EP0323759A2 - Olefinpolymerisationsverfahren mit Kontrolle der Viskosität und des Fliesspunktes des Produkts - Google Patents

Olefinpolymerisationsverfahren mit Kontrolle der Viskosität und des Fliesspunktes des Produkts Download PDF

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Publication number
EP0323759A2
EP0323759A2 EP88312436A EP88312436A EP0323759A2 EP 0323759 A2 EP0323759 A2 EP 0323759A2 EP 88312436 A EP88312436 A EP 88312436A EP 88312436 A EP88312436 A EP 88312436A EP 0323759 A2 EP0323759 A2 EP 0323759A2
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EP
European Patent Office
Prior art keywords
peroxide
process according
polymer
viscosity
treatment
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EP88312436A
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English (en)
French (fr)
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EP0323759A3 (de
Inventor
Henry Ashjian
Quang Ngoc Le
William Everett Garwood
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ExxonMobil Oil Corp
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Mobil Oil Corp
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Publication date
Application filed by Mobil Oil Corp filed Critical Mobil Oil Corp
Publication of EP0323759A2 publication Critical patent/EP0323759A2/de
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G50/00—Production of liquid hydrocarbon mixtures from lower carbon number hydrocarbons, e.g. by oligomerisation
    • C10G50/02—Production of liquid hydrocarbon mixtures from lower carbon number hydrocarbons, e.g. by oligomerisation of hydrocarbon oils for lubricating purposes
    • 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
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/10—Lubricating oil

Definitions

  • This invention relates to olefin polymerization processes; more particularly, this invention relates to olefin polymerization processes with product viscosity and pour point control.
  • peroxide treatment for modifying the viscosity of various lubestocks including distillates and hydrocracked resids has been described in U.S. 3,128,246 and 3,594,320. Other peroxide treatment processes are described in U.S. 4,594,172 and 4,618,737. Peroxide treatment has not, however, previously been proposed for use with light neutral viscosity range decene oligomers from a BF3 polymerization process.
  • the invention seeks to provide a process which eliminates the need for such alkyl aluminum chloride or esters thereof while providing a significant advance in the art by further reduction in pour point and increase in viscosity without significant change in viscosity index.
  • the present invention provides a process for producing a high viscosity index, low pour point synthetic lubricant from a 1-olefin feed, which process comprises:
  • the improved synthetic lubricants of the present invention are suitably produced from 1-decene, or from a mixture of 1-olefins, having between about 6 and about 12 carbon atoms, having a mean value of the olefin chain length of about 10 carbon atoms, although the 1-olefin charge can be any normally liquid 1-olefin having between about 5 and about 20 carbon atoms or mixtures of such 1-olefins.
  • Examples of the 1-olefin charge are 1-pentene; 3-methyl-1-butene; 1-hexene; 3,3-dimethyl-1-butene; 2,3-dimethyl-1-butene; 1-heptene; 1-octene; 2,3,3-trimethyl-1-pentene; 2-ethyl-1-hexene; 1-decene; 1-undecene; 1-dodecene; 1-tetradecene; 1-hexadecene; 1-octadecene; and 1-eicosene, with 1-decene being preferred.
  • a 1-olefin charge is saturated with BF3, suitably at room temperature, before it is charged to the reaction zone.
  • the second stream that is charged to the reactor is a 1:1 molar complex of BF3 and a promotor compound. This complex, upon contacting the first stream in the reactor, effects the polymerization reaction.
  • the promoter compound used to form BF3-promoter catalyst complexes include, by way of example, water; alcohols, such as octanol and 1-decanol; acids, such as acetic acid, propionic acid, and butyric acid; ethers, such as diethyl ether; acid anhydrides such as acetic acid anhydride and succinic anhydride; esters, such as ethyl acetate and methyl propionate; ketones, such as acetone; and aldehydes, such as benzaldehyde.
  • the rate of addition of stream (2) is conveniently expressed in terms of moles of promoter per weight unit of olefin. This rate will be between 0.006 mole promoter and 0.01 mole promoter per 100 g. of 1-olefin charge.
  • the reaction temperature employed is generally below 60°C and preferably between 0°C and 35°C.
  • the reaction can be carried out at atmospheric pressure, but moderate pressures from about 1 psig up to about 500 psig are preferred.
  • the present process is suitably used with neutral lube feeds, that is, a vacuum stripped bottoms fraction of the oily liquid polymer, ranging from light neutrals, that is, from 100 SUS at 100°F to heavy neutrals, that is, 700 SUS at 100°F.
  • Typical light to medium neutral stocks may have an IBP below 650°F (about 345°C) (ASTM D-2887) and the end point may be below 1000°F (about 540°C).
  • Heavier neutrals will generally boil in the range 650°F to 1050°F (about 345°C to 565°C, ASTM D-1160, 10 mm Hg), typically from 750°F to 1050°F (about 400°C to 565°C, ASTM D-1160).
  • FIG. 2 schematically depicts the process of the invention.
  • the first step is the BF3 polymerization process.
  • the oligomers formed (oily liquid polymer) includes the light neutral viscosity range oligomers.
  • This synthetic lubrication product can be washed as shown, using conventional techniques.
  • Figure 2 further shows a stripping step used to separate the light neutral viscosity range oligomer. It can occur in an autoclave under vacuum.
  • the peroxide treatment can precede or follow the distillation step. Treatment before stripping is preferred.
  • Catalysts typically comprise a base metal hydrogenation component such as nickel, tungsten, cobalt, nickel-tungsten, nickel-molybdenum or cobalt-molybdenum, on a inorganic oxide support of low acidity such as silica, alumina or silica-alumina, generally of a large pore, amorphous character.
  • Typical hydrotreating conditions use moderate temperatures and pressures, e.g.
  • the catalyst can be filtered after hydrogenation is complete.
  • the oily liquid polymer product is subjected to treatment with an organic peroxide compound at elevated temperature to affect a coupling between the polymer components to increase the viscosity of the lubricant.
  • the treatment preferably occurs before stripping but can occur afterwards. The treatment can be repeated.
  • the preferred class of organic peroxides are ditertiary alkyl peroxides represented by the formula ROOR1 where R and R1, which may be the same or different, each represent tertiary alkyl groups, preferably lower (C4 to C6) tertiary alkyl groups.
  • Suitable peroxides of this kind include ditertiary butyl peroxide, ditertiary amyl peroxide and tertiary butyl, tertiary amyl peroxide.
  • organic peroxides may also be used including dialkyl peroxides with one to ten carbon atoms such as dimethyl peroxide, diethyl peroxide, dipropyl peroxide, di-n-butyl peroxide, dihexyl peroxide and acetylperoxides such as dibenzoylperoxide.
  • the amount of peroxy compound used in the process is determined by the increase in viscosity which is desired in the treatment.
  • the increase in viscosity is related to the amount of peroxide used with greater increases resulting from greater amounts of peroxide.
  • the amount of peroxide catalyst used will be from 1 to 50, preferably from 4 to 30 weight percent of oil.
  • the presence of hydrogen may decrease peroxide utilization slightly, but significant increases in viscosity may still be obtained without other lube properties being significantly affected. The exception to this statement is that pour point is reduced.
  • the reaction between the lubricant component and the peroxide is carried out at elevated temperature, suitably at temperatures from 50°C to 300°C and in most cases from 100°C to 200°C.
  • the treatment duration will normally be from 1 hour to 6 hours. There is no fixed duration because various starting materials will vary in their reactivity and amenability to coupling by this method.
  • the pressure used depends upon the temperature and upon the reactants and, in most cases, needs to be sufficient only to maintain the reactants in the liquid phase during the reaction. Space velocity in continuous operation will normally be from 0.25 to 5.0 LHSV (hr ⁇ 1).
  • the peroxide is converted during the reaction primarily to an alcohol whose boiling point will depend upon the identity of the selected peroxide.
  • This alcohol by-product may be removed during the course of the reaction by simple choice of temperature and pressure. Accordingly, temperature and pressure may be selected together to ensure removal of this product.
  • the alcohol may be converted back to the peroxide in an external regeneration step and recycled for further use. If ditertiary butyl peroxide is used, the tertiary butyl alcohol formed may be used directly as a gasoline octane improver. Alternatively, it may be readily converted back to the original ditertiary butyl peroxide by reaction with butyl hydroperoxide in the presence of a mineral acid, as described in U.S. 2,862,973, with the butyl hydroperoxide being obtained by the direct oxidation of isobutane, as described in U.S. 2,862,973.
  • the reaction may be carried out batchwise or continuously. In either case, it is preferable to inject the peroxide compound incrementally to avoid exotherms and production of lower quality products associated with high reaction temperatures. If the reaction is carried out in a continuous tubular reactor, it is preferred to inject the peroxide compound at a number of points along the reactor to achieve the desired incremental addition.
  • the effect of the peroxide treatment is principally to increase the viscosity of the lubricant and reduce pour point without affecting a significant reduction in viscosity index or significant increase in cloud point.
  • the increase in viscosity implies an increase in molecular weight. It is thought that the action of the peroxide is by the removal of hydrogen atoms to form free radicals in non-terminal positions which then combine with each other to form branched chain dimers which are capable of reacting even more rapidly than the monomer. Thus, the viscosity of the treated material increases rapidly in the presence of additional amounts of peroxide which generate new free radicals.
  • the greater reactivity perceived with the initial dimer may be attributed to reactive tertiary hydrogens which are present in the dimers and higher reaction products but not on the paraffins present in the starting material.
  • the greater reactivity of the dimers indicates that the incremental addition of successively smaller amounts of peroxide, particularly in continuous tubular reactor synthesis, will produce relatively greater progressive increases in viscosity.
  • the reactivity also ensures that the range of molecular weights in the product will be narrower and that product quality will be more consistent.
  • the products of the present process are characterized by a high viscosity index coupled with a low pour point.
  • Viscosity indices of at least 130, for example, 140 or 150 are characteristic of the products but with low pour points indicating a significant quantity of iso-paraffinic components.
  • Pour points below 10°F for the base stock (that is, without pour point improvers or other additives) and in most cases below 5°F are readily obtained, for example, 0°F with correspondingly low Brookfield viscosities, for example, less than 2500b at -20°F.
  • a light neutral viscosity range lube is made from 1-decene as described in U.S. 3,382,291.
  • Properties before and after hydrogenation are as follows: After Hydrogenation Before Hydrogenation Gravity, API 39.9 38.0 Specific 0.8256 0.8348 Pour Point, °F less than -65 less than -65 K.V. 40°C, cs 28.54 27.98 K.V. 100°C, cs 5.55 5.47 K.V. 100°F, cs 31.1 30.5 K.V. 210°F, cs 5.67 5.58 SUS 100°F 147 144 SUS 210°F 44.8 44.5 Viscosity Index 135.9 135.1
  • the 99.6 g of lube product had the following properties: Gravity, °API 37.2 Specific 0.8388 Pour Point, °F less than -65 KV at 40°C, cs 68.8 KV at 100°C, cs 10.55 KV at 100°F, cs 75.9 KV at 210°F, cs 10.86 SUS at 100°F 352 SUS 210°F 62.1 Viscosity Index 141.1
  • Example 2 100 g of stock from Example 1, which is not hydrogenated, is reacted with 20 DTBP in the same manner as described in Example 2.
  • the 98.8 g of lube product had the following properties: Gravity, °API 35.0 Specific 0.8499 Pour Point, °F -65 KV at 40°C, cs 98.8 KV at 100°C, cs 13.6 KV at 100°F, cs 110.0 KV at 210°F, cs 14.0 SUS at 100°F 508 SUS at 210°F 74.0 Viscosity Index 138.5
  • the viscosity of this product charging the unhydrogenated oligomer is higher than that of Example 2, 508 vs. 352 SUS at 100°F.
  • Example 3 50 g of the lube product from Example 3 is reacted with 10 g DTBP in the same manner as described in Example 2.
  • the 49.8 g of lube product had the following properties: Gravity, °API 32.2 Specific 0.8639 Pour Point, °F -40 KV at 40°C, cs 385.5 KV at 100°C, cs 38.5 KV at 100°F, cs 435 KV at 210°F, cs 39.7 SUS at 100°F 2012 SUS at 210°F 187 Viscosity Index 147.7
  • the experiment in this example is carried out in a two gallon autoclave.
  • 4934 g of stock (unhydrogenated oligomers as in Example 3) and 1233 g. of DTBP are added together to the autoclave.
  • the autoclave is sealed with nitrogen at room pressure and gradually heated up to 150°C while stirring at 200 RPM.
  • the total liquid product is flashed at 150°C for 0.5 hour followed by nitrogen purging at 125°C for two hours to remove all by-products (alcohol and acetone).
  • the lube product is then cooled to room temperature and discharged.
  • the lube product had the following properties: Specific Gravity 0.854 Pour Point, °F -55 KV at 40°C, cs 210.4 KV at 100°C, cs 24.09 KV at 100°F, cs 235 KV at 210°F, cs 24.8 SUS at 100°F 1091 SUS at 210°F 119 Viscosity Index 142.5
  • the autoclave experiment shows much higher viscosity compared to the glassware experiment in Example 3 (1091 vs 508 SUS at 100°F and 143 vs 138.5 VI) although the DTBP dosage used is only slightly higher (20 wt% vs 16.7 wt% DTBP).
  • the peroxide utilization is improved with the closed autoclave experiment because of better contact and the elimination of peroxide loss due to evaporation.
  • BF3-DTBP process eliminates the need for alkyl aluminum chloride to make higher viscosity polyalpha olefin lubricants which cannot be made with BF3 alone. Additionally, because the need for alkyl aluminum chlorides is avoided, the process of the present invention avoids environmental and disposal problems incurred in the use of the alkyl aluminum chloride process. Thus, environmental problems in disposing of the alkyl aluminum chloride heel are avoided. Moreover, corrosion of vessels and lines and a complicated process utilizing extensive washing necessary with the alkyl aluminum chloride process are avoided.
  • the DTBP step can be integrated into the BF3 process preferably before the vacuum stripping step.
  • Product yield for the combined BF3-DTBP process will still be 99% compared to 90 to 93% for the alkyl aluminum chloride process.

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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)
  • Lubricants (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
EP88312436A 1988-01-06 1988-12-30 Olefinpolymerisationsverfahren mit Kontrolle der Viskosität und des Fliesspunktes des Produkts Withdrawn EP0323759A3 (de)

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US14118988A 1988-01-06 1988-01-06
US141189 1988-01-06

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EP0323759A2 true EP0323759A2 (de) 1989-07-12
EP0323759A3 EP0323759A3 (de) 1990-03-07

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5420373A (en) * 1994-03-24 1995-05-30 Chevron Chemical Company Controlled formation of olefin oligomers
EP0785245A3 (de) * 1996-01-12 1998-05-06 Chevron Chemical Company Olefin Oligomerizationsverfahren
WO1998024863A1 (en) * 1996-12-03 1998-06-11 Chevron Chemical Company Llc High viscosity polyalphaolefins

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4973789A (en) * 1987-07-30 1990-11-27 The Lubrizol Corporation Lower alkene polymers
DE502004005326D1 (de) * 2003-04-16 2007-12-06 Cognis Ip Man Gmbh Oligo-alpha-olefin-haltige kosmetische zusammensetzung

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3382291A (en) * 1965-04-23 1968-05-07 Mobil Oil Corp Polymerization of olefins with bf3
US3594320A (en) * 1968-02-19 1971-07-20 Mobil Oil Corp Hydrocracked lubricants
US4434309A (en) * 1982-06-18 1984-02-28 Texaco Inc. Oligomerization of predominantly low molecular weight olefins over boron trifluoride in the presence of a protonic promoter

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3382291A (en) * 1965-04-23 1968-05-07 Mobil Oil Corp Polymerization of olefins with bf3
US3594320A (en) * 1968-02-19 1971-07-20 Mobil Oil Corp Hydrocracked lubricants
US4434309A (en) * 1982-06-18 1984-02-28 Texaco Inc. Oligomerization of predominantly low molecular weight olefins over boron trifluoride in the presence of a protonic promoter

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5420373A (en) * 1994-03-24 1995-05-30 Chevron Chemical Company Controlled formation of olefin oligomers
EP0785245A3 (de) * 1996-01-12 1998-05-06 Chevron Chemical Company Olefin Oligomerizationsverfahren
WO1998024863A1 (en) * 1996-12-03 1998-06-11 Chevron Chemical Company Llc High viscosity polyalphaolefins

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JPH01247490A (ja) 1989-10-03
ZA89141B (en) 1990-09-26
AU2771389A (en) 1989-07-06
EP0323759A3 (de) 1990-03-07

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