US2567645A - Process of producing a detergent composition - Google Patents

Process of producing a detergent composition Download PDF

Info

Publication number
US2567645A
US2567645A US26719A US2671948A US2567645A US 2567645 A US2567645 A US 2567645A US 26719 A US26719 A US 26719A US 2671948 A US2671948 A US 2671948A US 2567645 A US2567645 A US 2567645A
Authority
US
United States
Prior art keywords
soap
fatty acid
alkyl sulfate
sulfate salt
fatty
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
US26719A
Other languages
English (en)
Inventor
Limburg Jozef
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.)
Shell Development Co
Original Assignee
Shell Development 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 Shell Development Co filed Critical Shell Development Co
Application granted granted Critical
Publication of US2567645A publication Critical patent/US2567645A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D10/00—Compositions of detergents, not provided for by one single preceding group
    • C11D10/04—Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap
    • C11D10/042—Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap based on anionic surface-active compounds and soap
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D11/00—Special methods for preparing compositions containing mixtures of detergents
    • C11D11/0082—Special methods for preparing compositions containing mixtures of detergents one or more of the detergent ingredients being in a liquefied state, e.g. slurry, paste or melt, and the process resulting in solid detergent particles such as granules, powders or beads
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols

Definitions

  • This invention relates to new detergent compositions comprising alkyl sulfate salts. deals with a method of improving the detergency of water-soluble salts of alkyl sulfuric acid esters having to 25 carbon atoms per molecule by admixing therewith under controlled conditions salts of higher fatty acids.
  • Alkyl sulfuric acid ester salts such as may be derived from fatty alcohols or olefins having 10 to 25 carbons per molecule are known to have certain advantages over ordinary soaps, particularly with respect to lime-resistance and wetting power.
  • the alkyl sulfate salts as a class are more or less inferior to the fatty acid soaps in regard to detergency.
  • An important object of the present invention is to overcome this disadvantage of prior alkyl sulfate salt compositions and to produce a new detergent which will not only have the advantageous lime-resistance and wetting power of the alkyl sulfate salts but also will have improved detergent properties.
  • compositions having the foregoing desirable combination of properties can be obtained from certain properly prepar ed mixtures of alkyl sulfate salts and fatty acid salts wherein the fatty acid content is at most equal to, and more preferably is considerably lower than, the alkyl sulfate salt content.
  • Simple mixing of the alkyl sulfate salt and fatty acid soap, as by grinding together or otherwise intermingling these two components in preformed conditions, is not a suitable method of preparation of the improved compositions.
  • the fatty acid soap must be formed in an aqueous medium containing the higher alkyl sulfate salt in order to obtain products of most desirable detergent power, lime-resistance and wetting characterist cs.
  • Products prepared in this manner namely, formation of the fatty acid soap in situ in an aqueous alkyl sulfate salt solution, have a different colloid-chemical structure from those obtained by later mixing of the alkyl sulfate salt with a previously prepared fatty acid soap.
  • the new compositions have been found to possess a combination of properties which is superior to those obtainable with other mixtures comprising alkyl sulfate salts.
  • the process is preferably carried out by mixing an aqueous solution of, for example, to of the alkyl sulfate salt with the desired quantity of one or more higher fatty acids, i. e. fatty acids containing at least 12 carbon atoms, and preferably about 14 to 20 carbon atoms, to the molecule, and neutralizing the mixture thus obtained by the addition of a base or some other basic substance.
  • higher fatty acids i. e. fatty acids containing at least 12 carbon atoms, and preferably about 14 to 20 carbon atoms
  • free fatty acids one may also take oils or fats, i. e. fatty acid glycerides, and convert the latter into fatty acid soap It also by means of a saponification agent after mixing them with the alkyl sulfate salt in an aqueous medium.
  • the fatty acids, or the oils or fats may be of any vegetable or animal origin.
  • the higher fatty acids prepared synthetically, for example by oxidation of paraffin wax, may also be used.
  • fatty acids or fatty acid mixtures witha comparatively high melting point such as palmitic acid, stearic acid, and palm oil fatty acids, and also oils or fats rich in these fatty acids, such as palm oil, tallow, bone fat, partially hardened linseed oil or train-oil and the like, have been found highly suitable.
  • the preparation of the products'according to the invention may take place at room temperature, it is preferably carried out at moderately elevated temperature, for example from about 50 C. to C., as this promotes a ready mixing of the fatty acids with the aqueous solution of the alkyl sulfate salt as well as a smoother progress of the neutralization. If oils or fats are employed, the process should take place at a sufficiently elevated temperature to cause the saponification of the glycerides; in general this makes it necessary to apply temperatures above 70 C., e. g. from about C. to C.
  • the quantity of fatty acids, oils or fats used in the preparation of the products according to the invention may vary within Wide limits. However. it is not allowed to use such large quantities as to make the content of fatty acid exceed that of the alkyl sulfate salt in the final product, because this gives rise to products with unsatisfactory properties, particularly as regards limeresistance.
  • compositions with substantially improved properties, particularly as to detergent power may be obtained by the process according to the invention, without an increa e of the said ratio involving any further improvement
  • the said ratio amounts to at least about 5:100, since no appreciable improvement is generally attained below this ratio.
  • the quantity of fatty acids which, starting from a given alkyl sulfate salt, is required for the preparation of products with the h ghest pos ible detergent power.
  • a ratio of fatty acid to alkyl sulfate salt in the final product lying'between about :90 and about 35:65 yields products with particularly favorable properties, which generally have the consistency of soft soap.
  • the higher secondary sulfuric acid alkyl ester salts of 10 to 18 carbon atoms per molecule such, for example, as may be produced by sulfating olefins and neutralizing the resulting esters with bases which yield water-soluble alkyl sulfate salts as described in U. S. Patent 2,152,292, for instance, are especially advantageous starting materials for thepreparation of the new compositions of the invention.
  • primary sulfuric acid alkyl ester salts such as sodium lauryl sulfate, ammonium myristyl sulfate, etc. which may be produced as described in U. S. Patent 1,968,79 for example, or tertiary sulfuric acid alkyl ester salts such as are disclosed in U. S. Patent 2,139,394, for instance, may also be used in the process of the invention.
  • the process is preferably carried out with such a quantity of fatty acid or fatty acid glyceride that the ratio of fatty acid to alkyl sulfate salt is about :85 to 20:80.
  • fatty acids or fatty acid glycerides used in the process according to the invention as a rule are completely converted into fatty acid soaps. If desired, however, it is also possible to apply only a partial neutralization or saponification, in which case'the final product will contain part of the fatty acids or glycerides in unconverted condition.
  • the neutralization of the fatty acids or saponiflcation of the fatty acid glycerides may be carried out with any suitable inorganic or organic base or other basic substance, such as sodium or potassium hydroxide or carbonate, or triethanol amine or other alkylol amines.
  • the fatty acid soap may thus be derived from the same base as the alkyl sulfate salt or from a different base.
  • the amount of the basic compound will be an amount of from the equivalent of about 5% byweight of the fatty acid soapbased upon the total amount of the alkyl sulfate salt and fatty acid soap to the substantially stoichiometric equivalent of the fatty acid or glyceride.
  • the products obtained according to the invention may be employed without undergoing any further treatment. If desired, they may also be subjected to an additional treatment; thus, it is, for example, poss ble to remove a portion of the water, e. g. by evaporation, in order to give them the desired consistency, or the products may be worked up to dry powders according to the rollerdrying process or by atomization-drying.
  • the properties of the capillary-active products prepared in the above manner may be enhanced even further by combining them .with water-soluble alkaline-reacting inorganic salts, such as alkali silicates, phosphates, borates and carbonates.
  • water-soluble alkaline-reacting inorganic salts such as alkali silicates, phosphates, borates and carbonates.
  • silicates in particular sodium metasilicate and waterglass or mixtures thereof, was found to exert a particularly strong influence, which not only gave rise to improved detergent power, but remarkably enough also to increased lime-resistance.
  • additions of, for example, 10% of the alkaline salts, calculated on the combined quantity of alkyl sulfate salt and fatty acid soap already bring about a distinct increase of the lime-resistance and of the detergent power.
  • the quantities of the salts added are increased, the effect increases up to a maximum, while after continued additions the properties of the products deteriorate again.
  • additions of more than 50% of the said salts are generally .not to be used.
  • soluble cellulose derivatives for example methoxy cellulose or any of the fillers, colorants or scents usually added to detergents.
  • the products are eminently suitable for use in laundries and further for domestic use in general. They may also be employed for other purposes, e. g. in the textile industry.
  • the process according to the invention is of particular importance for the preparation. of unctuous products resembling soft soap, in which case the fatty acid soap formed during the preparation may be sodium soap, such in contrast with the ordinary soft soap, which is known invariably to consist of fatty acid potassium soap.
  • these products of the invention display not only a substantially greater resistance to calcium ions and acid, and increased wetting power, but also a more favorable lathering effect, especially in hard water. Besides, they are superior to the ordinary soft soap in imparting no unpleasant smell to the clothes washed with them.
  • the process is not restricted to the preparation of products with the consistency of soft soap, but may also be applied to the preparation of products which are hard at ordinary temperatures.
  • Example I Three hundred and twenty parts by weight of a 25% aqueous solution of secondary sodium alkyl sulfates, produced by neutralization of the sulfation products of a Clo-C18 alkene cracking fraction, are mixed with 20 parts by weight bleached palm oil fatty acids (titer 44 C.) at a temperature of about 60 C. After this, sufilcient 25% sodium hydroxide lye is added, while stirring, to neutralize the fatty acids completely, and subsequently 23 parts by weight sodium metasilicate (Na2SiO3-9H2O) and 27 parts by weight waterglass of 38 B. The resulting mixture is then evaporated at 95 C.
  • bleached palm oil fatty acids titanium 44 C.
  • the product thus obtained has a particularly great lime-resistance, which even exceeds that of the secondary sodium alkyl sulfate solution from which it was derived, and very high wetting power, while the detergent effect also exceeds that of the secondary sodium alkyl sulfate solution.
  • the product constitutes an excellent detergent, particularly suitable for washing at comparatively low temperatures.
  • Example II One hundred and sixty parts by weight of the same alkyl sulfate salt solution as used in Example I are mixed at about 60 C. with 17 parts by weight bleached palm oil fatty acids (titer 44 C.) upon which about parts by weight 25 sodium hydroxide lye are added, while stirring, in order to neutralize the fatty acids. After this, 45 parts by weight sodium metasilicate are added, upon which the mixture is cooled and left to stand at room temperature for about 48 hours. About 230 parts by weight of a product resembling soft soap and having excellent properties were thus obtained, which product was eminently suitable to be used for washing at any temperature usually applied.
  • bleached palm oil fatty acids titanium 44 C.
  • Sodium lauryl sulfate may be used in place of the secondary alkyl sulfate salt with good results.
  • Example III Two hundred parts by weight of the alkyl sulfate salt solution of the preceding examples are mixed, while stirring vigorously, at about 90 C. with 50 parts by weight tallow (animal fat, titer 402 6.), upon which the fat is saponifled with 31 parts by weight 25% sodium hydroxide lye. After completion of the saponiflcation the mixture is cooled and left to stand at room temperature for about 48 hours. The product thus obtained is suillciently hard to be cut. The originally sticky surface of the bars hardens after a few hours. A highly neutral hard soap is obtained, which has an excellent detergent effect at any temperature. After the saponiflcation, 50 parts by weight tetra sodium pyrophosphate may. if desired, be added to the mixture obtained.
  • tallow animal fat, titer 402 6.
  • a process of producing a detergent of improved lime-resistance and detergent and wetting powers which comprises intimately mixing an aqueous solution of a water-soluble salt of a secondary alkyl sulfuric acid ester having 10 to 25 carbon atoms per molecule with a fatty acid of 12 to 20 carbon atoms per molecule in an amount such that the weight ratio of said acid to said secondary alkyl sulfate salt is 5:100 to 50 :50, adding to the mixture sodium hydroxide in an amount of from the equivalent of about 5% by weight of the sodium soap of the fatty acid based upon the total amount of said sodium soap and said secondary alkyl sulfate salt to the substantially stoichiometric equivalent of said fatty acid and maintaining the mixture at saponification temperature to effect saponification of said fatty acid.
  • a process of producing a detergent which comprises intimately mixing an aqueous solution of a water-soluble salt of an alkyl sulfuric acid ester having 10 to 25 carbon atoms per molecule with a fatty compound of the group consisting of soap-forming higher fatty acids and glycerides thereof in an amount equivalent to a weight ratio of fatty acid to said alkyl sulfate salt of 5:100 to 50:50, adding to the mixture a basic compound, the soap of which with the fatty acid of said fatty compound is water-soluble, in an amount of from the equivalent of about 5% by weight of said soap based upon the total amount of said soap and said alkyl sulfate salt to the substantially stoichiometric equivalent of the fatty acid and maintaining the mixture at saponification temperature to effect saponification.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)
US26719A 1947-05-16 1948-05-12 Process of producing a detergent composition Expired - Lifetime US2567645A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
NL654991X 1947-05-16

Publications (1)

Publication Number Publication Date
US2567645A true US2567645A (en) 1951-09-11

Family

ID=19795199

Family Applications (1)

Application Number Title Priority Date Filing Date
US26719A Expired - Lifetime US2567645A (en) 1947-05-16 1948-05-12 Process of producing a detergent composition

Country Status (4)

Country Link
US (1) US2567645A (fr)
BE (1) BE482509A (fr)
FR (1) FR966524A (fr)
GB (1) GB654991A (fr)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3625905A (en) * 1967-11-22 1971-12-07 Purex Corp Ltd Detergent composition having softening properties
US3625906A (en) * 1967-11-16 1971-12-07 Lever Brothers Ltd Soap-detergent tablets
US3765911A (en) * 1970-10-27 1973-10-16 London Oil Refining Co Processing of rubber and the like, and to processing compositions therefor
US3967924A (en) * 1974-01-23 1976-07-06 Ciba-Geigy Corporation Composition for use in the dyeing of polyester fibers
EP0505129A2 (fr) * 1991-03-18 1992-09-23 Hampshire Chemical Corporation Procédé pour la production d'une base pour savon synthétique à partir de N-acyl-sarcosine
US20150017311A1 (en) * 2013-07-02 2015-01-15 Milk Specialties Global Partial neutralization of free fatty acid mixtures with potassium, livestock feed compositions including them, and methods of making same

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
USD666394S1 (en) 2012-04-27 2012-09-04 Deckers Outdoor Corporation Footwear outsole

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1138230A (en) * 1912-03-28 1915-05-04 Joachim Leimdoerfer Process for the manufacture of hard soaps.
US1906484A (en) * 1930-04-08 1933-05-02 Ig Farbenindustrie Ag Soap preparation
US2009612A (en) * 1931-08-13 1935-07-30 Gen Aniline Works Inc Composition for oiling textile fibers
US2026816A (en) * 1930-10-06 1936-01-07 American Hyalsol Corp Soap preparation
US2152292A (en) * 1934-07-03 1939-03-28 Shell Dev Process for the production of alkyl ester salts
GB535809A (en) * 1938-04-22 1941-04-23 Colgate Palmolive Peet Co Improvements in or relating to detergents
GB584500A (en) * 1943-07-01 1947-01-16 Nat Oil Prod Co Improvements in or relating to detergents

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1138230A (en) * 1912-03-28 1915-05-04 Joachim Leimdoerfer Process for the manufacture of hard soaps.
US1906484A (en) * 1930-04-08 1933-05-02 Ig Farbenindustrie Ag Soap preparation
US2026816A (en) * 1930-10-06 1936-01-07 American Hyalsol Corp Soap preparation
US2009612A (en) * 1931-08-13 1935-07-30 Gen Aniline Works Inc Composition for oiling textile fibers
US2152292A (en) * 1934-07-03 1939-03-28 Shell Dev Process for the production of alkyl ester salts
GB535809A (en) * 1938-04-22 1941-04-23 Colgate Palmolive Peet Co Improvements in or relating to detergents
GB584500A (en) * 1943-07-01 1947-01-16 Nat Oil Prod Co Improvements in or relating to detergents

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3625906A (en) * 1967-11-16 1971-12-07 Lever Brothers Ltd Soap-detergent tablets
US3625905A (en) * 1967-11-22 1971-12-07 Purex Corp Ltd Detergent composition having softening properties
US3765911A (en) * 1970-10-27 1973-10-16 London Oil Refining Co Processing of rubber and the like, and to processing compositions therefor
US3967924A (en) * 1974-01-23 1976-07-06 Ciba-Geigy Corporation Composition for use in the dyeing of polyester fibers
EP0505129A2 (fr) * 1991-03-18 1992-09-23 Hampshire Chemical Corporation Procédé pour la production d'une base pour savon synthétique à partir de N-acyl-sarcosine
EP0505129A3 (en) * 1991-03-18 1993-01-07 W.R. Grace & Co.-Conn. A process for producing a synthetic detergent soap base from n-acyl sarcosine
US20150017311A1 (en) * 2013-07-02 2015-01-15 Milk Specialties Global Partial neutralization of free fatty acid mixtures with potassium, livestock feed compositions including them, and methods of making same

Also Published As

Publication number Publication date
GB654991A (en) 1951-07-04
FR966524A (fr) 1950-10-12
BE482509A (fr)

Similar Documents

Publication Publication Date Title
US2486922A (en) Stabilized detergent composition
US3376229A (en) Synthetic detergent bar
US3814692A (en) Free flowing soap-nonionic detergent
US2781321A (en) All purpose detergent bar
US3639286A (en) Synthetic detergent in bar or cake form and the method to manufacture same
US3442812A (en) Detergent bars
US2567645A (en) Process of producing a detergent composition
US2781320A (en) All purpose
US2653913A (en) Synthetic detergent cakes
US2867586A (en) Synthetic detergent bar compositions
US2875153A (en) Detergent compositions
US3291744A (en) Detergent bar
US2175285A (en) Detergent for toilet use containing incompletely esterified polyhydric alcohol
US3070547A (en) Soap-synthetic bar
US2714093A (en) Method of preparing detergent compositions
US3793215A (en) Soap bars
US3694367A (en) Superfatted soap
US1833899A (en) Soap
US3030310A (en) Combination soap-synthetic detergent bar
US2026816A (en) Soap preparation
US2316689A (en) Soapmaking
US4363740A (en) Process for making controlled sudsing detergent powder
US2374113A (en) Solvent emulsion cleaner
US2527075A (en) Detergent composition
US2278352A (en) Nonefflorescing bar soap