US3919125A - Method of preparing a highly concentrated solution of a higher secondary alcohol ethoxysulfate and such a concentrated solution - Google Patents

Method of preparing a highly concentrated solution of a higher secondary alcohol ethoxysulfate and such a concentrated solution Download PDF

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Publication number
US3919125A
US3919125A US362985A US36298573A US3919125A US 3919125 A US3919125 A US 3919125A US 362985 A US362985 A US 362985A US 36298573 A US36298573 A US 36298573A US 3919125 A US3919125 A US 3919125A
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higher secondary
secondary alcohol
ethoxysulfate
ethanol
solution
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US362985A
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Yoshiro Ashina
Takeshi Narita
Hiroshi Murata
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Nippon Unitol Co Ltd
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Nippon Unitol Co Ltd
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    • 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
    • C11D1/29—Sulfates of polyoxyalkylene ethers

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  • ABSTRACT A higher secondary alcohol ethoxysulfate.
  • an aqueous solution ofa caustic alkali and ethanol are fed continuously or batch-wise into a neutralization vessel to neutralize the higher secondary alcohol ethoxysulfate so that the three components ethanol (X).
  • water (Y) and the resulting neutralized higher secondary alcohol ethoxysulfate (Z) fall within the range surrounded with the lines connecting the following six points with each other on a triangular coordinate plot. whereby a highly concentrated solution of the neutralized higher secondary alcohol ethoxysulfate is obtained:
  • the present invention relates to a highly concentrated solution of a higher secondary alcohol ethoxysulfate and to a method of preparing the same, more precisely, to a salt of a higher secondary alcohol ethoxysulfate in an aqueous solution of high concentration and fluidity prepared by neutralizing a higher secondary alcohol ethoxysulfate with an aqueous solution of a caustic alkali in the presence of ethanol.
  • composition of the active ingredient in such detergents usually utilized is, in general, -20%, and the concentration of the active ingredient in the crude solutions of the ethoxysulfates during the manufacture thereof is about -30% or so. in the manufacture of the solutions of these ethoxysulfates, it is economical to make the concentration of the solution as high as possible. Accordingly, the makers of higher alcohol ethoxysulfates have desired an improved method of increasing the concentration of the ethoxysulfates as high as possible during the manufacture thereof.
  • the concentration of the higher alcohol ethoxysulfate increases, the viscosity thereof increases with an increase in concentration, and, in particular, if the concentration exceeds or more,'the ethoxysulfates form viscous pastes or non-fluid gels. These pastes or gels cannot be transported by a pump, and thus it be- 2 comes extremely difficult to deal with the resulting ethoxysulfates. Accordingly, the upper concentration limit of the ethoxysulfates is, in general, 30% when they are in the form of an aqueous solution.
  • the inventors observed that the viscosity of these ethoxysulfates was extremely high when the concentration thereof was 55-60% and a viscosity reducing agent was not present, and that it was necessary to add ethnnol '(as a viscosity reducing agent) to the ethoxylates in an amount of 12-15%, based on the solution of the ethoxysulfates, in order to impart a sufficient fluidity to the solution such that it could be transported by a pump.
  • the inventors conducted extensive investigations on the fluidity of a three-com ent system compril'ng an active ingredient (higher secondary alcohol ethoxysulfate), ethanol and water, in order to elimhate the above drawbacks in the preparation of a highly concentrated solution of a higher secondary alcohol ethoxysulfate, and discovered an unexpected characteristic of the three-component system. thus attaining the present invention.
  • the object of the present invention is to provide an improved method of preparing a highly concentrated solution of a neutralized higher secondary alcohol ethoxysulfate or such an ethoxysulfate mixture.
  • compositions in accordance with the invention have a viscosity such that pump transport is possible, usually a maximum of about 2,000 cp.
  • FIGURE is a triangular coordinate plot showing the range of the components constituting the products prepared according to the method of the present invention.
  • the concentration of the active ingredient of the solution is 60%, it is necessary to add 13% of ethanol to the solution, e.g., a solution of a higher primary alcohol ethoxysulfate as described above, in order to impart thereto fluidity sufficient for transporting by means of a pump.
  • the amount of ethanol added to impart the desired fluidity to the solution decreases, rather contrary to expectations, with a further increase in the concentration of the active ingredient in the solution, and when the concentration of the active ingredient is 75%, the object of the present invention of imparting a sufiicient fluidity to the solution is fully attained with a smaller amount of added ethanol, or only 3% thereof. This is quite an unexpected efi'ect.
  • the present invention thus is based upon the discovery of a specific characteristic of the higher secondary alcohol ethoxysulfates (such as a sodium salt) which has hitherto been unknown.
  • the higher secondary alcohol ethoxysulfates are obtained by adding I to 8 mols of ethylene oxide to 1 mol of a higher secondary alcohol containing 10 to l6 carbon atoms and sulfating the adduct.
  • the higher secondary alcohols of 10 to 16 carbon atoms are generally produced by oxidizing C m to C n-paraffins.
  • n+m+3 10 to 16 where n and m are integers.
  • They are commercially available, typically in mixture form, e.g., TergitoF' by Union Carbide Corporation, SoftanoP by Japan Catalytic Chemical Industry Co., Ltd. Unitol by Nitto Chemical Ind. Co., Ltd., etc.
  • the higher secondary alcohol ethoxysulfates can be prepared according to known procedures, e.g., U.S. Pat. No. 2,870,220 Carter.
  • a useful reaction product can be obtained at very mild reaction conditions, e.g., at normal pressure by reaction with chlorosulfonic acid at low temperatures, by contact with an SO -containing gas at low temperatures using a conventional thin-film reactor, etc.
  • a higher secondary alcohol ethoxylate, an aqueous solution of a caustic alkali (such as a caustic soda aqueous solution) and ethanol are treated for neutralization by a continuous operation or a batch operation so that the composition of the final product falls within the range surrounded by the lines connecting the six points A, B, C, D, E and F as shown in the drawing.
  • a caustic alkali such as a caustic soda aqueous solution
  • ethanol are treated for neutralization by a continuous operation or a batch operation so that the composition of the final product falls within the range surrounded by the lines connecting the six points A, B, C, D, E and F as shown in the drawing.
  • the viscosity of the solution exceeds 2000 centipoises at normal temperature (25C),. and thus it is difficult to handle such a solution.
  • the concentration of the ethanol therein exceeds 10%, and thus the solution in this upper region (containing a large amount of expensive ethanol) is economically disadvantageous.
  • the use of such a large amount of ethanol causes a lowering of the flash point of the resulting solution and increases the vaporization rate thereof, and thus, it becomes difficult to handle the resulting solution.
  • the temperature of the neutralization procedure of the present invention is not specifically limited, and the temperature can be any common neutralization temperature for higher alcohols ethoxysulfates, for example, about 0to about C or so.
  • the pressure of the neutralization procedure is also not specifically limited in any manner, and both suband super-atmospheric pressures can be used. However, as one skilled in the art will appreciate, such is not necessary for a neutralization procedure, and, generally speaking, little is to be gained by operation at other than atmospheric pressure, and for all practical commercial purposes such will be the case.
  • the time of operation is not overly critical so long as complete reaction is achieved, and, since the reaction is exothermic, so long as the ethoxysulfate material is not degraded.
  • the neutralization will be performed in a period of from about minutes to about 2 hours. If one wishes to use a longer time, a lower temperature will generally be used, while, on the other hand, if one wishes a shorter time, a higher temperature will generally be used, keeping in mind that under all circumstances ethoxysulfate material decomposition should be avoided.
  • the alkali material should be present in an amount at least stoichiometric to the ethoxysulfate for the neutralization.
  • a 10% excess of alkali over the stoichiometric amount will be used. This provides a safety factor for the reaction.
  • the amount of the ethanol added can be small and the concentration of the active ingredient in the solution can be made high, even with the use of only a small amount of ethanol. Therefore, the present method is economically and practically very advantageous.
  • the strength of the alkali material used is, of course, not overly important. Weak or strong alkali materials can be successfully used, and the concentration of the alkali basically only effects the rate of addition, i.e., the concentration does not effect the amount of alkali required. Practically speaking, one will use sodium hydroxide because of its low cost, ready availability and suitability for the neutralization. However, the present invention is by no means limited thereto, and one skilled in the art can select other alkali materials considering the economics of the reaction and the use of the concentrated product.
  • an aqueous sodium hydroxide solution most preferably at a sodium hydroxide concentration of to 50% by weight of the aqueous solution
  • other alkali metals such as potassium hydroxide, lower trialkanol amines, for instance, C C alkanol amines, ammonia, and the like, can also be used.
  • the method of the present invention is most profitably practiced with an undiluted caustic alkali solution as is typically available as an industrial raw material, and generally comprises about 45 to 48% caustic soda in an aqueous solution, based on aqueous solution weight.
  • the procedure of addition of the components is not especially limited.
  • the ethanol can be first added and then the remaining components added.
  • the aqueous alkali solution can be first added in a batch reaction and the ethoxysulfate and ethanol added thereto.
  • this latter procedure a tendency to partial reaction and difficulty of process control is encountered, and this nonpreferred.
  • Other modifications and additions to the procedures set above will be apparent to one skilled in the art.
  • Such additive materials can, if desired, be incorpo rated in the detergent composition, for example, in an amount of up to about 50% by weight of detergent composition, in order to achieve the above effects.
  • a specific example of one such formulation would be,
  • Ethoxysulfatc 35 parts by weight Alkylbenzcncsulfonatc 35 Alcohol Ethoxylate l0 Alkylolamidc 20 in an appropriate volume of water.
  • the concentrated detergent solution of the present invention can, of course, be blended with an alkylbenzene sulfonate, if desired.
  • EXAMPLE 1 Higher secondary alcohol ethoxylates (Tergitol 45- 3-8", product of the Union Carbide Corporation, having an average molecular weight of 356), which were obtained by adding 3 mols of ethylene oxide to higher secondary alcohols of 14 and 15 carbon atoms which 8 EXAMPLES 2 l0 AND REFERENCE EXAMPLES l 8 in a neutralization vessel provided with a stirrer there was fed ethanol in such an amount that the concentration thereof in the final product was at a predetermined value, and then, a caustic soda aqueous solution (source of water) and secondary alcohol ethoxysulfates (prepared by the addition of an average of three mols of ethylene oxide to one mole of a secondary alcohol mixture of 14 carbon atoms, followed by the sulfation of the resulting adduct with sulfur trioxide, available as Unitol 45-8-38 produced by Nitto Chemical 1nd.
  • a caustic soda aqueous solution source of water
  • a detergent composition comprising ethanol. the percentages being by weight of the three compowater and one or more sodium salt( s) of higher secondnents, said detergent composition having a viscosity of ary alcohol ethoxysulfate. said ethoxysulfate obtained 2000 centipoises or less at 25C. by adding I to 8 mols of ethylene oxide to 1 mol of g g t UNITED STATES PATENT AND TRADEMARK OFFICE CERTIFICATE OF CORRECTION PATENT N0. 3,919,125 DATED 1 November 11, 1975 INVENTOR( I Yoshiro Ashina. etaal H is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

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  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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US362985A 1972-05-23 1973-05-23 Method of preparing a highly concentrated solution of a higher secondary alcohol ethoxysulfate and such a concentrated solution Expired - Lifetime US3919125A (en)

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Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2935428A1 (de) * 1979-09-01 1981-03-26 Henkel KGaA, 40589 Düsseldorf Waessrige tensidkonzentrate und verfahren zur verbesserung des fliessverhaltens schwer beweglicher waessriger tensidkonzentrate
US4261917A (en) * 1978-11-10 1981-04-14 The Lion Fat & Oil Co., Ltd. Process for manufacturing a highly concentrated sulfate solution or slurry
US4404143A (en) * 1980-06-16 1983-09-13 Lion Corporation Process for producing high concentration solution of salt of alpha-sulfo fatty acid ester
US4412945A (en) * 1982-01-04 1983-11-01 Lion Corporation Aqueous high concentration slurry of alcohol ethoxylate
US4734221A (en) * 1984-05-11 1988-03-29 Lever Brothers Company Detergent compositions
US4734223A (en) * 1984-05-11 1988-03-29 Lever Brothers Company Detergent compositions
EP0211493A3 (en) * 1985-06-21 1988-10-12 Unilever Plc Liquid detergent composition
WO1993018123A1 (en) * 1992-03-10 1993-09-16 The Procter & Gamble Company High active detergent pastes
US5529722A (en) * 1992-03-10 1996-06-25 The Procter & Gamble Company High active detergent pastes
USH1632H (en) * 1994-08-15 1997-02-04 Shell Oil Company Liquid laundry detergent formulations
US6255275B1 (en) * 1996-12-06 2001-07-03 Nippon Shokubai Co., Ltd. Higher secondary alcohol alkoxylate compound composition, method for production thereof, and detergent and emulsifier using the composition
US6346509B1 (en) 1997-12-05 2002-02-12 Nippon Shokubai Co., Ltd. Higher secondary alcohol alkoxylate compound composition, method for production thereof, and detergent and emulsifier using the composition
US20080312121A1 (en) * 2005-09-08 2008-12-18 Kirk Herbert Raney Liquid Surface Active Compositions
US20100010251A1 (en) * 2008-07-10 2010-01-14 Jan Hermen Hendrik Meurs Preparation of alkoxysulfates
EP3176240B1 (en) 2015-12-04 2019-05-22 Chevron Oronite Company LLC Process for preparing alcohol ether sulfates

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS56141402U (en(2012)) * 1980-03-24 1981-10-26
JP5571367B2 (ja) 2008-12-25 2014-08-13 花王株式会社 界面活性剤組成物

Citations (9)

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US2644831A (en) * 1951-04-16 1953-07-07 Monsanto Chemicals Alkali metal and ammonium sulfates of hydroxy ethers
US2766212A (en) * 1952-09-16 1956-10-09 Gen Aniline & Film Corp Detergents
US2870220A (en) * 1953-08-11 1959-01-20 Union Carbide Corp Production of nonionic surface active agents
US3054820A (en) * 1957-02-02 1962-09-18 Chemische Fabriek Andrelon Nv Liquid, surface-active salts
US3376333A (en) * 1964-11-16 1968-04-02 Textilana Corp Sulfuric acid esters of linear secondary alcohol ethoxylates and salts thereof and method of producing same
US3468805A (en) * 1965-10-22 1969-09-23 Gaf Corp Detergent composition
US3513099A (en) * 1966-12-06 1970-05-19 Purex Corp Ltd Las detergents containing primary and secondary alkoxy alkanol ammonium sulfates
US3565939A (en) * 1967-06-09 1971-02-23 Standard Chem Products Inc Partial neutralization of sulfates of ethoxylated alcohols
US3786003A (en) * 1971-11-04 1974-01-15 Shell Oil Co Liquid detergent compositions

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2644831A (en) * 1951-04-16 1953-07-07 Monsanto Chemicals Alkali metal and ammonium sulfates of hydroxy ethers
US2766212A (en) * 1952-09-16 1956-10-09 Gen Aniline & Film Corp Detergents
US2870220A (en) * 1953-08-11 1959-01-20 Union Carbide Corp Production of nonionic surface active agents
US3054820A (en) * 1957-02-02 1962-09-18 Chemische Fabriek Andrelon Nv Liquid, surface-active salts
US3376333A (en) * 1964-11-16 1968-04-02 Textilana Corp Sulfuric acid esters of linear secondary alcohol ethoxylates and salts thereof and method of producing same
US3468805A (en) * 1965-10-22 1969-09-23 Gaf Corp Detergent composition
US3513099A (en) * 1966-12-06 1970-05-19 Purex Corp Ltd Las detergents containing primary and secondary alkoxy alkanol ammonium sulfates
US3565939A (en) * 1967-06-09 1971-02-23 Standard Chem Products Inc Partial neutralization of sulfates of ethoxylated alcohols
US3786003A (en) * 1971-11-04 1974-01-15 Shell Oil Co Liquid detergent compositions

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4261917A (en) * 1978-11-10 1981-04-14 The Lion Fat & Oil Co., Ltd. Process for manufacturing a highly concentrated sulfate solution or slurry
DE2935428A1 (de) * 1979-09-01 1981-03-26 Henkel KGaA, 40589 Düsseldorf Waessrige tensidkonzentrate und verfahren zur verbesserung des fliessverhaltens schwer beweglicher waessriger tensidkonzentrate
US4404143A (en) * 1980-06-16 1983-09-13 Lion Corporation Process for producing high concentration solution of salt of alpha-sulfo fatty acid ester
US4412945A (en) * 1982-01-04 1983-11-01 Lion Corporation Aqueous high concentration slurry of alcohol ethoxylate
US4734221A (en) * 1984-05-11 1988-03-29 Lever Brothers Company Detergent compositions
US4734223A (en) * 1984-05-11 1988-03-29 Lever Brothers Company Detergent compositions
EP0211493A3 (en) * 1985-06-21 1988-10-12 Unilever Plc Liquid detergent composition
US4880569A (en) * 1985-06-21 1989-11-14 Lever Brothers Company Concentrated liquid detergent composition containing anionic surfactants having non-terminal sulfonate groups
WO1993018123A1 (en) * 1992-03-10 1993-09-16 The Procter & Gamble Company High active detergent pastes
US5529722A (en) * 1992-03-10 1996-06-25 The Procter & Gamble Company High active detergent pastes
USH1632H (en) * 1994-08-15 1997-02-04 Shell Oil Company Liquid laundry detergent formulations
US6255275B1 (en) * 1996-12-06 2001-07-03 Nippon Shokubai Co., Ltd. Higher secondary alcohol alkoxylate compound composition, method for production thereof, and detergent and emulsifier using the composition
US6346509B1 (en) 1997-12-05 2002-02-12 Nippon Shokubai Co., Ltd. Higher secondary alcohol alkoxylate compound composition, method for production thereof, and detergent and emulsifier using the composition
US20080312121A1 (en) * 2005-09-08 2008-12-18 Kirk Herbert Raney Liquid Surface Active Compositions
US20100010251A1 (en) * 2008-07-10 2010-01-14 Jan Hermen Hendrik Meurs Preparation of alkoxysulfates
EP3176240B1 (en) 2015-12-04 2019-05-22 Chevron Oronite Company LLC Process for preparing alcohol ether sulfates
EP3176240B2 (en) † 2015-12-04 2022-09-07 Chevron Oronite Company LLC Process for preparing alcohol ether sulfates

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JPS5116036B2 (en(2012)) 1976-05-21
JPS4915706A (en(2012)) 1974-02-12

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