EP0761648A2 - Herstellung von Phenat-Stearat mit hohen Basenzahlen und geringer feiner Sedimentenformung - Google Patents

Herstellung von Phenat-Stearat mit hohen Basenzahlen und geringer feiner Sedimentenformung Download PDF

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Publication number
EP0761648A2
EP0761648A2 EP96306180A EP96306180A EP0761648A2 EP 0761648 A2 EP0761648 A2 EP 0761648A2 EP 96306180 A EP96306180 A EP 96306180A EP 96306180 A EP96306180 A EP 96306180A EP 0761648 A2 EP0761648 A2 EP 0761648A2
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EP
European Patent Office
Prior art keywords
stearate
overbased
phenate
mixture
overbasing
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.)
Granted
Application number
EP96306180A
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English (en)
French (fr)
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EP0761648B1 (de
EP0761648A3 (de
Inventor
Curtis B. Campbell
Christopher S. Fridia
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Chevron Phillips Chemical Co LP
Original Assignee
Chevron Chemical Co LLC
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Publication date
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Publication of EP0761648A3 publication Critical patent/EP0761648A3/de
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M159/00—Lubricating compositions characterised by the additive being of unknown or incompletely defined constitution
    • C10M159/12—Reaction products
    • C10M159/20—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products
    • C10M159/22—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products containing phenol radicals

Definitions

  • the present invention relates to the production of highly overbased phenate stearate.
  • the present invention comes out of work in the production of phenate stearate having a high Total Base Number (TBN). That production is hampered by the creation of a fine sediment. The fine sediment is virtually impossible to remove from the product by means common to the manufacture of phenate, such as filtration.
  • TBN Total Base Number
  • EPO 0,094,814 A2 teaches improving the stability of an overbased phenate by treating the phenate with a carboxylic acid having a C 10 to C 24 unbranched segment, such as stearic acid.
  • WO 88/03944 and 88/03945 teach an overbased phenate having a TBN of more than 300. This high TBN is achieved by using an additional component: either a carboxylic acid, such as stearic acid, or a di- or poly carboxylic acid having from 36 to 100 carbon atoms, or an anhydride, acid chloride, or ester thereof.
  • a carboxylic acid such as stearic acid
  • a di- or poly carboxylic acid having from 36 to 100 carbon atoms or an anhydride, acid chloride, or ester thereof.
  • the present invention provides a process that produces an overbased sulfurized phenate stearate without producing fine sediments. That process controls the degree of agitation and the ratio of ethylene glycol to water during the overbasing process to prevent the formation of fine sediments.
  • a mixture having a sulfurized phenate, a metal stearate (such as calcium stearate), at least one solvent, calcium hydroxide, and water is overbased by contacting the mixture with carbon dioxide in the presence of an alkyl polyhydric alcohol.
  • the level of agitation is sufficiently high so that all solids are suspended over the length of the overbasing step.
  • the overbased mixture is stripped to produce an overbased phenate stearate having less than 0.10 vol.% fine sediments.
  • the polyhydric alcohol to water ratio is maintained sufficiently high so that the ratio is at least 4:1 at the end of the overbasing step. More preferably, the polyhydric alcohol to water ratio is maintained sufficiently high so that the ratio is at least 9:1 at the end of the overbasing step.
  • the overbased phenate stearate has less than 0.05 vol.% fine sediments.
  • the alkyl group of the alcohol has from one to five carbon atoms.
  • the alkyl polyhydric alcohol is ethylene glycol.
  • the sulfurized phenate to be overbased can comprise a partially overbased sulfurized phenate.
  • Figure 1 shows how fine sediment varies as a function of degree of agitation and the weight ratio of ethylene glycol to water at the end of the carbonation step in the process, in a reactor operating with poor agitation.
  • Figure 2 shows how the fine sediment varies as a function of the weight ratio of ethylene glycol to water at the end of the carbonation step in the process, in a reactor operating with good agitation.
  • the present invention involves a process for producing an overbased phenate stearate without the production of fine sediments. That process comprises overbasing a mixture that comprises sulfurized phenate, metal stearate, at least one solvent, calcium hydroxide, and water, by contacting the mixture with carbon dioxide in the presence of an alkyl polyhydric alcohol, and stripping the overbased mixture to produce an overbased phenate stearate having less than 0.10 vol.% fine sediments.
  • one In order to achieve less than 0.10 vol.% fine sediments, one must maintain the level of agitation sufficiently high so that all solids are suspended over the length of the overbasing step. Preferably, one should also maintain a polyhydric alcohol to water ratio sufficiently high so that the ratio is at least 4:1 at the end of the overbasing step.
  • the alkyl group of the alkyl polyhydric alcohol should have from one to five carbon atoms.
  • One such useful alkyl polyhydric alcohol is ethylene glycol.
  • the stearate can calcium stearate, and the sulfurized phenate can comprises an sulfurized phenate that has been previously overbased.
  • the fine sediment was determined by following a modification of the ASTM Test Method D 2273 ( Standard Test Method for Trace Sediment in Lubricating Oils).
  • the degree to which the carbon dioxide gas is dispersed, or mixed, into the reaction depends on the effectiveness of the gas-liquid mixing in a particular reactor.
  • Engineering analysis of the gas-liquid mixing occuring during overbasing revealed that one contributing factor to the formation of this fine sediment was localized overoverbasing or inadequate gas-liquid mixing. During carbonation, adequate gas-liquid mixing is necessary to prevent the formation of a fine sediment.
  • ASL Agitation Scale Level
  • the effectiveness of gas-liquid mixing for a specific reactor can be expressed as an Agitation Scale Level (ASL) value, a term often used in the industry.
  • ASL value for a given reactor is a function of reactor diameter, liquid volume, impeller diameter, number of impeller blades, impeller blade pitch, impeller blade height, liquid density, liquid viscosity, impeller RPM and gas flow rate.
  • the ASL scale ranges between 0 and 10 and can be broken into four groups:
  • polyhydric alcohol such as ethylene glycol
  • polyhydric alcohol such as ethylene glycol
  • water is produced by the neutralization reactions between the calcium hydroxide and the alkylphenol and stearic acid and also between the reaction of calcium hydroxide with carbon dioxide.
  • the bulk of this water is removed during the reaction.
  • the reactor temperature and pressure is such that ethylene glycol should not be distilling. This removal of the ethylene glycol is also increased during the overbasing step if inefficient gas-liquid mixing is present.
  • the weight percent ethylene glycol and water present in the reactor is determined by removing a sample of the reactor contents and subjecting the sample to an azeotropic distillation using Xylene and collecting the distillate which then contains the ethylene glycol and water as a separate phase. The amount of ethylene glycol present in this separate phase is determined by refractive index.
  • the reactor was heated to 290° F ⁇ 5° F (143° C ⁇ 2° C) over 1.5 ⁇ 0.25 hours.
  • 290° F ⁇ 5°F 803 pounds (364 kilograms) of liquid sulfur was charged to the reactor and allowed to mix for 10 - 20 minutes to ensure complete incorporation of the sulfur into the reactor.
  • the reactor was then heated to 300° F (148° C).
  • 300° F ⁇ 5° F 148° C ⁇ 2° C
  • 580 pounds (263 kilograms) of ethylene glycol was added over 1.5 hours while the reactor was heated to 350° F ⁇ 5° F (176° C ⁇ 2° C).
  • a 1 quart (0.946 liter) sample was removed from the reactor and the water and ethylene glycol in a 100 gram aliquot of this sample was subjected to azeotropic distillation to afford 2.6 mls of azeotrope.
  • the ethylene glycol content of this azeotrope was determined by refractive index to be 90.0 %, or 2.3 grams of ethylene glycol.
  • the reactor vacuum was reduced to 0.5 - 1.5 psia (0.035 - 0.11 kg/cm 2 ) gradually over 30 minutes while heating the reactor temperature to 425° F ⁇ 5° F (218° C ⁇ 2° C) .
  • the reactor reached 425° F ⁇ 5° F and 0.5 - 1.5 psia, it was held for 1.5 hours.
  • the reactor vacuum was broken with purge nitrogen and the reactor was cooled to 350° F ⁇ 5° F (176° C ⁇ 2° C), and the contents of the reactor (18,603 pounds or 8,438 kilograms) was pumped to a storage tank. Following this, 718 pounds (325 kilograms) of diluent oil was flushed through the reactor and pump into the storage tank.
  • FIG. 1 a series of runs were made to show how fine sediment varies as a function of degree of agitation and the weight ratio of ethylene glycol to water (EG/H 2 O) at the end of the carbonation step in the process, in a reactor operating with poor agitation (an Agitation Scale Level of between 1 and 2).
  • Figure 1 shows that as the EG/H 2 O ratio increases; the level of fine sediment decreases dramatically. For example, at an EG/H 2 O ratio of 4.7, a fine sediment content of 5.9 volume % is observed while at an EG/H 2 O ratio of 9.0, an average fine sediment of 0.026 volume % is observed (average of three different reactions showing 0.02, 0.02 and 0.04 volume % fine sediment).
  • Figure 2 shows how the fine sediment varies as a function of the weight ratio of ethylene glycol to water (EG/H 2 O) at the end of the carbonation step in the process, in a reactor operating with good agitation (an Agitation Scale Level of between 3 and 4).
  • Figure 2 shows that as the EG/H 2 O ratio increases; the level of fine sediment decreases but not as dramatically as when an the reactor is operating at a low ASL level (between 1 and 2 - see Figure 1).
  • Figure 2 shows that with an EG/H 2 O ratio of 4.0, the fine water.sediment content is 0.14 volume % while at an EG/H 2 O ratio of 7.3, a 0.04 volume % fine sediment is observed.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Lubricants (AREA)
EP19960306180 1995-08-23 1996-08-23 Herstellung von Phenat-Stearat mit hohen Basenzahlen und geringer feiner Sedimentenformung Expired - Lifetime EP0761648B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US271695P 1995-08-23 1995-08-23
US2716 1995-08-23

Publications (3)

Publication Number Publication Date
EP0761648A2 true EP0761648A2 (de) 1997-03-12
EP0761648A3 EP0761648A3 (de) 1997-03-26
EP0761648B1 EP0761648B1 (de) 1999-06-30

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EP19960306180 Expired - Lifetime EP0761648B1 (de) 1995-08-23 1996-08-23 Herstellung von Phenat-Stearat mit hohen Basenzahlen und geringer feiner Sedimentenformung

Country Status (4)

Country Link
EP (1) EP0761648B1 (de)
JP (1) JPH09104887A (de)
CA (1) CA2183906A1 (de)
DE (1) DE69603055T2 (de)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1710294A1 (de) 2005-04-06 2006-10-11 Infineum International Limited Verfahren zur Verbesserung der Stabilität oder der Kompatibilität von Tensiden

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3372116A (en) * 1965-10-05 1968-03-05 Lubrizol Corp Preparation of basic metal phenates and salicylates
EP0273588A1 (de) * 1986-11-29 1988-07-06 Bp Chemicals (Additives) Limited Geschwefelt Erdalkalimetallalkylphenolate, ihre Herstellung und ihre Verwendung
EP0410648A2 (de) * 1989-07-26 1991-01-30 Bp Chemicals (Additives) Limited Verfahren zur Herstellung eines Schmierölzusatzkonzentrats
EP0486893A1 (de) * 1990-11-19 1992-05-27 Idemitsu Kosan Company Limited Uberbanisches geschwefelten Erdalkalimetallphenolate und Verfahren zu ihrer Herstellung
EP0558021A2 (de) * 1992-02-26 1993-09-01 Cosmo Research Institute Verfahren zur Herstellung eines überbasischen Erdalkaliphenats
EP0601721A2 (de) * 1992-12-07 1994-06-15 Ethyl Petroleum Additives, Inc. Verfahren zur Herstellung von überbasischen Phenolaten
EP0640682A1 (de) * 1993-08-25 1995-03-01 Cosmo Research Institute Überbasisches sulfuniertes Erdalkaliphenat und Verfahren zu seiner Herstellung

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3372116A (en) * 1965-10-05 1968-03-05 Lubrizol Corp Preparation of basic metal phenates and salicylates
EP0273588A1 (de) * 1986-11-29 1988-07-06 Bp Chemicals (Additives) Limited Geschwefelt Erdalkalimetallalkylphenolate, ihre Herstellung und ihre Verwendung
EP0410648A2 (de) * 1989-07-26 1991-01-30 Bp Chemicals (Additives) Limited Verfahren zur Herstellung eines Schmierölzusatzkonzentrats
EP0486893A1 (de) * 1990-11-19 1992-05-27 Idemitsu Kosan Company Limited Uberbanisches geschwefelten Erdalkalimetallphenolate und Verfahren zu ihrer Herstellung
EP0558021A2 (de) * 1992-02-26 1993-09-01 Cosmo Research Institute Verfahren zur Herstellung eines überbasischen Erdalkaliphenats
EP0601721A2 (de) * 1992-12-07 1994-06-15 Ethyl Petroleum Additives, Inc. Verfahren zur Herstellung von überbasischen Phenolaten
EP0640682A1 (de) * 1993-08-25 1995-03-01 Cosmo Research Institute Überbasisches sulfuniertes Erdalkaliphenat und Verfahren zu seiner Herstellung

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1710294A1 (de) 2005-04-06 2006-10-11 Infineum International Limited Verfahren zur Verbesserung der Stabilität oder der Kompatibilität von Tensiden

Also Published As

Publication number Publication date
DE69603055D1 (de) 1999-08-05
JPH09104887A (ja) 1997-04-22
CA2183906A1 (en) 1997-02-24
EP0761648B1 (de) 1999-06-30
EP0761648A3 (de) 1997-03-26
DE69603055T2 (de) 1999-10-21

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