This invention relates both to deodorant products of special character and to the method for using such special products.

A principal object of the invention is to provide special deodorant products having unique capabilities, and which are effective for neutralizing or masking a variety of molodors over an extended period of time. A further object is to provide such deodorant products which are substantially completely dissipated when their deodorizing capabilities have been exhausted.

More specifically it is an object to provide a gel type of product which will adhere to a surface and solidify, a solid product which can be handled readily and a solid floating product which can include both deodorant for deodorizing airborne malodors and biodegradants for treating over an extended period of time material in the liquid on which the product floats.

Another object is to provide a method of handling and placing deodorant for local deodorizing such as in rest rooms. It is also an object to provide a method for treating effectively over an extended period of time malodorous gas escaping from a sewage lagoon, and also to provide a source of biodegradant material, such as bacteria, fungi and enzymes, which will be supplied to the liquid of the lagoon over a prolonged period.

A principal purpose of the products of the present invention is to deodorize a wide variety of malodors.

In this description the word "deodorize" is used broadly to refer to chemical neutralization of malodorous substances, such as by providing an acid substance to react with a malodorous base and produce a salt having an inoffensive odor, or reodorizing by providing a substance which will react with a malodorous substance to produce a pleasant odor, or simply masking an unpleasant odor by mixing with it material having a more pronounced pleasant odor so as to overcome the effect of the objectionable odor.

Odors which the products of the present invention are capable of deodorizing are trimethylamine having a fishy odor, skatole and indole having the odor of feces and sewage, acrolein having an acrid ordor such as produced by rendering animal, poultry and fish waste, butyric acid having the odor of rancid butter, secondary and tertiary ammonia compounds, putescence having the odor of rotting vegetation, and cadaverine having the odor of decaying flesh. While the product of the present invention will not eliminate all of such malodors, such products will at least counteract or mask those odors so as to provide an aesthetically acceptable atmosphere to breathe.

The drawing is a top perspective of a floater product with parts broken away.

All of the deodorant products include deodorant such as musk xylene crystals, C₁₂ H₁₅ N₃ O₆, vanillin, CH₃ O(OH)C₆ H₃ CHO, lemon oil or limonene, C₁₀ H₁₆, and 2,3 butanedione or biacetyl, CH₃ COCOCH₃ ; release retardant including paradichlorobenzene, C₆ H₄ Cl₂, (See U.S. Pat. No. 1,346,337), paranitrochlorobenzene, C₆ H₄ ClNO₂, (See U.S. Pat. No. 1,515,364), dinitrobenzene, C₆ H₄ (NO₂)₂, dinitrotoluene, C₇ H₆ O₄ N₂, dinitronaphthalene, C₁₀ H₆ O₄ N₂, dichloronitrobenzene, C₆ H₃ Cl₂ NO₂ dinitrochlorobenzene, C₆ H₃ O₄ N₂ Cl, benzophenone, C₆ H₅ COC₆ H₅, and 2,3 butanedione solidified with phosphoric acid, C₄ H₆ O₂ -2H₃ PO₄ ; and binder and/or plasticizer such as paraffin, gelatin, agar-agar, carrageenin, pectin, cellulose derivatives such as methylcellulose, carboxymethylcellulose, hydroxypropyl methylcellulose and sodium carboxy-methylcellulose, and sorbitan derivatives and complexes such as sorbitan polyoxyethylene monooleate, sorbitan polyoxyethylene monostearate and sorbitan monostearate. The 2,3 butanedione deodorant could be used in the solid compound form of phosphoric acid and biacetyl crystals, C₄ H₆ O₂.2H₃ PO₄, instead of in the liquid form. Other ingredients particularly suitable for incorporation in special products will be pointed out in connection with such products.

Gel Product

A problem of deodorizing a limited space, such as a rest room, involves providing a form of or container for deodorant which is visually unobtrusive and a deodorant which is persistently effective for a long period of time, can be located where it is most effective and is not apt to be vanadlized. When deodorant is placed in a container secured to a wall, it is considered to be unpleasantly obtrusive by many, and provides a challenge to others inviting the container to be removed or broken. Moreover, such containers can practically be placed at only one or two locations in most public rest rooms so that their effectiveness is not at all uniformly or appropriately distributed. The gel product of the present invention can be extruded from a collapsible tube or plastic bottle onto a surface whether horizontal, vertical or inverted to form a daub or ribbon of material which will solidify quickly after it is exposed to the air.

Consequently, any amount of the gel can be placed at any location and at as many locations as may be desired without reliance on any holding and/or dispensing device. A daub or daubs or a ribbon or ribbons may, for example, be applied to the underside of a toilet seat, or to the underside of or alongside a urinal. Such a daub or ribbon would not particularly challenge a person to remove it. The material can be applied quickly. Action of the material to deodorize involves the material being dissipated slowly, which automatically removes the material of the daub or ribbon. When the material has been completely spent, little or no residue remains to be cleaned off the surface.

The gel includes deodorant of one or more of the types recited above, release retardant which greatly deters and prolongs the volatilization of the deodorant component, and binder and/or plasticizer. The binder plasticizes the deodorant and the release retardant so as to form a gel that can be extruded readily. Optionally soap and ammonia can be included as deodorant absorbent carrier in the gel. A representative formula for the gel product contains the following ingredients by weight:

______________________________________deodorant           0.1 to 50 percentrelease retardant   10 to 80 percentbinder and/or       1 to 50 percentplasticizer______________________________________

A formula specifying representative ingredients by weight is:

______________________________________deodorantmusk xylene         0.1 to 30 percentvanillin            0.1 to 30 percentlimonene            0.1 to 35 percentrelease retardantparadichlorobenzene 5 to 65 percentbinder & plasticizerparaffin            5 to 70 percentabsorbentsoap                0 to 30 percentammonia             0 to 3 percent______________________________________

Preferred proportions of the aforesaid representative ingredients are:

______________________________________musk xylene      15 percentvanillin         15 percentlimonene         30 percentparadichlorobenzene            15 percentparaffin (low melt)            15 percentsoap              9 percentammonia           1 percenttotal            100 percent______________________________________

Ammonium hydroxide and soap are heated to 150° F. and mixed, followed by cooling to room temperature. The paraffin is melted and the various ingredients are added, the total mixture is mixed together, poured into tubes or squeezable bottles and sealed.

From a gel of this general type which has been solidified in a daub or a ribbon, deodorant will be vaporized over a long period of time, such as a week to several months, depending upon the particular composition of the gel and the size and thickness of the daub or ribbon. The volatile deodorant will be released more rapidly at higher temperatures and less rapidly at cooler temperatures. In order to release the deodorant, the release retardant must also be vaporized so that the daub or ribbon is progressively dissipated until it has virtually disappeared when all of the deodorant has been released.

Ordinarily the gel product of the present invention will not contain 2,3 butanedione, except for industrial operations, because the deodorizing capability of such substance is much greater than normally is required for deodorizing locations in which the extrudable gel would normally be used.

The gel type of carrier can be used as a carrier for insecticide instead of or in addition to serving as a vehicle for deodorant. If the gel is to be used for dispensing both deodorant and insecticide, an appropriate insecticide can simply be added to the gel formula. Suitable insecticides include 2,2-dichlorovinyl dimethyl phosphate or dichlorovos, C₄ H₇ Cl₂ O₄ P, which is sold under the trade name "Vapona", dieldrin, C₁₂ H₈ OCl₆, malathion, C₁₀ H₁₉ O₆ PS₂, pyrethrin I, C₂₁ H₂₈ O₃, and pyrethrin II, C₂₂ H₂₈ O₅. The insecticides are effective to kill mosquitos, carpenter ants, termites and cockroaches, for example. The amount of insecticide included in a deodorant gel could be from 0 to 25 percent, a preferred proportion being approximately 4 percent. Such insecticides could also be dispensed in the gel as a carrier without the deodorants such as musk xylene, vanillin and limonene, in which instance the proportion of insecticide could be greater, such as approximately 8 percent. In addition, the gel could include with the insecticide attractants for insects such as pheromones, which include geraniol, eugenol anisyl acetone, methyl eugenol, sec-butyl 6-methyl-3-cyclohexene-1-carboxylate (siglure), anethole, 10-trans-12-cis-hexadecadien-1-OL 9-octadecene, and sec-butyl 4 (or 5) -chloro-2. The proportion of such pheromones in liquid form would be 0 to 35 percent by weight, a preferred proportion being 15 percent.

The gel could also be used as a vehicle for insect repellent, such as dinitropropylisocinchomeranate, n-propyl N,N-diethylsuccinamate benzyl benzoate, 2-phenylcyclohexanol, 2-ethylhexanediol-1,3, 2-ethyl-2-butyl-propanediol-1,3, dimethyl phthalate, and N-butylacetanilide. The proportion of such repellent could be within the range of 0 to 40 percent by weight by weight, a preferred proportion being approximately 20 to 25%.

Solid

A principal use for the initially solid product of the present invention is for deodorizing conditions in which malodors are acute, or produced in a large volume in a concentrated area. An example of such a situation is in a rendering plant for animal, poultry and/or fish products. The solid deodorant product can be supplied in formed or molded elements of block, pellet or stick form which can be placed in the material being rendered. Such rendering may be for the purpose of producing animal feed, fertilizer, lard, tallow, soap or adhesives. Because such rendering is accomplished at rather high temperatures, such as 150° F. to 250° F., the release of the volatile deodorant will be retarded much less than at lower temperatures. The deodorant acts to deodorize the gas and steam liberated from the organic material being rendered by the rendering process.

Because of the high volume of malodorous gas evolved from a large rendering cook, use of a powerful deodorant is appropriate and justified. Consequently, for such purposes as deodorizing organic rendering cooks, utilization of 2,3 butanedione is recommended. Ordinarily it is preferred that such deodorant be used in conjunction with other deodorant such as musk xylene and/or vanillin. Because the 2,3 butanedione is in the form of liquid, instead of being crystalline like musk xylene and vanillin, the binder and/or plasticizer component will provide a binding action which will enhance the firmness of the product even at higher temperatures to increase the volatilization retarding action of the release retarant.

A representative formula for the solid product of the present invention is by weight:

______________________________________2,3 butanedione     0.01 to 10 percentcrystalline         1 to 30 percentdeodorantrelease retardant   1 to 30 percentbinder              1 to 50 percent______________________________________

Representative ingreidents which could be used in such a formula are by weight:

______________________________________deodorant2,3 butanedione     0.01 to 10 percentmusk xylene         1 to 30 percentvanillin            1 to 30 percentlimonene            0.01 to 20 percentrelease retardantparadichlorobenzene 1 to 30 percentbinderparaffin (low melt) 3 to 50 percent______________________________________

A preferred specific formula includes the following proportions of the ingredients by weight:

______________________________________2,3 butanedione    8 percentmusk xylene       15 percentvanillin          15 percentlimonene           7 percentparadichlorobenzene             25 percentparaffin (low melt)             30 percent______________________________________

The solid product is made by melting the paraffin, adding the paradichlorobenzene, the musk xylene and the vanillin and mixing them together at a temperature sufficiently high to maintain the paraffin melted, such as approximately 160° F., and then mixing in the liquid 2,3 butanedione and the liquid limonene while the mixture is cooling. After the ingredients have been thoroughly mixed together, the still fluid or plastic body is poured or packed into molds to cool and set into blocks, pellets or sticks of desired size. A pellet or a stick of substantial size, such as one weighing approximately seven ounces will deodorize satisfactorily effluent gas from an organic material rendering cook of three tons of animal, fish and/or poultry waste material.

Floater

Especially near or in inhabited communities odors from a sewage lagoon, or a lagoon receiving waste from an industrial plant, produces malodors offensive to the neighborhood. Stabilization by natural processes to a point where malodor is negligible may require a period of several months. Some lagoons relying on the action of aerobic bacteria are shallow and may be agitated mechanically and/or aerated. Such lagoons are designated activated sludge lagoons.

Other lagoons are deeper and are quiescent. Such lagoons are usually used seasonally by food processors and renderers as natural sewage-settling tanks, and on farms. Especially such lagoons can create objectionable odors and problems, particularly downwind from the lagoon.

The floater of the present invention is particularly efficacious for deodorizing effluent gases from lagoons over an extended period of time. Preferably the floater attacks the odor problem in two ways: first that of deodorizing effluent gas and, second, providing biodegradant material to the lagoon, that is, material which will promote and expedite the biodegradation of organic material in the lagoon liquid. In addition, the floater can incorporate an ingredient to cover the surface of the lagoon for deterring escape of gas from it.

A representative type of durable floater is shown in the drawing in which the float component 1 is illustrated as being a form-sustaining solid of annular shape. Preferably its exterior periphery tapers downward, so as to identify top and bottom of the article. The central aperture tapers from top to bottom to receive and hold a downwardly tapered core plug 2 as an adjunct to the float 1.

A representative formula for the composition of the annulus 1 by weight is as follows:

______________________________________deodorant            5 to 50 percentrelease retardant    5 to 35 percentbinder substantially 2 to 40 percentnonreactive chemicallywith water andsubstantially insolublesin watersurface coating      5 to 65 percentmaterialBuoyant material     10 to 90 percent.substantially nonreactivechemically with waterand substantiallyinsoluble in water______________________________________

Specific ingreidents for the floater could include the following by weight:

______________________________________deodorantmusk xylene          0 to 20 percentvanillin             0 to 20 percent2,3 butanedione      0.01 to 15 percentlimonene             0 to 15 percentrelease retardantparadichlorobenzene  0 to 25 percentbinderparaffin             2 to 30 percentsurface coatingcetyl alcohol        0.01 to 15 percentC16 H33 OHor mineral oilbuoyant material which issubstantially nonsoluble inwater and which issubstantially nonreactivechemically with watersawdust              10 to 90 percent______________________________________

The paraffin and sawdust, which are the principal ingredients, do not react chemically with water and are not appreciably soluble in water, provide buoyancy for the floater so that the entire specific gravity of the composite floater is less than 1. Such ingredients form a body of substantial size stably form-sustaining when floating in contact with water.

A specific suitable formula for the float component of the floater could include the following ingredients in the proportions specified by weight:

______________________________________musk xylene      2 percentvanillin         8 percent2,3 butanedione  2 percentlimonene         2 percentparadichlorobenzene            8 percentparaffin         47 percentcetyl alcohol    2 percentC16 H33 OHsawdust          29 percenttotal            100 percent______________________________________

The float component is made by heating the paraffin until it is melted, mixing with it the musk xylene, vanillin and the paradichlorobenzene. When these ingredients have been thoroughly mixed the liquid ingredient 2,3 butanedione, limonene and cetyl alcohol are mixed, added to the mixture and, finally, the sawdust is mixed in. The resulting mixture is sufficiently plastic so that it can be packed into molds to set.

The core portion 2 of the floater provides biodegradants which will assist in biodegrading carbohydrate, protein, fat, hair, polysaccharides and other material dissolved or suspended in the liquid of the lagoon. The core can supply bacteria, fugi and enzymes for this purpose. The bacteria, for example, may be Streptococcus fecealis and/or Streptococcus diacelylactis. The fungi, for example, may be yeast such as candida pseudotropicalis or saccharomyces cereviseae. The enzymes, for example, may include lipase, chitinase, proteinase and carbohydrase. The core may include sawdust, clay and/or papier-mache' serving as absorbents to provide body for the core. These materials are substantially insoluble in water and substantially nonreactive chemically with water. The clay serves as insert filler and binder. Also, it may be desirable to provide nutrients for the bacteria and fungi in the form of sugar.

A representative formula for the core 2 can include the following ingredients by weight:

______________________________________sawdust             0 to 5 percentclay                5 to 80 percentmixed culture of    1 to 50 percentbacteria andfungienzymes             0 to 50 percentsugar               0 to 50 percent______________________________________

A satisfactory formula for the core may include:

______________________________________sawdust, clay   50 percentand/or papier-mache'clay            10 percentmixed culture of           35 percentbacteria, fungiand yeastenzymes          4 percentsugar            1 percenttotal           100 percent______________________________________

In addition, the float component 1 or the core 2 or both may include buffer material for adjusting the pH of the lagoon liquid.

Composite floaters can simply be placed at strategic locations on a lagoon, and may either be anchored or may float freely. The surface covering ingredient will be released to provide an essentially monomolecular coating on the surface of the lagoon to deter escape of the gas from the liquid. The deodorants of the float will deodorize such gas as does escape. Particularly the 2,3 butanedione is a very powerful and effective deodorant which will deodorize over a wide area. In a typical situation a single floater will deodorize gas escaping from a lagoon over an area of approximately 10,000 square feet at a temperature of 70° F. persistently throughout an extended period of time, such as approximately a month because it is in the form of a body of substantial size stably form-maintaining when floating in contact with water. Consequently, floaters should be placed on a lagoon not over 100 feet apart to be most effective. The surface coating should also cover approximately the same area. Alternatively, the floaters can simply be stationed near the prevailing downwind edge of the lagoon, or be free to be blown by wind toward such edge so that windborne gases leaving the lagoon area will be properly deodorized.

The bacteria, fungi, and enzymes of the core will be leached into the liquid of the lagoon. If the lagoon liquid contains a large amount of grease or tallow, an exceptionally large proportion of lipase should be included in the core.

The floater will be effective to deodorize the atmosphere over a lagoon throughout a temperature range of 35° F. to 105° F. and for pH values of the lagoon liquid between 5.0 and 10.8, and preferabloy within the range of 6.5 to 8.0, the optimum being approximately 7.4. The bacteria and enzymes will function effectively if the temperature of the liquid in the lagoon is between 55° F. and 98° F. Acid or alkali may be supplied by the floater to adjust the pH of the liquid to the extent necessary for effective treatment of the liquid.

The higher the temperature, the more malodorous gas will escape from the lagoon, but the retarding action of the release retardant is also reduced at higher temperatures so that more deodorant will be released from the floater to counteract the increased quantity of malodorous gas escaping.

2,3 butanedione

An important deodorant for deodorizing large volumes of concentrated or widespread malodors is 2,3 butanedione, discussed above as being incorporated in products of the present invention. In many instances malodorous materials are of basic character. Consequently, it is desirable for the 2,3 butanedione to be incorporated in an acidic complex, preferably having a pH between 0.5 and 1.8.