and a kind of carrier that contains amorphous material (as amorphous silicon oxide-aluminum oxide, silicon oxide or aluminum oxide) and/or zeolite of at least a VIII family metal.The zeolite of particularly suitable comprises the y-type zeolite of y-type zeolite or modification in this respect, as ultrastable Y.Back one class zeolite is the most suitable.The combination of amorphous material and zeolite also is suitable for.The VI family metal that is suitable for is tungsten (W) and molybdenum (Mo), and the VIII family metal that is suitable for is base metal nickel (Ni) and cobalt (Co) and noble metal platinum (Pt) and palladium (Pd).The example of the amorphous catalyst that is suitable for is to contain NiMo, CoMo, NiW, CoW, Pt, Pd or the PtPd catalyzer as hydrogenation component.The hydrocracking operation can be single stage operation (using a beds) or double-stage operation (using different catalysts bed on two).Hydrogenation wax oil as raw material can be made by any hydrocracking operation in principle in the methods of the invention.
In the step (a) of the inventive method, the hydrogenation wax oil is contacting under such condition in the presence of the hydrogen with the catalyzer of platiniferous and/or palladium/refractory oxide, obtains 370 ℃ +Transformation efficiency is at least 10% (weight), preferably at least 25% (weight), more preferably at least 35% (weight).Suitable is 370 ℃ +Transformation efficiency remains on below 80% (weight), preferably remaining on below 70% (weight), so transformation efficiency is when too high, from economic point of view, VI be the production of the lubrication base oil production more than 125 or 125 become be worth little.Most preferred 370 ℃ +Transformation efficiency is in 40~70% (weight) scope.Here the term of Shi Yonging is " 370 ℃ +Transformation efficiency " refer at hydrogenation wax oil mid-boiling point to be that the hydrocarbon conversion more than 370 ℃ or 370 ℃ becomes the weight percentage than low boiling point hydrocarbon.This just means that hydrogenation and hydrocracking all take place in step (a).The reaction conditions that is fit to comprises 350~550 ℃ of temperature (preferred 365~500 ℃), hydrogen dividing potential drop 10~300 crust (preferred 25~250 crust), 0.1~10 kilogram/liters per hour of weight space-time speed (preferred 0.2~5 kilogram/liters per hour) and hydrogen/charge ratio 100~5000 mark liter/kilograms (preferred 250~2000 mark liter/kilograms).
The catalyzer that is used for step (a) is the noble metal catalyst that contains platinum and/or palladium/refractory oxide.By the carrier total amount, platinum and/or the palladium total amount (by element) in catalyzer is preferably 0.1~5.0% (weight), more preferably 0.2~2.0% (weight).If two kinds of metals all exist, the weight ratio of platinum/palladium (by element) can change in wide range, but preferably in 0.05~10 scope, more preferably in 0.1~5 scope.In a preferred embodiment of the invention, the catalyzer platiniferous is as unique catalytically-active metals, and in another embodiment preferred of the present invention, the combination of catalyzer platiniferous and palladium.Platinum and palladium can elements, oxide compound and/or sulphided form exist.
Except that precious metal, the catalyzer that is used for step (a) also can contain at least a group vib metal component.Particularly, when palladium was used as precious metal, the existence of group vib metal component may be favourable.The group vib metal component that is suitable for comprises the oxide compound and the sulfide of chromium, molybdenum or tungsten, but also comprises the element form of these metals.Wherein, tungsten and chromium component are preferred.If the group vib metal component exists, press total restatement of carrier, its consumption is preferably 1~35% (weight), more preferably 5~30% (weight) (by element).Therefore, the example of optimal noble metal catalyst is to contain palladium and tungsten or contain palladium and the catalyzer of chromium.
The carrier that uses is refractory oxide.The refractory oxide that is fit to comprises two or more mixture of zeolite, aluminum oxide, amorphous silicon oxide-aluminum oxide, fluorizated aluminum oxide or its.Wherein, amorphous silicon oxide-aluminum oxide, zeolite and composition thereof are preferred, and the use of amorphous silicon oxide aluminum oxide is particularly preferred.The zeolite that is fit to is the above-mentioned zeolite that is applicable in the hydrocracking catalyst, i.e. (modification) y-type zeolite.Amorphous silicon oxide-the alumina supporting material that is fit to contains 10~70% (weight) aluminum oxide, and is commercially available.If carrier contains unformed silica-alumina and/or zeolite as refractory oxide, it also can contain tackiness agent.In this specialty, the use of adhesive material is known.Typical adhesive material is silicon oxide and aluminum oxide.Usually, the weight ratio of tackiness agent and refractory oxide can change in wide range, but preferably in the scope of 0 (being adhesive-free)~5, and more preferably 0~4.Particularly preferred catalyzer platiniferous and palladium/amorphous silicon oxide-alumina supporter.
The product that makes in the step (a) is separated at least one lighter oil distillate and heavy oil fraction subsequently in step (b), the latter's VI is (more than preferred 135 or 135) more than 125 or 125,100 ℃ of kinetic viscosities (VK100) at least 3.5 centistokes, and VK100 preferably is no more than 12.0 centistokes(cst)s.Surpass 135 when being intended to obtain VI, when VK100 is 4.5~7.5 heavy ends, obtained good result.Those skilled in the art should be understood that effective cut point of the combination decision heavy ends of above-mentioned VI and VK100, i.e. at least 85% (weight), the preferred temperature that surpasses of the boiling point of at least 90% (weight) hydro carbons in described heavy ends.In practice, this effective cut point in 350~500 ℃ of scopes, preferred 375~475 ℃.The light oil fraction that obtains is lower than the VI of heavy ends and has lower VK100.These light ends also have attractive character commercial, and they as lubricating base oil, not needing to be used for the application scenario of too high VI value after dewaxing.
The dewaxing step of carrying out in step (c) can realize by any known process for dewaxing in principle.The example of the dewaxing operation that is fit to is traditional solvent dewaxing process, particularly uses methylethylketone, toluene or its mixture those solvent dewaxing processes as dewaxing solvent, and the catalytic dewaxing method.These two kinds of wax fractionation processes all are big fixed familiar in this specialty.The most generally the solvent dewaxing process of Shi Yonging is methylethylketone (MEK) solvent dewaxing process, and wherein MEK also can mix with toluene as dewaxing solvent.Catalytic dewaxing is usually directed to straight chain and slight cracking and/or the isomerization of branched paraffins hydrocarbon molecule in the presence of hydrogen and dewaxing catalyst.Above-mentioned molecule has detrimentally affect to the cold flow performance of base oil.It is those catalyzer that contain ZSM-5, magnesium scolecite and/or silicon zeolite and optional hydrogenation component that mainly containing of being fit to is beneficial to paraffinic hydrocarbon cracked dewaxing catalyst.The example that mainly contains the catalyzer of the hydrocarbon isomerization that is beneficial to straight chain or slight side chain comprises the catalyzer that contains silicoaluminophosphates (SAPO is as SAPO-11, SAPO-31 and SAPO-41), ZSM-23 and SSZ-32.Should carry out the hydrofining step after the catalyzer dewaxing step, with any undersaturated species (alkene, the aromatic hydrocarbons) hydrogenation that still stays.For the present invention, preferably make solvent dewaxing or be used for isomerized catalytic dewaxing, i.e. shortening isomerization.
Following examples are used for further example and separate explanation the present invention.
Embodiment 1
The hydrogenation wax oil that boiling point distributes as shown in Table I contacts with the catalyzer that contains 1.0% (weight) palladium and 0.3% (weight) platinum (both weight percentage are all by total restatement of carrier)/amorphous silicon oxide-alumina supporter (alumina content is 45% (weight)).Operational condition is such, so that 370 ℃ +Transformation efficiency is 49.5% (weight).This corresponding operational condition is 390 ℃ of temperature, hydrogen dividing potential drop 190 crust, 1.0 kilograms/liters per hour of weight space-time speed (WHSV) and gas flow rate 750 mark liter/kilograms.Having than cut point is that 400 ℃ of following cracked stream of separating are fuel-displaced, 400 ℃ +Cut carries out solvent dewaxing with traditional M E K/ toluene wax fractionation process.The VI of dewaxed product is 140.1, and VK40 (kinetic viscosities under 40 ℃) is 23.8 centistokes, and VK100 is 4.98 centistokes, and its productive rate is counted 36.7% (weight) by charging.
The composition of Table I hydrogenation wax oil
Boiling point distributes
℃ 544-588 ℃ of 588 ℃-end point of distillation end point of distillation of initial boiling point IBP-370 ℃ 370-410 ℃ 410-480 ℃ 480-544 329 ℃ of 8% (weight) 22% (weight), 40% (weight) 20% (weight), 6% (weight) 4% (weight)>620 ℃
Embodiment 2
Boiling point distributes, and identical catalyzer contacts among as shown in Table I hydrogenation wax oil and the embodiment 1.Operational condition is such, so that 370 ℃ +Transformation efficiency is 28.8% (weight).This corresponding operational condition is 380 ℃ of temperature, hydrogen dividing potential drop 190 crust, 1.0 kilograms/liters per hour of weight space-time speed (WHSV), gas flow rate 750 mark liter/kilograms.Be separated into 385 ℃ with cracked stream is fuel-displaced -Cut, 385~450 ℃ of cuts and 450 ℃ +Cut.With 385~450 ℃ of cuts and 450 ℃ +Cut carries out solvent dewaxing with traditional MEK/ toluene wax fractionation process.The character of two kinds of dewaxing cuts is listed Table II in.
Table II
Product characteristics
Character 385-450 ℃ of cut 450 ℃+cut
VI Vk40 (centistoke) Vk100 (centistoke) productive rate (by charging restatement % (weight)) ????116.0 ????15.9 ????3.67 ????36.7 ????135.1 ????34.4 ????6.45 ????25.7
Table II shows, can obtain that good dynamics viscosity is arranged under 40 ℃ and 100 ℃, VI is greater than 135 product, and another dewaxed product that obtains also has attractive character as the oily base oil of profit, not needing to be used for the application scenario of too high VI (being that VI is more than 125 or 125).

Claims (7)

1. method of producing lubricating base oil, this method may further comprise the steps:
(a) the hydrogenation wax oil that the residual oil fraction of hydrocracking effluent oil is obtained contacts under such condition with the catalyzer that contains platinum and/or palladium/refractory oxide, so that the boiling point in the hydroeracking unit residual oil fraction is at least 10% (weight) of the hydro carbons more than 370 ℃ or 370 ℃, preferably at least 25% (weight) has been converted to more lower boiling hydro carbons
(b) product that obtains in the step (a) is separated at least a lighter oil distillate and heavy ends, the latter's VI is more than 125 or 125, more than preferred 135 or 135, and its 100 ℃ of kinetic viscosities are at least 3.5 centistokes, and
(c) with the heavy ends dewaxing that obtains in the step (b).
2. according to claim 1 method, wherein the hydrogenation wax oil is to be made by the hydrocracking effluent oil under 300~450 ℃, preferred 310~380 ℃ at effective cut point.
3. according to the method for claim 1 or 2, wherein refractory oxide is that amorphous silicon oxide-aluminum oxide, y-type zeolite are basic carrier or its mixture.
4. each method in requiring according to aforesaid right, wherein used catalyzer platiniferous and palladium/amorphous silicon oxide-alumina supporter in step (a).
5. each method in requiring according to aforesaid right, wherein step (a) is carried out under 350~500 ℃ of temperature (preferred 365~500 ℃), hydrogen dividing potential drop 10~300 crust (preferred 25~250 crust), 0.1~10 kilogram/liters per hour of weight space-time speed (preferred 0.2~5 kilogram/liters per hour), hydrogen/charge ratio 100~5000 mark liter/kilograms (preferred 250~2000 mark liter/kilograms).
6. each method in requiring according to aforesaid right, wherein dewaxing solvent dewaxing method is carried out in the step (c).
7. according to each method in the claim 1~5, wherein the dewaxing in the step (c) is carried out with catalyst hydrogenation isomery facture, the optional hydrofining step of then carrying out.
CN96106271A 1995-04-28 1996-04-26 Process for producing lubricating base oils Expired - Fee Related CN1102641C (en)

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EP95400991.6 1995-04-28
EP95400991 1995-04-28

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CN1102641C CN1102641C (en) 2003-03-05

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SA (1) SA96170146B1 (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1075549C (en) * 1998-12-16 2001-11-28 中国石油化工集团公司 Method for producing base oil of high viscosity index lubricant
CN101775331A (en) * 2010-03-01 2010-07-14 闫涛 Method for extracting base oil from used oil by catalytic oxidation
CN103102946A (en) * 2011-11-10 2013-05-15 中国石油化工股份有限公司 Production method for light lubricant base oil and heavy lubricant base oil

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KR100857364B1 (en) * 2006-11-08 2008-09-05 현대자동차주식회사 Air-filter unit of folding type and air cleaner device for vehicle
CN102911726B (en) * 2011-08-01 2015-04-15 中国石油化工股份有限公司 Production method for base oil of high velocity index lubricating oil

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CA1203225A (en) * 1981-08-07 1986-04-15 Stephen M. Oleck Two-stage hydrocarbon dewaxing hydrotreating process
FR2624525B1 (en) * 1987-12-11 1993-09-03 Pradom Ltd FIBER COATING PROCESS AND ITS APPLICATIONS FOR THE PRODUCTION OF COMPOSITE MATERIALS
CA1328635C (en) * 1987-12-18 1994-04-19 Ian Alfred Cody Method for stabilizing hydroisomerates
FR2626005A1 (en) * 1988-01-14 1989-07-21 Shell Int Research PROCESS FOR PREPARING A BASIC LUBRICATING OIL
US5098551A (en) * 1989-05-30 1992-03-24 Bertaux Jean Marie A Process for the manufacture of lubricating base oils
US5275719A (en) * 1992-06-08 1994-01-04 Mobil Oil Corporation Production of high viscosity index lubricants
JP3065816B2 (en) * 1992-10-02 2000-07-17 日石三菱株式会社 Production method of high viscosity index low viscosity lubricating base oil
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1075549C (en) * 1998-12-16 2001-11-28 中国石油化工集团公司 Method for producing base oil of high viscosity index lubricant
CN101775331A (en) * 2010-03-01 2010-07-14 闫涛 Method for extracting base oil from used oil by catalytic oxidation
CN103102946A (en) * 2011-11-10 2013-05-15 中国石油化工股份有限公司 Production method for light lubricant base oil and heavy lubricant base oil
CN103102946B (en) * 2011-11-10 2015-07-22 中国石油化工股份有限公司 Production method for light lubricant base oil and heavy lubricant base oil

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DE69605852D1 (en) 2000-02-03
DE69605852T2 (en) 2000-06-15
KR100426263B1 (en) 2004-05-31
CA2175020A1 (en) 1996-10-29
CA2175020C (en) 2007-06-19
SA96170146B1 (en) 2006-05-06
BR9602049A (en) 1998-10-06
KR960037807A (en) 1996-11-19

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