US2174246A - Method for producing wax modifying agents - Google Patents

Method for producing wax modifying agents Download PDF

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Publication number
US2174246A
US2174246A US144870A US14487037A US2174246A US 2174246 A US2174246 A US 2174246A US 144870 A US144870 A US 144870A US 14487037 A US14487037 A US 14487037A US 2174246 A US2174246 A US 2174246A
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United States
Prior art keywords
solvent
wax
chlorinated
reaction
oil
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 - Lifetime
Application number
US144870A
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English (en)
Inventor
Lieber Eugene
Martin M Sadlon
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Standard Oil Development Co
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Standard Oil Development Co
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Publication date
Application filed by Standard Oil Development Co filed Critical Standard Oil Development Co
Priority to US144870A priority Critical patent/US2174246A/en
Priority to GB6235/38A priority patent/GB511207A/en
Priority to FR834992D priority patent/FR834992A/fr
Application granted granted Critical
Publication of US2174246A publication Critical patent/US2174246A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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
    • C10M1/00—Liquid compositions essentially based on mineral lubricating oils or fatty oils; Their use as lubricants
    • C10M1/08—Liquid compositions essentially based on mineral lubricating oils or fatty oils; Their use as lubricants with additives
    • 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
    • C10G73/00—Recovery or refining of mineral waxes, e.g. montan wax
    • C10G73/02—Recovery of petroleum waxes from hydrocarbon oils; Dewaxing of hydrocarbon oils
    • C10G73/04—Recovery of petroleum waxes from hydrocarbon oils; Dewaxing of hydrocarbon oils with the use of filter aids
    • 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
    • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/06—Well-defined aromatic compounds
    • 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
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/22—Alkylation reaction products with aromatic type compounds, e.g. Friedel-crafts
    • 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
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/02—Hydroxy compounds
    • C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
    • 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
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/02—Hydroxy compounds
    • C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/025—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings with condensed rings
    • 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
    • C10M2211/00—Organic non-macromolecular compounds containing halogen as ingredients in lubricant compositions
    • C10M2211/02—Organic non-macromolecular compounds containing halogen as ingredients in lubricant compositions containing carbon, hydrogen and halogen only
    • 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
    • C10M2211/00—Organic non-macromolecular compounds containing halogen as ingredients in lubricant compositions
    • C10M2211/04—Organic non-macromolecular compounds containing halogen as ingredients in lubricant compositions containing carbon, hydrogen, halogen, and oxygen
    • C10M2211/042—Alcohols; Ethers; Aldehydes; Ketones
    • 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
    • C10M2211/00—Organic non-macromolecular compounds containing halogen as ingredients in lubricant compositions
    • C10M2211/06—Perfluorinated compounds
    • 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
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions
    • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings

Definitions

  • the present invention relates to an improved method for producirg wax modifying agents for use in waxy lubricating oils as pour depressants and as crystallization inhibitors to be employed in the process of separating wax from mineral oils.
  • Wax. modifying. agents are now produced by condensation of parafilnic compounds having 10 long hydrocarbon chains such as paraffin wax on aromatic hydrocarbons or other cyclic compounds.
  • the reaction is ordinarily conducted by means of Fliedel-Craft type catalysts such as aluminum chloride and it is customary to use a dilucut during the condensation step.
  • Fliedel-Craft type catalysts such as aluminum chloride and it is customary to use a dilucut during the condensation step.
  • petroleum, naphthas, kerosenes and the like have been employed as diluents, but ethylene dichloride and propylene dichloride have also been suggested.
  • halogenated hydrocarbon solvents during the condensation leads to greatly improved results.
  • these solvents give the least amountof oil insoluble waste materials and, on the other hand, if proper solvents and conditions are employed, products of a high degree of potency can be obtained, even with waxes of high halogen content, and without the production of oil insoluble products.
  • theparticular solvent media do not have to be those which are completely incapable of reacting but are such that do not react readily under the conditions prevailing so that they are in effect substantially inert to the reactants.
  • the particular solvent media which are found to best fulfill the requirements belong to two groups; first, aliphatic hydrocarbon derivatives of two or more carbon atoms in which three or more halogen atoms are attached to the same or to adjacent carbon atoms of the molecule.
  • solvents may be specifically mentioned trichlorethane, tetrachlorethane, trichlorethylene, tetrachlorethylene, penta and hexachlorethanes.
  • Similar derivatives of propane, propylene and the butanes and butylenes may also be used, as well as the higher boiling halogenated hydrocarbons, but it is preferable to use the lower boiling derivatives of 2 to 4.
  • the other group of solvents consist of the halogenated aromatic hydrocarbons. These compounds should contain at least two halogen atoms on the same ring but it is not of great importance whether these halogen atoms are attached to adjacent carbon atoms of the ring. It is preferred to use monocyclic aromatic hydrocarbons, that is to say derivatives of benzol, but the substituted derivatives of naphthalene can also be used. Specific examples of the most desirable compounds are dichlorhenzol, trichlorbenzol, penta or hexa chlorbenzol, di and trichlornaphthalenes.
  • the wax modifying agents are prepared by reaction of at least two types of ingredients.
  • a parafiinic material that is to say the various paraflinic materials chlorinated paraflin wax, usually containing from 10 to 15% or 20% of chlorine, is preferred.
  • Dechlorinated wax that is to say the olefins obtained from chlorinated wax, can also be used, but they are less reactive than the chlorine containing compound and for that reason are not so useful.
  • Acid chlorides may also be used where there is a long hydrocarbon chain, for example, having at least 10 or 12 carbon atoms, such as stearyl or oleyl chloride.
  • Chlorinated alcohols, ethers or esters may also be employed in the same way so long as they have relatively long hydrocarbon chains and contain an amount of chlorine comparable to the 10 to 20% of the chlorinated paraflin wax.
  • the second reactant is a cyclic compound which may be a hydrocarbon suchas benzol, naphthalene or anthracene, or a hydroxy aromatic such as a phenol or a naphthol, or an amine such as aniline or naphthylamine may be used.
  • the parafiinicmaterial is used in excess of the aromatic, ordinarily to 100 parts of the chlorinated parafiinic material from 10 to 20 partsof the arcmatic are used although there may be considerable variation.
  • the catalytic agents employed in the condensation are in general the Friedel-Craft catalysts as mentioned above.
  • Aluminum chloride is perhaps the best and the most generally available, but others of the same type can be used such as zinc chloride, iron chloride, aluminum bromide, boron fluoride or titanium fluoride.
  • the catalyst is used in proportion of l. to 5%, or more, based on the chlorinated parafllnic material.
  • the reactants may be admixed in any order; for example, the chlorinated or otherwise halogenated wax and the aromatic, say naphthalene, may be mixed with the solvent and the catalyst may then be slowly added as the reaction progresses or, on the other hand, naphthalene and catalyst may be mixed with the solvent and the chlor wax added thereto slowly and the mixture kept in thorough agitation during the reaction.
  • This latter method has marked advantages because it even permits the use of more highly chlorinated waxes, for example waxes containing 15 or even 20% of chlorine or more, and the products produced by such reactions are substantially free from oil insoluble products or, at least, the amount of insoluble product is very greatly reducedover the amount produced by mixing the reactants in any other way.
  • chlorinated solvents disclosed herein is beneficial for the reaction whatever the particular method or order of adding the reagents, but is particularly beneficial when high chlorine content waxes are used and when the chlorinated wax is added to the mixture of aromatic and catalyst in the manner disclosed above.
  • the temperature of condensation may vary considerably, preferably from room temperature to about 200 F., the optimum temperatures depending on the particular reactants and to a lesser extent on the particular solvent medium which are used, but in general the optimum is in the range specified and well below the temperature at which the potency of the oil soluble product is found to decrease. Temperature likewise depends to some extent on the amount of catalyst used-and on the time of reaction. Ordinarily in the preferred temperature range, the time of reaction to give the most potent product should be less than about six hours, although good pour inhibitors may be obtained at longer times especially where less catalyst is used and where other factors are modified.
  • the reaction product is preferably finished by hydrolyzing either with acid or alkali in water or alcohol and is washed free of the catalyst sludge.
  • the temperature was maintained at F. for a period of three hours and both products were finished in the same way by hydrolyzing the remaining catalyst and withdrawing the sludge.
  • reaction product produced without the use of a solvent was reduced to a final content of about 2 /2% of an oil insoluble material, while there was no oil insoluble material whatever found in the reaction product made in presence of the chlorinated solvent medium.
  • Example II The same experimental procedure was used as in the previous example (No. 1). Here benzotrichloride, benzene, mono-chlor-benzene and dichlor-benrene were used respectively as solvent media. The oil soluble products were recovered as previously described The following' table illustrates the results obtained: I
  • Example III to two difierent oils, each having a pour point of +30 F.
  • the first of these oils, No. 1 was of a type more susceptible to reduction of pour point than No. 2.
  • the comparison of the two products is given in the table below which shows that the product made in the presence of the chlorinated solvent produced a pour depression on an average of to 25 below that produced by an equal quantity of the material made in the presence of the kerosene:
  • Example V The conditions of the present example closely approximated those of the prior example except that 15 parts by volume ot'ortho dichlorbenzene was used as the solvent, and the reaction period was three hours. No insoluble product was produced where this solvent was employed and the potency was such as to give a pour reduction of 5 to 10'' more on the average than could be obtained with an equal amount oi product made without the solvent.
  • Example VI Two condensatlons were made with the same ingredients in the sameproportions, the difference between the tests being that in the first the catalyst was added to a mixture of ohlorwax and naphthalene in the presence of the solvent while in the second the chlorwax was added to the mixture of the naphthalene and catalyst in the presence of the solvent.-
  • the ingredients were:
  • the temperature during the condensation was maintained at 125 F. and the time of reaction was three hours in each case.
  • the finishing procedure was substantially the same in both instances and consistedin neutralizing the reaction mixture with caustic settling the catalyst sludge and reducing with fire and steam to a temperature of 600 F. in order to remove solvent and unreacted waxy material.
  • Emmple VII Parailin wax (122 M. P.) was chlorinated to a chlorine content of about 15%.
  • the ingredients were:
  • Example VI The finishing procedure described in Example VI, and consisted in neutralizing the. reaction mixture with caustic settling the catalyst sludge and reducing the clear oil with fire and steam to a temperature of 609 F. in order to remove solvent and unreacted waxy material.
  • the improvements comprising preparing a mixture of the aromatic compound and the catalyst in a saturated polyhalogenated hydrocarbon solvent of two to three carbon atoms, adding thereto chlorinated paraflin wax and maintaining the temperature below 200 F. to

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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)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
US144870A 1937-05-26 1937-05-26 Method for producing wax modifying agents Expired - Lifetime US2174246A (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
US144870A US2174246A (en) 1937-05-26 1937-05-26 Method for producing wax modifying agents
GB6235/38A GB511207A (en) 1937-05-26 1938-02-28 An improved manufacture of wax modifying agents
FR834992D FR834992A (fr) 1937-05-26 1938-03-08 Procédé perfectionné de fabrication d'agents modificateurs de la paraffine

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US144870A US2174246A (en) 1937-05-26 1937-05-26 Method for producing wax modifying agents

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2422247A (en) * 1940-12-27 1947-06-17 Standard Oil Dev Co Lubricants, etc., containing waxy hydrocarbons and a ketone-aromatic condensation product as wax modifier
US2436491A (en) * 1944-04-27 1948-02-24 Universal Oil Prod Co Method of producing a cyclo-olefin
US2468500A (en) * 1944-12-28 1949-04-26 Standard Oil Dev Co Lubricant containing pour point depressant
US2502390A (en) * 1945-03-02 1950-03-28 Socony Vacuum Oil Co Inc Wax-substituted polyalkylthiophene
US3245766A (en) * 1962-06-08 1966-04-12 Exxon Research Engineering Co Chlorowax-naphthalene condensation product pour depressant for middle distillate fuels
US3249539A (en) * 1962-07-30 1966-05-03 Exxon Research Engineering Co Lubricating oil additive concentrates
US4259193A (en) * 1977-08-04 1981-03-31 Exxon Research & Engineering Co. Overbased sulphonates
CN107032557A (zh) * 2017-04-01 2017-08-11 西安石油大学 一种改性粘土辅助微生物处理高结垢油气田采出水的方法

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2422247A (en) * 1940-12-27 1947-06-17 Standard Oil Dev Co Lubricants, etc., containing waxy hydrocarbons and a ketone-aromatic condensation product as wax modifier
US2436491A (en) * 1944-04-27 1948-02-24 Universal Oil Prod Co Method of producing a cyclo-olefin
US2468500A (en) * 1944-12-28 1949-04-26 Standard Oil Dev Co Lubricant containing pour point depressant
US2502390A (en) * 1945-03-02 1950-03-28 Socony Vacuum Oil Co Inc Wax-substituted polyalkylthiophene
US3245766A (en) * 1962-06-08 1966-04-12 Exxon Research Engineering Co Chlorowax-naphthalene condensation product pour depressant for middle distillate fuels
US3249539A (en) * 1962-07-30 1966-05-03 Exxon Research Engineering Co Lubricating oil additive concentrates
US4259193A (en) * 1977-08-04 1981-03-31 Exxon Research & Engineering Co. Overbased sulphonates
CN107032557A (zh) * 2017-04-01 2017-08-11 西安石油大学 一种改性粘土辅助微生物处理高结垢油气田采出水的方法

Also Published As

Publication number Publication date
GB511207A (en) 1939-08-15
FR834992A (fr) 1938-12-08

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