US3298963A - Detergent breaker composition - Google Patents

Detergent breaker composition Download PDF

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US3298963A
US3298963A US488813A US48881365A US3298963A US 3298963 A US3298963 A US 3298963A US 488813 A US488813 A US 488813A US 48881365 A US48881365 A US 48881365A US 3298963 A US3298963 A US 3298963A
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detergent
aluminum
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Frank James Stuart
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D19/00Degasification of liquids
    • B01D19/02Foam dispersion or prevention
    • B01D19/04Foam dispersion or prevention by addition of chemical substances
    • B01D19/0404Foam dispersion or prevention by addition of chemical substances characterised by the nature of the chemical substance
    • B01D19/0409Foam dispersion or prevention by addition of chemical substances characterised by the nature of the chemical substance compounds containing Si-atoms

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  • This invention relates to the degradation of synthetic detergents, and particularly to the treatment of waters containing synthetic detergents so as to inhibit foaming and to cause the breakdown of the synthetic detergent molecules.
  • R(OSO -Na+) The generic formula of anionic aliphatic sulfonates can be written R(OSO -Na+) in which R contains one or more hydrophobic groups.
  • R contains one or more hydrophobic groups.
  • One example is sodium dodecyl benzene sulfonate. These are the alkyl benzene sulfonates commonly termed ABS.
  • the cationic surface active agents like the anionic agents, have hydrophilic and hydrophobic groups, ionization occurring in the cation. Examples of this class are the salts of strong quaternary bases.
  • the nonionic surface active agents are ones wherein an adequate degree of hydration can be achieved if a sufficient number of nonionizing polar groups are present. An example of such are the polyethoxy agents having the general formula R,(CH CH O) mH
  • One of the objects of the invention is to provide a synthetic detergent degradation compound which will efficiently break down the synthetic detergent molecule in aqueous solution without contaminating the liquid to be separated from the synthetic detergent.
  • Another object of the invention is to provide a compound which can be applied in diluted form or directly to the waters to be treated.
  • a semisoluble complex synthetic detergent breaker composition comprising 2 to 60% by Weight, dialkylpolysiloxane having the general formula (RSiO) with R alkyl radicals at the chain ends, where the alkyl is selected from the group consisting of methyl, ethyl, propyl, up to 6 carbon atoms, and where n isan integer representing the degree of polymerization or association and n may range, for example, from 2 to 100 or more; .2 to 70%, by weight, alkyl-siloxymetallic complex where the complex chain (organo-silicon) has the general formula (RSiO) M where M is the metallic ion selected from the group consisting of aluminum, ferrous, ferric,,coba1t, etc., and R is an alkyl selected from ICC the group methyl, ethyl, propyl, up to 6 carbon atoms; 10 to by weight, metallic sulfate where the metallic ion is
  • dialkylpolysiloxane generally preferred are the relatively high molecular weight polymers wherein It may be, for instance, 30 to 50.
  • One dialkylpolysiloxane which can be used is dimethylpolysiloxane, such being prepared by adding dimethyldichlorosilane to water (demineralized) which yields dimethylsilanol. The dimethylsilanol upon standing will decompose to dimethylpolysiloxane and hydrogen chloride gas, with just the dimethylpolysiloxane remaining in the reacting vessel.
  • Another dialkylpolysiloxane that can be used is diethyldichlorosilane instead of dimethyldichlorosilane, such yielding diethylsilanol and diethylpolysiloxane.
  • trialkylsiloxymetallic complex is triethylsiloxyaluminum formed by adding powdered aluminum to t-riethylsilanol which upon the application of heat yields triethylsiloxyaluminum plus hydrogen gas. Sulfuric acid is then added in a small quantity to keep the pH down.
  • a further example of a trialkylsiloxymetallic complex is trimethylsiloxyaluminum formed by reacting trimethylsilanol with powdered aluminum, yielding the desired trimethylsiloxyaluminum. Again sulfuric acid is added in small quantity to control pH.
  • Example I A synthetic detergent breaker composition was formed from 40%, by weight, aluminum sulfate added to 30%, by weight, dimethylpolysiloxane. After thorough mixing, 20%, by weight, triethylsiloxyaluminum was added along with 1.5%, by weight, sulfuric acid. Then 8.5%, by weight, silica gel was added.
  • Example II To 20%, by weight, dimethylpolysiloxane 50%, by weight, aluminum sulfate was added. After complete mixing, 25%, by weight, triethylsiloxyaluminum was added. A trace (less than 0.3%), of sulfuric acid was added, followed immediately by the addition of silica gel, 5% by weight.
  • Example Ill To 25%, by weight, dimethylpolysiloxane, there was added 50%, by weight, aluminum sulfate. After complete mixing, 15%, by weight, trimethylsiloxyaluminum was added, followed by 2%, by weight, sulfuric acid and silica gel, 8% by weight.
  • Example IV To 18%, by weight, diethylpolysiloxane, 42%, by weight, aluminum sulfate was added and completely mixed. Then 31%, by weight, triethylsiloxyaluminum was added, followed by 9%, by weight, silica gel and a trace of sulfuric acid.
  • the dialkylpolysiloxanes mentioned were found to have excellent defoaming characteristics, the defoaming apparently being a surface effect without chemical reaction between the polysiloxanes and the alkyl benzene sulfonates.
  • the alkylsiloxymetallic complex as described was Patented Jan; 17, 1967 found to be, along with a metallic sulfate, an efficient cogel; and 0.2 to 0.5 by weight of pH controlling mateagulant but without good defoaming characteristics.
  • rial where the pH controlling material is selected from Following is an example of test results using the synthe group consisting of sulfuric acid, sulfurous acid and thetic detergent breaker of Example I of the invention: ascorbic acid.
  • a synthetic detergent breaker composition as in Timein minutes claim 1 consisting of 30% by weight dimethylpolysiloxgg gg g ane; 20% by weight triethylsiloxyaluminum complex; Breaker 90% Breaker 40% by weight aluminum sulfate; 8.5% by weight silica gel; and 1.5% by weight sulfuric acid.
  • a synthetic detergent breaker composition as in g 2 claim 1 consisting of 20% by weight dimethylpolysilox- 1 7 ane; 20% by weight triethylsiloxyaluminum complex; g3 14 50% by weight aluminum sulfate; by weight silica gel; and 0.2 to 0.3% by weight sulfuric acid. 15 4.
  • a synthetic detergent breaker composition as in Preferably the pH controlling substance should be claim 1 consisting bf y Weight.dimethylpblysilbxadded in sufficient quantity to bring the pH between 4.;5 21116; 15% b Welgbt tnmetbylsiloxyalbminbm cbmblbm and 5.5 although the breaker remained effective to pH by Welght aluminum Sulfate; 8% y Welgbt slllca 7.1 where hydrolysis became a major problem.
  • a synthetic detergent breaker composition consisting gel; and to 5% of sulfuric acidessentially of 2 to by weight dialkylpolysiloxane 25 having the general formula (RSiO) where n is a posi- References Cited by the Examiner tive integer of 2 to and, where the R radicals are UNITED STATES PATENTS alkyl and at the chain 6ndS, the alkyl radicals being SC- 2 217 4 6 10/1940 B li 252 lected from the group Consisting of y y P py 2 435 124 1 194 Boninger 2 52-32 butyl, pentyl and hexyl; 2 to 70% by weight alkylsiloxy- 30 2 632 736 3/1953 Currie metallic complex having the general formula (RSiO) M 289722O 7/1959 Jenkner 260448 where M is the metallic ion selected from the group con- 2:964:466 12/1960 Famham 252 175 sisting of aluminum, ferrous, ferric
  • BLECI-I Primary Examiner. by weight metallic sulfate where the metallic ion thereof is selected from the group consisting of aluminum, fer- ALBERT MEYERS Examiner rous, ferric, and cobalt; 0.5% to 20% by weight silica W.
  • E. SCHULZ Assistant Examiner.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Dispersion Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Detergent Compositions (AREA)

Description

cule remaining in the waste water.
United 5 States Patent 3,298,963 DETERGENT BREAKER COMPOSITION James Stuart Frank, 7051N. Fairchild Circle,
. .Milwaukee, Wis. 53217 No Drawing. Filed Sept. 20, 1965, Ser. No. 488,813 j 5 Claims. (Cl. 252-358) This application is a continuation-in-part of Ser. No. 321,676 filed November 6, 1963, now abandoned.
This invention relates to the degradation of synthetic detergents, and particularly to the treatment of waters containing synthetic detergents so as to inhibit foaming and to cause the breakdown of the synthetic detergent molecules.
One of the problems in,present day water supplies is that foam appears on the rivers or in the drinking water because the synthetic detergents now used do not decompose under conventional disposal or sewage treatment. Previously known materials or compounds have not satisfactorily solved the problem of effectively inhibiting foam and of breaking down the synthetic detergent mole- Such a degradation material must be inexpensive, non-poisonous and effective. Synthetic detergents of anionic, cationic and nonionic categories have come into quite general use. The detergent molecule has a dual character in that part of the molecule has water attracting or hydrophilic tendencies, while the other part has hydrophobic properties. It is because of this peculiar molecular structure that detergent solutions possess good wetting and emulsifying power, that they foam and are adapted to clean soiled surfaces. The generic formula of anionic aliphatic sulfonates can be written R(OSO -Na+) in which R contains one or more hydrophobic groups. One example is sodium dodecyl benzene sulfonate. These are the alkyl benzene sulfonates commonly termed ABS.
The cationic surface active agents, like the anionic agents, have hydrophilic and hydrophobic groups, ionization occurring in the cation. Examples of this class are the salts of strong quaternary bases. The nonionic surface active agents are ones wherein an adequate degree of hydration can be achieved if a sufficient number of nonionizing polar groups are present. An example of such are the polyethoxy agents having the general formula R,(CH CH O) mH One of the objects of the invention is to provide a synthetic detergent degradation compound which will efficiently break down the synthetic detergent molecule in aqueous solution without contaminating the liquid to be separated from the synthetic detergent.
Another object of the invention is to provide a compound which can be applied in diluted form or directly to the waters to be treated.
The above and other objects of the invention can be accomplished by the provision of a semisoluble complex synthetic detergent breaker composition comprising 2 to 60% by Weight, dialkylpolysiloxane having the general formula (RSiO) with R alkyl radicals at the chain ends, where the alkyl is selected from the group consisting of methyl, ethyl, propyl, up to 6 carbon atoms, and where n isan integer representing the degree of polymerization or association and n may range, for example, from 2 to 100 or more; .2 to 70%, by weight, alkyl-siloxymetallic complex where the complex chain (organo-silicon) has the general formula (RSiO) M where M is the metallic ion selected from the group consisting of aluminum, ferrous, ferric,,coba1t, etc., and R is an alkyl selected from ICC the group methyl, ethyl, propyl, up to 6 carbon atoms; 10 to by weight, metallic sulfate where the metallic ion is selected from the group of aluminum, ferrous, ferric, cobalt, etc. (and usually corresponds to the metal in the alkylsiloxymetallic complex); 0.5 to 20%, by weight, silica gel as a common base; and 0.2 to 5.0%, by weight, sulfuric acid or other sulfurous acid or ascorbic acid to control the pH. In the case of dialkylpolysiloxane, generally preferred are the relatively high molecular weight polymers wherein It may be, for instance, 30 to 50.
One dialkylpolysiloxane which can be used is dimethylpolysiloxane, such being prepared by adding dimethyldichlorosilane to water (demineralized) which yields dimethylsilanol. The dimethylsilanol upon standing will decompose to dimethylpolysiloxane and hydrogen chloride gas, with just the dimethylpolysiloxane remaining in the reacting vessel. Another dialkylpolysiloxane that can be used is diethyldichlorosilane instead of dimethyldichlorosilane, such yielding diethylsilanol and diethylpolysiloxane.
An example of a trialkylsiloxymetallic complex is triethylsiloxyaluminum formed by adding powdered aluminum to t-riethylsilanol which upon the application of heat yields triethylsiloxyaluminum plus hydrogen gas. Sulfuric acid is then added in a small quantity to keep the pH down.
A further example of a trialkylsiloxymetallic complex is trimethylsiloxyaluminum formed by reacting trimethylsilanol with powdered aluminum, yielding the desired trimethylsiloxyaluminum. Again sulfuric acid is added in small quantity to control pH.
Example I A synthetic detergent breaker composition was formed from 40%, by weight, aluminum sulfate added to 30%, by weight, dimethylpolysiloxane. After thorough mixing, 20%, by weight, triethylsiloxyaluminum was added along with 1.5%, by weight, sulfuric acid. Then 8.5%, by weight, silica gel was added.
Example II To 20%, by weight, dimethylpolysiloxane 50%, by weight, aluminum sulfate was added. After complete mixing, 25%, by weight, triethylsiloxyaluminum was added. A trace (less than 0.3%), of sulfuric acid was added, followed immediately by the addition of silica gel, 5% by weight.
Example Ill To 25%, by weight, dimethylpolysiloxane, there was added 50%, by weight, aluminum sulfate. After complete mixing, 15%, by weight, trimethylsiloxyaluminum was added, followed by 2%, by weight, sulfuric acid and silica gel, 8% by weight.
Example IV To 18%, by weight, diethylpolysiloxane, 42%, by weight, aluminum sulfate was added and completely mixed. Then 31%, by weight, triethylsiloxyaluminum was added, followed by 9%, by weight, silica gel and a trace of sulfuric acid.
The dialkylpolysiloxanes mentioned were found to have excellent defoaming characteristics, the defoaming apparently being a surface effect without chemical reaction between the polysiloxanes and the alkyl benzene sulfonates. The alkylsiloxymetallic complex as described was Patented Jan; 17, 1967 found to be, along with a metallic sulfate, an efficient cogel; and 0.2 to 0.5 by weight of pH controlling mateagulant but without good defoaming characteristics. rial where the pH controlling material is selected from Following is an example of test results using the synthe group consisting of sulfuric acid, sulfurous acid and thetic detergent breaker of Example I of the invention: ascorbic acid.
5 2. A synthetic detergent breaker composition as in Timein minutes claim 1 consisting of 30% by weight dimethylpolysiloxgg gg g ane; 20% by weight triethylsiloxyaluminum complex; Breaker 90% Breaker 40% by weight aluminum sulfate; 8.5% by weight silica gel; and 1.5% by weight sulfuric acid.
3. A synthetic detergent breaker composition as in g 2 claim 1 consisting of 20% by weight dimethylpolysilox- 1 7 ane; 20% by weight triethylsiloxyaluminum complex; g3 14 50% by weight aluminum sulfate; by weight silica gel; and 0.2 to 0.3% by weight sulfuric acid. 15 4. A synthetic detergent breaker composition as in Preferably the pH controlling substance should be claim 1 consisting bf y Weight.dimethylpblysilbxadded in sufficient quantity to bring the pH between 4.;5 21116; 15% b Welgbt tnmetbylsiloxyalbminbm cbmblbm and 5.5 although the breaker remained effective to pH by Welght aluminum Sulfate; 8% y Welgbt slllca 7.1 where hydrolysis became a major problem. and 2% y Weight of Sulfuric acid- It should be apparent that variations may be made 20 A b b detergent brealfel cqmposltlon 1n without departing from the spirit of the invention, exclalm 1 bbnslstmg 9 y f f y p y Cept as d fi d in the appended 1 ane; 31% by weight triethylsiloxyaluminum complex; What is claimed 42% by weight aluminum sulfate; 9% by weight silica 1. A synthetic detergent breaker composition consisting gel; and to 5% of sulfuric acidessentially of 2 to by weight dialkylpolysiloxane 25 having the general formula (RSiO) where n is a posi- References Cited by the Examiner tive integer of 2 to and, where the R radicals are UNITED STATES PATENTS alkyl and at the chain 6ndS, the alkyl radicals being SC- 2 217 4 6 10/1940 B li 252 lected from the group Consisting of y y P py 2 435 124 1 194 Boninger 2 52-32 butyl, pentyl and hexyl; 2 to 70% by weight alkylsiloxy- 30 2 632 736 3/1953 Currie metallic complex having the general formula (RSiO) M 289722O 7/1959 Jenkner 260448 where M is the metallic ion selected from the group con- 2:964:466 12/1960 Famham 252 175 sisting of aluminum, ferrous, ferric and cobalt and the R 3,131,143 4/1964 Tauni radicals are alkyl selected from the group consisting of methyl, ethyl, p py butyl, p y and y 0 o 70% 35 SAMUEL H. BLECI-I, Primary Examiner. by weight metallic sulfate where the metallic ion thereof is selected from the group consisting of aluminum, fer- ALBERT MEYERS Examiner rous, ferric, and cobalt; 0.5% to 20% by weight silica W. E. SCHULZ, Assistant Examiner.

Claims (1)

1. A SYNTHETIC DETERGENT BREAKER COMPOSITION CONSISTING ESSENTIALLY OF 2 TO 60% BY WEIGHT DIALKYLPOLYSILOXANE HAVING ATHE GENERAL FORMULA (RSIO)N WHERE N IS A POSITIVE INTEGER OF 2 TO 100 AND, WHERE THE R RADICALS ARE ALKYL AND AT THE CHAIN ENDS, THE ALKYL RADICALS BEING SELECTED FROM THE GROP CONSISITING OF EMTHYL, ETHYL, PROPYL, BUTL, PENTYL AND HEXYL; 2 TO 70% BY WEIGHT ALKYLSILOXYMETALLIC COMPLEX HAVING THE GENERAL FORMULA (RSIO)3M WHERE M IS THE METALLIC ION SELECTED FROM THE GROUP CONSISTING OF ALUMINUM, FERROUS, FERRIC AND COBALT AND THE R RADICALS ARE ALKYL SELECTED FROM THE GROUP CONSISTING OF METHYL, ETHYL, PROPYL, BUTYL, PENTYL AND HEXYL; 10 TO 70% BY WEIGHT METALLIC SULFATE WHERE THE METALLIC ION THEREOF IS SELECTED FROM THE GROUP CONSISTING OF ALUMINUM, FERROUS, FERRIC, AND COBLAT; 0.5% TO 20% BY WEIGHT SILICA GEL; AND 0.2 TO 0.5% BY WEIGHT OF PH CONTROLLING MATERIAL WHERE THE PH CONTROLLING MATERIAL IS SELECTED FROM THE GROUP CONSISTING OF SULFURIC ACID, SULFUROUS ACID AND ASCORBIC ACID.
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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2217466A (en) * 1937-09-17 1940-10-08 City Of Chicago Composition of matter for water treatment
US2435124A (en) * 1945-01-22 1948-01-27 Shell Dev Method of dispersing a foam-reducing silicon-containing compound
US2632736A (en) * 1946-08-22 1953-03-24 Dow Chemical Co Antifoaming composition
US2897220A (en) * 1955-05-28 1959-07-28 Kali Chemie Ag Preparation of triorganosilanes
US2964466A (en) * 1956-03-06 1960-12-13 Farnham Willard Process of clarifying turbid water using cottrell flour and acidifying coagulant
US3131148A (en) * 1961-01-13 1964-04-28 Monsanto Chemicals Thickened compositions

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2217466A (en) * 1937-09-17 1940-10-08 City Of Chicago Composition of matter for water treatment
US2435124A (en) * 1945-01-22 1948-01-27 Shell Dev Method of dispersing a foam-reducing silicon-containing compound
US2632736A (en) * 1946-08-22 1953-03-24 Dow Chemical Co Antifoaming composition
US2897220A (en) * 1955-05-28 1959-07-28 Kali Chemie Ag Preparation of triorganosilanes
US2964466A (en) * 1956-03-06 1960-12-13 Farnham Willard Process of clarifying turbid water using cottrell flour and acidifying coagulant
US3131148A (en) * 1961-01-13 1964-04-28 Monsanto Chemicals Thickened compositions

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