IL44118A - Deodorizing method by employing a tetraazaheterocycle and a quaternary ammonium salt - Google Patents

Description

KiBoa rcin*© »"y mn»*i nan nnn no*© Novel deodorizing method by employing a tetraazaheterocycle audaquaternary ammonium salt , .

DR. HERBERT SCHWARTZ NOVEL DEODORIZING METHOD ABSTRACT OF THE DISCLOSURE A method of combatting offensive odors comprising coa tacting the odor causing component with a solution containing' a quaternary ammonium salt catalyst and a tetracyclic hetero-| cycle containing four nitrogen atoms which .is capable of re-! moving malodors by, reaction therewith.

STATE OF THE ART As population increases, there is a concurrent increase in air pollution. The term "air pollution" includes toxic substances in the air and malodors. Of course, the toxic subS'ta-nces- could be- odorless- but may not be, and the malodors could be either toxic or safe at the concentrations present.

Although toxic air pollution is very serious, more attention is directed to the control of malodors for the j effects of malodors are immediately noticeable and very annoy- I ing. Also, certain odors, such as the fetid odors of garbage' i and sewage, could present a health problem to the community by attracting disease-carrying insects and other vermin. ij I Generally, the discharge of malodors into the atmosphere from' I a chemical or biological process can be controlled by modi-fication*of ■ the process, but where such modification is impractical or impossible, the malodors are combined with masking agents modifying them sufficiently to make them less offensive. Recently, however, attempts are being made to they ore no longer annoying to the human nose. These method consist of thermal oxidation and chemical oxidation with ozone, chlorine, potassium permanganate, etc. The value of such procedures is questionable since the odorless products \ ■ could be more injurious to health than the original malodors Although the oxidation of malodor causing component i an attempt at odor control rather than- masking, it has serious defects causing adverse effects on the environment. Mal odors consist of many compounds, some of which contain eithe nitrogen or sulfur or both, usually in the reduced state, e. sulfides, mercaptans, skatoles, amines, etc. The thermal an cold oxidation of these odoriferous compounds would yield ttie toxic oxides of sulfur and nitrogen while with the therm oxidation process the yield of nitrogen oxides would be some . what higher since the high temperatures cause oxidation of . atmospheric nitrogen as well. Lower temperatures have been found to give incomplete oxidation of the organic compounds to yield such toxic products as carbon monoxide, aldehydes, acids, ketones, and water.

Chemical oxidation is usually carried out in an aqu- ■'· ■ ' . ' eous system, primarily in wet scrubbers. The volatile oxl- ■ dation products would then be carried through the system and out the exhaust system into the environment. Thus, this may be some improvement over thermal oxidation but not a full and safe solution to the problem.

British Patent Specification No. 1,327,353 describes a method of combatting odors due to matter by contacting the composition comprised of tracyclic heterocycle con . salts Is that of a germicide killing the bacteria re3ponsTb Tor the decomposition of organic matter thereby generating odors. The3e salts are generally prepared by causing the reaction of a benzyl or alkyl. halide, sulfonate, or sulfate with a ternary base (e.g, a tertiary amine). The usual sal are the halides, such as chloride and bromide, sulfates, methosulfates., and benzenesulfonates.

Among the preferred quaternary ammonium salts for th compositions of the nvention are those having the formula Wherein R Is an alkyl radical of 8 to 20 carbon a oms, X Is any anion such as halide, sulfate, nitrate, carbonate, phosphate, "lower alkyl sulfate, alkanesulfonate, saccharin at£, sulfamate, benzenesul onate, alkylbenzenesulfonates wi 1 to 10 alkyl carbon atoms, etc., and a, b and c may differ ent and are selected from the group consisting of lower alk 'phenyl lower alkyl, naphthyl-lower alkyl and a and b could form together with the nitrogen atom a morpholine ring with c being an alkyl radical of 1 to 20 carbon atoms. .

These and other suitable quaternary ammonium salts are described in Schwartz et al, Surface Active Agents and Detergents, Vol. II, (1958), pp..112-118.

Examples of specific quaternary ammonium salts are BT 2125 (equal parts of n-alkyl dimethyl benzyl ammonium chlorides where the h-alkyl is .14 to 18 carbon atoms and n-alkyl' dimethyl ethyl benzyl ammonium chlorides where h-alkyl is 12 to l4 carbon atoms T h- - amount of the quaternary ammonium salt since the products the Invention can be used at great dilutions. Sufficient quaternar ammonium salt must be available so that a molecule of the quaternary ammonium salt is available to catalyze each contact of a molecule of malodor causing component with an heterocyclic molecule. Accordingly, the ratios of heterocycle to quaternary ammonium salt can vary as much as 10:1 to 1:10 depending upon the application although it was found that for reasons of solubility and physical characteristics the usual ratios will be 5:1 to 1:5. Howeverj this is not to be interpreted as indicating that the higher ratios are not operative but that they are reserved for special applications.

The compositions of the invention may contain any conventional carrier such as water, aqueous alkanols, alkanols, organic solvents, wetting agents, emulsifiers, perfumes, and other standard ingredients for commercial pro-, ducts and formulations • The preferred novel method for controlling malodors comprises contacting the malodor causing component with a stoichiometric amount of a cage-type, nitrogen-containing heterocycle and quaternary ammonium salt. Such mixtures, can economically be used in wet scrubbers to remove the malodors from exhausted air.

The novel method of the invention for removing odors from the air may also be effected by the dilution or solution of the mixture of the cage-type tetracyclic heterocycle containing four nitrogen atoms plus a quaternary ammonium salt and the dispersion of this solution through the air by fogging and/or spraying or by directly spraying the c f h d r x l s re r nd in l nts k nn s manure or sewage lagoons , field toilets , etc . Other methods-may include washing and immersion of the odor source.

In the following examples there are described s everal' preferred embodiments to illustrate the invention. However,1 it should be understood that the invention is not intended to be limited to the specific embodiments., . ·..

·· ** · ·· ■ EXAMPLE 1 A solution of 25 parts by weight of 1,3 , 5,7-tetra- in 52 parts by weight of of 0.5 parts by weight of perfume, 10.0 parts by weight of a polyethylene oxide -alkylphenol adduct as an emulsifier, and 12.5 parts by weight of technical (80$) alkyldimethylbenzylammonium chloride j (alkyl of 12 to 16 carbon atoms ) to form a clear solution. ; This solution was dripped into a lagoon of wash water from j a plant that processes chickens from the live fowl-to dres- ! ί sed poultry and .chicken parts . The plant would collect the : wash water from the cleaning of the chickens and the daily j wash-up, thus containing blood, fats , dirt, etc. , in a large lagoon of about 190, 000 liters with sufficient drainage to j keep its contents constant . The full quantity of water flushed through is approximately 760,000 liters daily. The product of this invention was dripped into this lagoon at j the rate of 220 kilograms every 3 months to control com- ! I pletely the foul odor that usually spreads throughout the j neighborhood of this lagoon.

EXAMPLE 2 V exception of the heterocvp.le so that the 1,3, 6, 8-tetra- azatrlcylo [ ,4^ 1, l^ * 8] . dodecane was substituted . After dilution of this product 440 times with water, the resulti solution was sprayed about the interior of chicken coops, an particularly on the manure covered floors . This treatment deodorized the coops to the point that it was difficult to believe that chickens have ever been in the coops.

EXAMPLE 3 The solution of Example 1 was prepared with ,5, 9, 10-dlbenzo-l>3> 6, 8-tetraazatricyclo [4,4, l, l-> * 8 ] dodecane a the heterocycle. After dilution of this solution 400 times with water, the resulting solution was sprayed over piled ' . chicken manure intended for use as fertilizer. Within 15 . minutes, strong odor control was detected, and Just a few minutes later the entire pile had been deodorized .

EXAMPLE 4 A solution , of 25 parts by weight of 1,3, 5,7-tetra- ··... :."·-■' ! Y ' * azatricyclo - [3,3, 1, 1 ] decane in 75 parts by weight of " ■ ' ' water was added to a solution of 125 parts by weight of technical (80$) alkyldimethylbenzylammonlum chloride (alkyl 8 to 18 carbon atoms ) , 100 parts by weight of polyethylene oxide -alkyl phenol adduct, parts by weight of perfume, 30 parts by weight of jD-dichlorobenzene, &nd 120 parts by . weight of -dichlorobenzene to form a clear solution. This • solution was then diluted 1 '0 times with alcohol and placed in aerosol cans with the correct amount of propellant of the Freon (halocarbon) type. A wine cellar was s prayed EXAMPLE 5 A solution of 5 parts by weight of p-dichlorobenzenei In 10 parts by weight of o_-dichlorqbenzene was added to solution of 72 parts by weight of a 35 solution (in anhy- i drous alcohol) of N,N-cetylethylmorpholinium ethosulfate, 10 parts by weight of N,N-diethyl-m-toluamide, 23 parts by weight of polyethylene oxide-alkyl henol adduct, 255 parts by weight of alcohol, 50 parts by weight of l,3,5j7-tetra-azatricyclo [3,3,1,1^*^] decane, 75 parts by weight of water, and 25 parts by weight of perfume to make a clear solution. This solution was then diluted 10 times with alcohol and placed In aerosol cans along with Freon type propellant. This aerosol was applied to a dog that had had an unfortunate encounter with a skunk. One application neutralized about 80 of the odor, and a second application] eliminated the odor completely.

EXAMPLE 6 A solution of 5 parts by weight of 1,3,5,7-tetra-azatricyclo/[3,3,l,l J decane, 20 parts by weight of alkyl' dlmethylbenzylammonium chloride, 43 parts by weight of water 2 parts by weight of sodium carbonate, 15 parts by weight o polyethylene oxide-alkylphenol adduct, 14 parts by weight of technical N,N-diethanolamides of long-chain fatty acids, and: 1 part by weight of perfume was prepared and then diluted ' j with water 400 times. This dilute solution was then applied! to the floor and walls of animal cages. This single application removed the clinging odors of animal wastes (both liquid and solid) from both dogs and cats.

■ EXAMPLE 14 The product of Example 13, when diluted 1 part to 440 parts by weight of water, can be sprayed into a truck, trailer, or other cargo container in which spoiled food or seafood had left a lingering odor that cannot be washed out. A truck had stood in the hot sun for 2 weeks after the refrigeration unit had broken down. Although the truck was . unloaded and washed out, a repulsive odor prevented further use of the truck, but the interior was then.: sprayed with this solution and closed for 30 to 40 minutes. When opened^ the container had no trace of odor and could be used almost · immediately for the transporation of more food.

EXAMPLE 15 Using the dilution of Example l4,the product was found to remove the odor of smoke from clothes and building i after a fire. Likewise the solution was fogged into the stacks of a municipal incinerator to deodorize the exhausted! air.

EXAMPLE 16 V Using the dilution of Example 14 sufficient product was placed in the vaults of park latrines to cover the bottom to a depth of several centimeters. The latrine remained odor free between clean-ups.

Various modifications of the products and compositions of this invention may be made without departing from I the spirit or scope thereof, and it is to be understood that the invention is to be limited only as defined in the 44118/3

Claims (1)

1. CLAIMS 1. A method of combatting offensive odors comprising reacting the odor causing component with a solution containing tetraazaheterocycles with four rings and each ring sharing its sides with the other three rings forming an enclosed ent and are selected from the group consisting of lov/er alky phenyl lower alkyl, naphthyl-lower ' alkyl and a and b could form together with the nitrogen atom a morpholine' ring with c being an alkyl radical of 1 to 20 carbon atoms. 5. The method of claim 4 wherein the heterocycle 3 7 s 1,3,5,7 tetraazatricyclo.3,3,1,1 * ]decane. cle is cle is ]-