EP0761648B1 - Production de phénate stéarate à indice de base totale élevé ayant une formation de sédiments fins basse - Google Patents

Production de phénate stéarate à indice de base totale élevé ayant une formation de sédiments fins basse Download PDF

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Publication number
EP0761648B1
EP0761648B1 EP19960306180 EP96306180A EP0761648B1 EP 0761648 B1 EP0761648 B1 EP 0761648B1 EP 19960306180 EP19960306180 EP 19960306180 EP 96306180 A EP96306180 A EP 96306180A EP 0761648 B1 EP0761648 B1 EP 0761648B1
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EP
European Patent Office
Prior art keywords
stearate
overbased
phenate
reactor
ratio
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Expired - Lifetime
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EP19960306180
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German (de)
English (en)
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EP0761648A3 (fr
EP0761648A2 (fr
Inventor
Curtis B. Campbell
Christopher S. Fridia
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Chevron Phillips Chemical Co LP
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Chevron Chemical Co LLC
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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.
  • the 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: ASL Description 0 Indicates a flooded impeller. 1-2 Provides nonflooded impeller conditions for coarse dispersion of gas. Typical applications are ones in which mass transfer or gas dispersion is not critical.
  • 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 ⁇ C) . 2°
  • 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)

Claims (8)

  1. Procédé pour la production d'un phénate-stéarate surbasique, comprenant les étapes consistant :
    (a) à rendre surbasique un mélange qui comprend un phénate sulfuré, un stéarate métallique, au moins un solvant, de l'hydroxyde de calcium et de l'eau, en mettant en contact ledit mélange avec du dioxyde de carbone en présence d'un alcool alkylique polyhydroxylique, tout en maintenant un degré d'agitation suffisamment fort pour que toutes les substances solides soient en suspension au cours de l'étape de formation d'un mélange surbasique, le groupe alkyle de l'alcool ayant un à cinq atomes de carbone ; et
    (b) à soumettre à un entraínement ledit mélange surbasique pour produire un phénate-stéarate surbasique renfermant moins de 0,10 % en volume de sédiments fins.
  2. Procédé suivant la revendication 1, dans lequel l'alcool alkylique polyhydroxylique consiste en éthylène-glycol.
  3. Procédé suivant la revendication 1, dans lequel le stéarate consiste en stéarate de calcium.
  4. Procédé suivant la revendication 1, dans lequel le phénate sulfuré comprend un phénate sulfuré surbasique.
  5. Procédé suivant la revendication 1, dans lequel le rapport de l'alcool polyhydroxylique à l'eau est maintenu suffisamment élevé pour que le rapport soit au moins égal à 4:1 à la fin de l'étape de formation d'un mélange surbasique.
  6. Procédé suivant la revendication 5, dans lequel le rapport de l'alcool polyhydroxylique à l'eau est maintenu suffisamment élevé pour que le rapport soit au moins égal à 9:1 à la fin de l'étape de formation d'un mélange surbasique.
  7. Procédé suivant la revendication 1, dans lequel le phénate-stéarate surbasique renferme moins de 0,05 % en volume de sédiments fins.
  8. Procédé pour la production d'un phénatestéarate surbasique, comprenant les étapes consistant :
    (a) à rendre surbasique un mélange qui comprend un phénate sulfuré, du stéarate de calcium, au moins un solvant, de l'hydroxyde de calcium et de l'eau, en mettant en contact ledit mélange avec du dioxyde de carbone en présence d'un éthylène-glycol,
    (1) tout en maintenant un degré d'agitation suffisamment fort pour que toutes les substances solides soient en suspension au cours de l'étape de formation d'un mélange surbasique, et
    (2) tout en maintenant le rapport de l'alcool polyhydroxylique à l'eau suffisamment élevé pour que le rapport soit au moins égal à 9:1 à la fin de l'étape de formation d'un mélange surbasique ; et
    (b) à soumettre à un entraínement ledit mélange surbasique pour produire un phénate-stéarate surbasique renfermant moins de 0,05 % en volume de sédiments fins.
EP19960306180 1995-08-23 1996-08-23 Production de phénate stéarate à indice de base totale élevé ayant une formation de sédiments fins basse Expired - Lifetime EP0761648B1 (fr)

Applications Claiming Priority (2)

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

Publications (3)

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EP0761648A2 EP0761648A2 (fr) 1997-03-12
EP0761648A3 EP0761648A3 (fr) 1997-03-26
EP0761648B1 true EP0761648B1 (fr) 1999-06-30

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EP (1) EP0761648B1 (fr)
JP (1) JPH09104887A (fr)
CA (1) CA2183906A1 (fr)
DE (1) DE69603055T2 (fr)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1710294B1 (fr) 2005-04-06 2013-03-06 Infineum International Limited Une méthode pour améliorer la stabilité ou la compatibilité des tensioactifs

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1105217A (en) * 1965-10-05 1968-03-06 Lubrizol Corp Process for preparing basic metal phenates
GB8628609D0 (en) * 1986-11-29 1987-01-07 Bp Chemicals Additives Lubricating oil additives
GB8917094D0 (en) * 1989-07-26 1989-09-13 Bp Chemicals Additives Chemical process
JPH04183792A (ja) * 1990-11-19 1992-06-30 Idemitsu Kosan Co Ltd 過塩基性硫化アルカリ土類金属フェネート及びその用途
US5292968A (en) * 1992-02-26 1994-03-08 Cosmo Research Institute Process for producing over-based alkaline earth metal phenate
DE69327515T2 (de) * 1992-12-07 2000-06-21 Ethyl Petroleum Additives, Inc. Verfahren zur Herstellung von überbasischen Phenolaten
TW277057B (fr) * 1993-08-25 1996-06-01 Cosmo Sogo Kenkyusho Kk

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Publication number Publication date
DE69603055T2 (de) 1999-10-21
EP0761648A3 (fr) 1997-03-26
JPH09104887A (ja) 1997-04-22
DE69603055D1 (de) 1999-08-05
EP0761648A2 (fr) 1997-03-12
CA2183906A1 (fr) 1997-02-24

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