EP0000264B1 - The production of highly basic calcium sulphonates. - Google Patents

The production of highly basic calcium sulphonates. Download PDF

Info

Publication number
EP0000264B1
EP0000264B1 EP78300065A EP78300065A EP0000264B1 EP 0000264 B1 EP0000264 B1 EP 0000264B1 EP 78300065 A EP78300065 A EP 78300065A EP 78300065 A EP78300065 A EP 78300065A EP 0000264 B1 EP0000264 B1 EP 0000264B1
Authority
EP
European Patent Office
Prior art keywords
calcium hydroxide
calcium
weight
parts
process according
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
Application number
EP78300065A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP0000264A1 (en
Inventor
Alain Louis Pierre Lenack
Robert Tirtiaux
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.)
ExxonMobil Technology and Engineering Co
Original Assignee
Exxon Research and Engineering Co
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Exxon Research and Engineering Co filed Critical Exxon Research and Engineering Co
Priority to IT5014578A priority Critical patent/IT1156889B/it
Publication of EP0000264A1 publication Critical patent/EP0000264A1/en
Application granted granted Critical
Publication of EP0000264B1 publication Critical patent/EP0000264B1/en
Expired legal-status Critical Current

Links

Classifications

    • 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
    • C10M159/24—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products containing sulfonic radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07G—COMPOUNDS OF UNKNOWN CONSTITUTION
    • C07G99/00—Subject matter not provided for in other groups of this subclass
    • C07G99/002—Compounds of unknown constitution containing sulfur
    • C07G99/0024—Overbased compounds

Definitions

  • the present invention relates to the production of highly basic calcium sulphonates and to lubricating oils containing such highly basic sulphonates.
  • highly basic calcium sulphonate refers to the calcium salt of a sulphonic acid which contains a stoichiometric excess of calcium over and above that required to neutralise the sulphonic acid. Frequently the excess calcium is present in the form of colloidal calcium carbonate suspended in the calcium salt of the sulphonic acid.
  • the present invention therefore provides a process for the production of highly basic calcium sulphonates comprising treating with carbon dioxide the reaction product of mixing
  • the sulphonic acid that may be used in the reaction mixture includes oil soluble sulphonic acids and these may be natural or synthetic sulphonic acids, e.g. a mahogany or petroleum alkyl sulphonic acid, and alkyl sulphonic acid, or an alkaryl sulphonic acid.
  • the alkyl sulphonic acid should preferably have at least 25 carbon atoms per molecule
  • the alkaryl sulphonic acid e.g. alkyl benzene sulphonic acid
  • Most suitable are sulphonic acids having a molecular weight of between 300 and 700, e.g. between 400 and 500.
  • an alkaline earth metal sulphonate (preferably having a molecular weight of between 300 and 700) can be used, for example a calcium sulphonate.
  • the sulphonic acid or sulphonate is generally obtained as a mineral oil solution preferably consisting of 50% to 90% more preferably 60% to 80% by weight of the sulphonic acid or sulphonate.
  • the hydrocarbon solvent may be an aromatic or aliphatic hydrocarbon.
  • Aromatic hydrocarbons are preferred, and examples of these are toluene, xylene and ethyl benzene.
  • Suitable aliphatic hydrocarbons include paraffinic hydrocarbons such as n-hexane, n-heptane, n-decane, n-dodecane, white spirit, naphtha or iso-paraffins and cyclic paraffins such as cyclohexane.
  • the C 1 -C 3 alcohol that is used is preferably methanol since if other alcohols are used there is a tendency for gel formation to occur during carbonation.
  • This amount of water generally corresponds to about 2.5 to 5 wt.% preferably 3 to 4 wt.% of water based on the total reaction mixture. We find that the presence of this amount of water enables a product with acceptable solubility in heavy paraffinic base stocks to be obtained.
  • oils generally contain more than 50% paraffinic carbon atoms as determined by infra-red spectroscopy by the method of GOnther Brandes described in the October and November of 1958 editions of Erdöl und Kohle.
  • our invention yields products soluble in such paraffinic oils which have a viscosity at 38°C greater or equal to 500 SUS.
  • the products also have improved filterability.
  • the exact amount of water that should be used depends upon the amount of excess calcium hydroxide used and the purity of the calcium hydroxide.
  • stoichiometric excess of calcium hydroxide leads to a pmduct of improved oil solubility particularly in paraffinic mineral oils.
  • stoichiometric excess we mean an excess over that required to react with the sulphonic acid and the carbon dioxide.
  • the improved oil solubility may be achieved by introducing the excess of calcium hydroxide into the reaction mixture and controlling carbonation so that some unreacted calcium hydroxide remains or by carbonating the reaction mixture to completion of uptake of carbon dioxide and then adding extra calcium hydroxide before filtration, in this case the amount of water present at the start of carbonation should be 4 wt.% to 35 wt.% based on the total amount of calcium hydroxide used.
  • the product should exhibit alkalinity to phenolphthalein.
  • the rate at which the product filters and its solubility in heavy paraffinic oils depends upon the amount of water added and the quality of the calcium hydroxide and we prefer to use a calcium hydroxide containing less than 3 wt.% of calcium carbonate impurity preferably less than 1 wt.% of calcium carbonate.
  • Suitable diluent oils include hydrocarbon oils, particularly those of mineral origin. Oils which have viscosities of 15 to 30 cS at 38°C are very suitable. Alternatively other oils which may be used are the lubricating oils which are described later in the specification.
  • the relative proportions of the materials in the reaction mixture are not critical but we prefer that for every 350 parts by weight of the sulphonic acid from 150 to 350, preferably 250 to 300 parts by weight of the alcohol be used together with 300 to 800, preferably 400 to 600 part by weight of the hydrocarbon solvent and 180 to 210 parts by weight of calcium hydroxide.
  • the reaction mixture is at a temperature in the range 20°C to 35°C preferably 20°C to 30°C during carbonation since we find that if higher temperatures e.g. 50°C are used the product tends to be a grease whilst if lower temperatures such as 10°C are used the product tends to be milky.
  • higher temperatures e.g. 50°C are used the product tends to be a grease whilst if lower temperatures such as 10°C are used the product tends to be milky.
  • carbonation is continued to saturation point and the excess calcium hydroxide added later we find that from 95 to 115 parts by weight of carbon dioxide are taken up for every 350 parts by weight of sulphonic acid present in the reaction mixture.
  • the reaction mixture After carbonation is complete and any excess calcium hydroxide added, we prefer to subject the reaction mixture to a soaking period before adding the diluent oil and before filtering since we find that this significantly increases the rate at which the mixture will filter.
  • the diluent oil may be added to the reaction mixture before the soaking step.
  • the reaction mixture is then heated to remove the volatiles, being the hydrocarbon solvent and the C 1 -C 3 alcohol and then filtered generally using a filter aid to obtain the highly basic calcium sulphonate as the filtrate.
  • overbased calcium sulphonate detergents prepared by the process of this invention are suitable for use as additives in lubricating oils, both mineral and synthetic.
  • the lubricating oil may be any animal, vegetable or mineral oil, for example petroleum oil fractions ranging from naphthas to spindle oil to SAE 30, 40 or 50 lubricating oil grades, castor oil, fish oils or oxidised mineral oil.
  • the products are useful in the paraffinic mineral oils as hereinbefore described in which previously known calcium sulphonates have limited solubility.
  • Suitable synthetic ester lubricating oils include diesters such as di-octyl adipate, dioctyl sebacate, didecyl azelate, didecyl adipate, didecyl succinate, didecyl glutarate and mixtures thereof.
  • the synthetic ester can be a polyester such as that prepared by reacting polyhydric alcohols such as trimethylolpropane and pentaerythritol with monocarboxylic acids such as butyric acid, caproic acid, caprylic acid and perlargonic acid to the corresponding tri- and tetra-esters.
  • complex esters may be used as base oils such as those formed by esterification reactions between a dicarboxylic acid, a glycol, and an alcohol and/or a monocarboxylic acid.
  • additives may be included in the lubricating oil together with the additive prepared by the process of this invention.
  • suitable additives include the alkyl succinimide dispersants, copolymeric viscosity index improvers and the zinc dialkyldithiophosphate antiwear additives.
  • filtration rate was measured in a Buchner funnel for either 1 hour or until 500 grams of filtrate was obtained, whichever occurred sooner.
  • a filter paper of 77 sq centimeters area was used at 150°C and 7 grams of filter aid Clarcel (Registered Trade Mark) DCB were formed into a layer over the filter paper.
  • Carbon dioxide was then passed through the reaction mixture at a rate of 4.2 parts per hour until no further carbon dioxide was absorbed which occurred after about 4 hours.
  • the temperature was held in the range 25 to 30°C during the introduction of the carbon dioxide.
  • Solubility is assessed by adding 5 grams of the filtrate to 95 grams of the oil and visual observation of room temperature solubility.
  • Example 2 The process of Example 1 was repeated using a calcium hydroxide from a different source which was 98% pure and contained less than 1 wt.% calcium carbonate. In this Example all the calcium hydroxide was included in the initial reaction mixture and carbonation was stopped when 82% of the stoichiometric amount of carbon dioxide required to react with all the free calcium hydroxide had been taken up by the reaction mixture. Various quantites of water were added and the products obtained had the following properties:-
  • Oil 1 was the paraffinic oil used in Example 1 whilst oil 2 was a blend of 70 parts of the oil of Example 1 with 30 parts of a paraffinic oil containing 60% paraffinic carbon atoms and having a viscosity at 38°C of 2500 SUS.
  • Example 2 The process of Example 2 was repeated using the calcium hydroxide of Example 1 and including 7.5 wt.% water based on the weight of calcium hydroxide. The time for which the mixture was held at about 30°C before filtration was varied with the following results:-

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Lubricants (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
EP78300065A 1977-07-04 1978-06-22 The production of highly basic calcium sulphonates. Expired EP0000264B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
IT5014578A IT1156889B (it) 1977-07-04 1978-07-03 Procedimento per la produzione di solfonati di calcio fortemente basici come additivi per olii lubrificanti e prodotto ottenuto

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB2793277 1977-07-04
GB2793277 1977-07-04

Publications (2)

Publication Number Publication Date
EP0000264A1 EP0000264A1 (en) 1979-01-10
EP0000264B1 true EP0000264B1 (en) 1982-02-10

Family

ID=10267609

Family Applications (1)

Application Number Title Priority Date Filing Date
EP78300065A Expired EP0000264B1 (en) 1977-07-04 1978-06-22 The production of highly basic calcium sulphonates.

Country Status (6)

Country Link
EP (1) EP0000264B1 (enrdf_load_stackoverflow)
JP (1) JPS5414919A (enrdf_load_stackoverflow)
BR (1) BR7804263A (enrdf_load_stackoverflow)
CA (1) CA1139078A (enrdf_load_stackoverflow)
DE (1) DE2861618D1 (enrdf_load_stackoverflow)
SU (1) SU919592A3 (enrdf_load_stackoverflow)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4165291A (en) * 1978-06-20 1979-08-21 Phillips Petroleum Company Overbasing calcium petroleum sulfonates in lubricating oils employing monoalkylbenzene
GB2036781A (en) * 1978-12-13 1980-07-02 Exxon Research Engineering Co Preparation of basic magnesium sulphonates
GB2058118A (en) * 1979-08-31 1981-04-08 Exxon Research Engineering Co Overbased calcium sulphonate production
DE3370356D1 (en) * 1982-12-08 1987-04-23 Exxon Research Engineering Co Preparation of overbased calcium sulphonates
DE3461791D1 (en) * 1983-04-08 1987-02-05 Shell Int Research Process for preparing an alkyl aryl sulphonate concentrate composition
JPH0735515B2 (ja) * 1990-03-30 1995-04-19 株式会社松村石油研究所 塩基性カルシウムスルホネートの製造方法
CA2067842A1 (en) * 1991-05-23 1992-11-24 Peggy Jo Harris Process for overbased calcium sulfonate

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3170880A (en) * 1959-02-20 1965-02-23 Bray Oil Co Dispersions of calcium compounds in oils
US3429811A (en) * 1966-08-17 1969-02-25 Exxon Research Engineering Co Preparation of overbased sulfonates
US3830739A (en) * 1970-07-17 1974-08-20 Witco Chemical Corp Preparation of hyperbasic dispersions
JPS5040525A (enrdf_load_stackoverflow) * 1973-08-15 1975-04-14

Also Published As

Publication number Publication date
CA1139078A (en) 1983-01-11
DE2861618D1 (en) 1982-03-18
SU919592A3 (ru) 1982-04-07
JPS5414919A (en) 1979-02-03
JPH034599B2 (enrdf_load_stackoverflow) 1991-01-23
BR7804263A (pt) 1979-02-28
EP0000264A1 (en) 1979-01-10

Similar Documents

Publication Publication Date Title
EP0273588B1 (en) Sulphurised alkaline earth metal hydrocarbyl phenates, their production and use thereof
USRE35461E (en) Lubricating oil additives
US5162085A (en) Process for the production of an overbased phenate concentrate
EP0047126B1 (en) Improved calcium sulphonate process
EP0212922B1 (en) Overbased additives
US4302342A (en) Process for the preparation of detergent dispersants of high alkalinity for lubricating oils and the product obtained therefrom
US5716914A (en) Alkaline earth metal hydrocarbyl phenates, their sulphurized derivatives, their production and use thereof
US4664824A (en) Phenate product and process
US5451331A (en) Process for the production of a lubricating oil additive concentrate
JP2941377B2 (ja) 潤滑油添加濃縮物の製造方法
US5714443A (en) Sulphurised alkaline earth metal hydrocarbyl phenates, their production and use thereof
EP0812313B1 (en) Low base number sulphonates
EP0000264B1 (en) The production of highly basic calcium sulphonates.
EP0354647A2 (en) A process for the production of a lubricating oil additive concentrate
EP0473200B1 (en) Process for carbonate overbasing of an alkali or alkaline earth metal sulfonate, phenate or salicylate, the obtained products and their use
CA1253873A (en) Process for the preparation of sulphurized overbased salicylates
EP0025328B1 (en) Production of overbased calcium sulphonate, product thus obtained and lubricating oil containing it
EP0351053B1 (en) A process for the production of a lubricating oil additive concentrate
EP0121024B1 (en) Preparation of overbased calcium sulphonates

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Designated state(s): BE DE FR GB

17P Request for examination filed
GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Designated state(s): BE DE FR GB

REF Corresponds to:

Ref document number: 2861618

Country of ref document: DE

Date of ref document: 19820318

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 19930401

Year of fee payment: 16

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 19940322

Year of fee payment: 17

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 19940331

Year of fee payment: 17

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 19940413

Year of fee payment: 17

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Effective date: 19940622

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 19940622

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Effective date: 19950630

BERE Be: lapsed

Owner name: EXXON RESEARCH AND ENGINEERING CY

Effective date: 19950630

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Effective date: 19960229

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Effective date: 19960301

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT