CA1233120A - Broad-spectrum deodorant composition - Google Patents

Abstract

BROAD-SPECTRUM DEODORANT COMPOSITION
ABSTRACT OF THE DISCLOSURE
A germicidally-active, deodorant composition is comprised of a germicidal-effective amount of a phenol and a deodorizing-effective amount of 2,3-butanedione. The deodorant composition may also include propylene glycol as a carrier and which acts, for certain odors, as an absorbent of con-stituents comprising the malodor; and may also optionally, but preferably, include a characterizing agent. This broad-spectrum deodorizing composition may be adapted for specific utilities as a source-specific deodorant by further incorporation of an acid selected from the group consisting of hydrochloric and acetic acids, a deodorizing-effective, water-soluble metal compound selected from the group consisting of aluminum, barium, bismuth, cobalt, chromium, copper, iron, magnesium, manganese, nickel, potassium, titanium and zinc compounds and selective uses of dichlorobenzene or amyl acetate. Gel carriers may optionally be utilized to dispense the deodorants, in a gel, paste or pellet form; which carriers include acacia gum, agar, alginate, amylopectin, gum arabic, carrageenan, chitosan, dextrin, fucoidan, gum ghatt, guar gum, locust bean gum, methyl cellulose, gum tragacanth and xanthan gum.

Description

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BACKGROUND OF THE INVENTION

Field of the Invention .
The present invention relates, generally, to deodorant compositions and, more especially, to broad-spectrum, germi-cidally-active deodorant compositions which may be further suitably tailored to combat the odors characterized by the degeneration or putrefaction of organic materials, including fecal and sewage odors, odors associated with animal feedlots, the waste by-products of food processing plants, those odors associated with poultry including poultry waste, kennel odors and grease trap/septic system odors.
Description of the Background Art Human olfactory response to various odors may be quite varied and is incompletely urderstood. Odors can cause both psychological and physiological responses in humans which vary not only from odor to odor but from individual to individualO Indeed, such factors as sex and age have been noted to cause variation in perception of given odors.
See, e.~., Cox, "Odor Control and Olfaction," at 20 (Pollution Sciences Pub. Co. 1975). Thus, the test of "smell" is a highly subjective one.
Numerous theories have been proposed to explain the chemical and/or perceptual underpinnings of odor and mammalian response thereto. Indeed, there have been nearly as many theories proposed to explain these factors as there have been investigators See, e.~, Cox, ~ ~ at 27-32.
Yet, no clearly accepted unified theory has come to the foreground in complete explanation of why a given sub--.tance smells the way it i5 perceived by different individuals.

Con~equently, odor control is ad hoc; the endeavor of combatting odor remains a black art necessitating the resort to empirical

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experimentation.
Sources o odors are also quite varied. Oftentimes noxious or putrid malodors are generated by industrial plants involved in food production, food processing and associated endeavors. Among the more common sources of objectionable odors are rendering plants, food processing plants (especially fish, but also beef and poultry), feedlots, vegetable processing plants, pet food manufacturing plants, and the like. To a lesser, but nonetheless significant extent, animal quartering spaces, such as kennels, can pose significant problems as odor sources. Sewage systems are characteristic of still other sources of malodor which require effective deodoriza-tion.
The problems of malodor associated with the foregoing are oftentimes compounded since olfactory response is by no means confined to humans. These malodorous sources provide powerful attractants for rodent-s and also insects; as it is known that insects have perceptual olfac-tory response, they too are attracted to a malodorous source.
If one were to focus simply on animal raising operations, the problems of odor control can reach staggering proportions. For example, a large poultry operation may generate as much as 250 tons of chi~ken droppings per day while even a small feedlot with only ten thousand head of beef may be faced with up to 30 tons o* waste on a daily basis. The solutions offered to date to combat the odor associated with these vast quantities of ecal wastes have been costly and not particularly efficient. Masking chemicals (l.e., disguising compositions) have been sprayed as a means to cover the offensive odor, but without an effective neutral-ization thereof. Another method, suggested in U.S. PatentNo. 3,706,663, relies on the addition of sulpha cmd sulpha . -3-~333~2C~

guanidine, along with diluants in an acidic solution, to feedlot wastes. U.S. Patent No. 3,816,577 suggests the use of water-soluble constituents of cherry pits as a means for deodorizing animal waste. U.S. Patent No. 3,720,606 discloses the use of a mixed culture of Bacillus, including the Bacillus megaterium and~or Bacillus subtilis 7 and an odor supressing agent such as amyl acetate. This '606 patent continues with the suggestion to prepare a mixture of pecan oil, amyl acetate, and a concentrate of these bacteria cultures, diluted with water, which is said to suppress the undesirable odors from holding pits for livestock and poultry upon appli-cation thereto.
Odors associated with rendering plants are treated in accordance with the disclosure of U.S. Patent No. 2,893,95~
15 by first adding small amounts (e.g., 0.002-0.05%~ of aliphatic alcohols to the malodorant in order to amplify the objectionable odor and then treating the same with aliphatic methyl ketones ranging from hexyl to nonyl. A preferred composition in accordance with this '958 patent is a 3% aqueous solution of about equal mixtures of methylhexyl ketone and n-hexanol with a wetting agent (Tergitol).
U.S. Patent No. 3,527,798 discloses the use of the cis-form of calcium succinates as deodorants. A disclosed utility for the deodorant is combatting fish odors.
Fecal odors are treated in accordance with the disclosure of U.S. Patent No. 3,509,254 by a mix-ture of water-soluble zinc salts and water-soluble chelating acids for zinc ions. ~he zinc salts include the sulfate, chloride, nitrate, and acetate forms and the recommended chelating acids are rnalic, c~tric, fumaric, hydroxyacetic, tar~clric!, lactic, gluconic, racemic, succinic, oxalic, malonic, glutaric, ~233~

adipic, and ethylene diamine tetraacetic acids.
Sewage disposal odors are treated by compositions disclosed in U.S. Patent No. 3,459,852 which include a sulfide active ~ , ~ unsaturated aldehyde or ketone in an amount sufficient to form sulfur-containing reaction products.
Among those suggested for use are 3~buten-2-one, 3-hydroxy-2-cycloxen-l-one~ 4-methoxy-3-buten-2-one, 4-(2-furyl)-3-buten-2-one and 5-phenyl-2, 4-pentadienophenone.
Although not specific to odors normally associated with, e.~., the degeneration of organic materials, U.S.
Patent No. 3,172,817 is of interest for its disclosure of, inter alia, deodorant compositions which may include butanedione constituents. That patent suggests the use of water soluble ~ -diketone metal salts of polyvalent metals as personal hygenic deodorants. Among the preferred compositions for that purpose are 2,4-pentanedione, 3-chloro-~,4-pentanedione, 4-p-methylphenyl-2,4-butanedione, 4-p-aminophenyl-2,4-butane-dione, 3-n-dodecyl-2,4-pentanedione and 4-phenyl-2,4-butanedione.
The foregoing exemplify various patented approaches toward the control of specific odor sources. Others have proposed broader spectrum deodori~ing compositions. For example, U~S. Patent No. 3,413,218 suggests the use of biphenyl (C6H5C6H5) in amounts ranging from about 0.5 to about 15 PPM to neutralize -~he malodors from sewage, fats, oils, greases, proteins, carbohydrates, rendering odors and general odors found in the atmosphere without regard to the type or origin thereof. U.S. Patent No. 3,074,a72 discloses the use of odor control agents having activated methylene groups such as esters of ~ -keto carboxylic acid in which the carbonyl groups are separated by a rnethylene group or an ester of malonic acid. l`hese compounds are said to neutralize , -5-(by masking) odors within a broad spectrum. The preferred materials disclosed in this '~72 patent are 2-ethylhexyl-aceto-acetate, geranyl aceto-acetate, anisyl-aceto-acetate, ethyl-benzoyl acetate, isoamyl benzoyl acetate and di-n-hexyl-malonateO
Despite the efforts of others to provide a com-mercially realistic and efficient broad-spectrum deodorant, those efforts h~ve not been entirely fruitful. Likewise, those compositions pointed more specifically to particular odor sources~ while generally efficacious within a very limi-ted range of odors, find little adaptability outside that small context and, within it, do not always live up to expectations~
Accordingly, the need exists to provide a broad-spectrum, preferably germicidally-active~ deodorizing compo-sition which, with appropriate selection of suitable additional constituents, may be adapted for particular treatments of odor sources, especially where the same are odor sources associated with animals whether the same be in the nature of food processing, rendering animal parts, treat1ng waste by-products including fecal odors, and treating organic greases and fats.
SUMMARY OF THE INVENTION
The present invention advantageously provides a broad-spectrum, germicidally-active deodorant composition which may be applied to good advantage in deodorizing odors emanating from a wide variety of sources. The composition of the present invention may advantageously be used to treat odors arising from or associated with animals, whether the same be feedlots, poultry houses, rendering plants, processing plants or the like. By the addition of other constituents, ~233~

source-specific deodorants may be tailored from the basic composition to be specifically effective for treating poultry wastes, grease trap and septic tank wastes, kennel wastes, and other similar odor sources. Yet other variations permit the deodorizing compositions of the present invention to be applied to animal wastes which are destined for fertilizer or feed sources to eliminate or minimize the malodorous attributes of same before, during and after such processing, and to retard if not prevent degredation of the nitrogen values thereof. The deodorizing composition of the instant invention may be delivered to the odorant source in any of a number of physical forms, including liquids, gels, pastes, semi-solids or solid pellets~
These and other advantages of the present invention are provided by a germicidally-active deodorant composition comprising a germicidal-effective amount of a phenol and a deodorizing-eifective amount oi` 2,3-butanedione (C4H602).
This composition also preferably includes a characterizing agent; among the useful characterizing agents being Siberian ir needle oil (Abies Siberica), anise oil (Japanese Star), - balsam tolu oil, bay oil, bergamot oil, cassia oil (Chinese cinnamon), cedar leaf oil, cedar wood oil, citronella oil, clove oil, me-thyl salicylate, ocotea oil, pennyroyal oil (both American and European), pine oil, pine needle oil, sassaras oil, thyme oil, and turpentine~ A particularly preferred characterizing agent is a mixture of pine oil, and preferably a water-soluble pine oil, along with turpentine.
A carrier is optionally, but preferably, also included;
and more preferably a carrier which also has odor-absorbent characteristics such as propIyene glycol. A preferr~d solvent for the composition is water; in which case, an emulsifying ~233~L2~3 agent, such as a surfactant and preferably a nonionic sur-factant, may be desirable or necessary.
The Z,3-butanedione may be either a commercially-available product or, more preferably, one compounded as the reaction product of about 61 parts methylethyl ketone, about 4 parts nitric acid, about 4 parts sulfuric acid, about 6 parts hydrochloric acid and about 25 parts of a mixture of about 5 parts of a saturated aqueous solution of sodium nitrate and 3 parts formaldehyde.
Source-specific deodorants may be tailored by suitable adaptation of the broad-spectrum deodorizing compo-sitions aforesaid. In one aspect of the present invention, a water-soluble metallic compound is included for source-specific applications. Compounds capable of providing deodorizing--effective ions selected from the group consisting of aluminum, barium, bismuch, cobalt, chromium, copper, iron, magnesium, manganese, nickel, potassium, titanium, and zinc are suitable.
In general, but for odors with sulfur constituents (e.~., H2S, mercaptans, etc.) in particular, the metallic compound is most pre~erably a copper compound and especially one effective as a reducing agent for thiols. Suitable copper compounds include copper acetate (Cu(C2H302)2 Cu0-6H20 or Cu(C2H302)2~H20), copper hexaminedichloride (Cu(NH3)6C12), copper tetraamine dithionate ([Cu(NH3~4]5206)~ copper tetraamine nitrate ([Cu(NH3)4](N03)2), copper amine nitrate (~Cu(NH3)~](N02)2), copper tetraamine sulfate ([Cu(NH3)4]S0 H20), copper benzoate (Cu(C7H502)2~2H20), copper metaborate (Cu(B0~)2), copper bromate (Cu(BrO3)2-6H20), copper bromide (CuBr2), copper chlorate (Cu~C103)2-6H20), copper perchlora-te (Cu(C104)2 or hydrate Cu(C104)2~6H20), copper chloride (CuC12 or hydrate CuC12~2H20), copper chloride thioureate (CuCl ~233~2~

3[CS(NH2)2]), copper dichromate (~uCr207^2H20), copper fluoride (CuF2 or hydrate CuF~-2H20), copper fluosilicate (CuSiF6~
4H20 or CuSiF6-6H20), copper formate (Cu(CH02)2 or hydrate Cu(CH02)2~4H2o3, copper lactate (Cu(C3H503)2~2H2o3, copper 3~2 3H20 or Cu(No3)2~6H2o)~ copper dipyridine hloride (Cu(C6~5N)2C12), copper salicylate (Cu(C H 0 ) 4 4H20), copper selenate (CuSeO4~5H20), copper sulfate (CUSO4 or hydrates CuS04-H2o or CuS04~5H20); and the amino salts of copper gluconate (Cu~CH2OH(CHOH)~C02~2~H~0 or Cu(H2NCH2C00) H20 or Cu(H2NCH2C00)2~2H20)o The preferred copper compounds are the acetate, chloride, nitrate and sulfate forms. The most preferred copper compounds are the copper sulfates, and particularly'the anhydrous form thereof. Depending on the particular odor to be combatted, others of the aforementioned metallic ions might be used to good advantage; e.g., zinc an'd aluminum being quite effective in the treatment of odors associated with organic acids such as the degenerative products of fatty acids.
Further additions of an acid, preferably a volatile acid and most preferably an acid selected from the group consisting of hydrochloric and acetic acids, provide deodorizing compositions particularly well suited for the treatmen-t of raw poultry wastes or the treatment of such wastes for further processing as fertilizer material or the like, respec-tively. Adjustments to solvent level and surfactant content adapt the copper/hydrochloric acid-containing compositions for use as a deodorizing cleaner for treatment of clothing or the like worn by workers in food processin~ areas or rendering plants.
~ep'Laccment of the acid constituent by dic'hloro-benzene, and preferably ortho-diochlorobenzene, adapts t;he cornpositlon for good utility in the treatment of trap grease _g_ 33~2~

and septic tank odors. Further adjustments, where the acid component is replaced by amyl acetate, permit the use of the composition to extend to the treatment of kennel wastes.
The deodorant compositions of the present invention may be delivered to the odor source in any one of a number of convenient physical forms. The composition may be formulated as a liquid for spray or wash application. The composition may be delivered as a gel, paste, or similar semi-solid by the inclusion of a gel-forming carrier. The preferred carriers include acacia gum, agar, alginate, amylopectin, gum arabic, carrageenan, chitosan, dextrin, fucoidan, gum gha-tti, guar gum, locust bean gum, methyl cellulose, gum tragacanth, and xanthan gum; of which, the alginates are most preferred. Depending upon the combination of desirable metal ions included within the deodorant composition and the gel-forming c~rrier selected, there may be expected an undesirable and otherwise generally uncontrollable transition from a soluble gel form to an insoluble one; in which case a blocking agent must be included to prevent such a transition.
The blocking agent can be a volatile agent, whereupon exposure to the ambient will allow for dissipation upon application;
or the blocking agent may comprise a permanent constituent to maintain the gel form over extended periods. Another option in the selection of a suitable blocking agent is one which directly interacts with the metallic constituent to prevent its affect on the gel carrier where the latter i5 metal-sensitive or by the regulation of pH of the composition within the range of about 5 to 9 to maintain gel stability in that manner. Suitable volatile blocking agen-ts include the volatile amines; the preferred being trimethylamirle or methylamine. The most preferred volatile blocking agent :~233~

is ammonia. Within the category of blocking agents which remain active as gel stabilizers may be mentioned sodium hexametaphosphate or the chelating agents slelected from the group consisting of condensed phosphates, citric acid, oxalic acid, tartaric acid, gluconates, cit:rates, ethylene-diaminetetraacetic acid, nitrilotriacetic acid and diethylene-triaminepentaacetic acid.
The deodorant compositions of the present invention can also be delivered in pellet form. Small size pellets may be sprayed upon the odor source, large size pellets may be deposited therein for interaction therewith. The pellets may be formed simply by impregnation of clay or the like with the desirable deodorant composition in liquid form. More preferably, one of the aforementioned gel forms is reacted specifically to cross-link the carrier into an insoluble gel. The most preferred pelletizing procedure includes the cross-linking of an alginate carrier by means of calcium ion.

Other advantages of the present invention will become apparent, and a fuller understanding of specific compositions gained, upon an examination of the following detailed description.
DETAILED DESCRIPTION OF THE INVENTION

The present invention relates, generally, to broad-spectrum deodorizing compositions and, more especially, to a base composition which is effective in combatting the odors emanating from, or associated with, a wide variety of sources, particularly those associated with animals;

and which is al.so specifically adaptable by the addition of suitable constituents to be source-speciEic in treati.ng such odor sources as poultry waste, animal processing wastes, --1 1-- "

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fecal odors, trap grease and septic tank wastes, kennel wastes and the like. Accordingly, the invention will now be described with reference to certain preferred embodiments within the aforementioned contexts; although, those skilled 5 in the art will appreciate that such a description is meant to be exemplary only and not limitative.
In one aspect o-f the present invention, the deodor-izing compositions are based upon and built around a base of germicidally-active deodorant in its own right, comprising a germicidal-effective amount of phenol and a deodorizlng-effective amount of 2,3-butanedione. While described in terms of its germicidal activity, the phenol constituent of the present composition also provides a deodorizing activity augmenting that of the 2,3-butanedione. The phenol may be simply carbolic acid (C6H50H) or an equivalent hydroxyl derivative of an aromatic hydrocarbon, but the carbolic acid form is most preferred. The 2,3-butanedione may be procured commercially, but it is more preferably compounded in accordance with the formulations set forth below; in which case, it alone may constitute the base without the complementary presence of phenol. As respects these two components alone, it is preferred that the ratio of 2,3-butane-dione to phenol be in the range of from about 4:1 to 5:1, and most preferably at about 9:2 to achieve optimum deodorizing efficiency. [Note: As used herein, all parts and percentages are by volume unless otherwise specified. As respects dry constituents, the same are added as saturated solutions in a solvent, which is water unless otherwise specified, at STP.3 As will be seen below, these general proportions may vary (in some cases considerably) in tailoring specific compositions for specific tasks.

The phenol component will provide both a germicidal ~33~2~

activity insofar as the same is known to be a good disinfectant, while the 2,3-butanedione will provide good deodorizing characteristics. Additionally, the phenol will have an active deodorizing role in the composition but this is subordinated to that of the 2,3-butanedione. Fairly dilute solutions of these components may be employed to good advantage; albeit, the ~oncentration will be dictated in large measure by the odor source. As the minimum identifiable odor value for phenol is about 1.2 x 10 3 parts per cubic centimeter of air with a vapor pressure of 121.4 (at 100 mm Hg.), for relatively mild odors, such as household or restroom odors, this will dictate the threshhold value for determining the precise quantity necessary for deodorization. Normally, for germicidal activity, greater a~ounts will be desirable, ranging up to about 3-5%. As respects the 2,3-butanedione, the same is known to have a peaking osmogenic characteristic.
In other words, after a threshhold value is reached where the same is perceptible t increasing concentrations do not result in proportionately increasing perception. Accordingly, solutions as dilute as from about 0.0001 to about 0~01%
2,3-butanedione with from about 0.05 to about 5.0% phenol may be generally efficacious; the increased concentrations of butanedione being necessitated to combat increasingly powerful odor sources such as those associated with degenerating offal or characterized by the presence of substantial quan-tities of cadaverine.
In some instance it is preferred to apply the 2,3-butanedione/phenol deodorizing composition as a liquid solution, and preferably as an aqueous solution. The active constituents may be diluted with water by as much as 50 parts water to 1 part of a mixture of butanedione and phenol -13- ~

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without loss of germicidal activity or deodorizing efficiency for most applications. Water is the preferrecl solvent principally for ease of manufacture of the overall composition, availability, and cost considerations.
The base composition may advantageously and preferably include other active components. Thus, in order to impart a desirable or pleasing scent to the deodorant, the broad-spectrum deodorant may also preferably include a characterizing agent. Suitable characterizing agents include those in the group consisting of Siberian fir needle oil (Abies Siberica~, anise oil (Japanese star), balsarn tolu oil, bay oil, bergamot oil, cassia oil (Chinese cinnamon), cedar leaf oil, cedar wood oil, citronella oil, clove oil, methyl salicylate, ocotea oil, pennyroyal oil (both American and European), pine oil, pine needle oil, sassafras oil, thyme oil and -turpentine. The preferred characterizing agent for the deodorants of the present invention is a mixture of pine oil and turpen-tine which provides a widely acceptable and pleasing scent.
This combination is also preferred since it is relatively inexpensiv~, highly aromatic, provides a bacteriostatic effect, is generally emulsifiable with ease in aqueous solutions, and is, in its own right, an insect repellent. Most preferred is the use of a water-soluble pine oil such as the ones available for household cleaning, e.~., the product sold under the name "Pine Sol." To insure stability of the oil/
turpentine mixture in an aqueous solution, it is sometimes desirable and most often preferable to include an emulsifying agent. Any conventional emulsifier for oil in water wi]l normally be effective, the preEerred emulsiEiers being sur-factants and the ~ost preferred being the honionlc surfactants;ordinary household detergent being a good source. It may ~Z33~26~

also be found preferable to include propylene glycol as a constituent in the broad-spectrum composition as the same will act as a carrier for the active components and also provide a modest amount of odor absorbing activity itself, particularly as respects sulfur-based odors However, the inclusion of propylene glycol is optional, and other equivalent compositions could be used in its stead if those activities, or either one, might be desired~
When the broad-spectrum composition is formulated to include the characterizing agents, emulsifiers, and optional carrier of propylene glycol, a generally efficacious composition is comprised of from about 5 to about 40% 2,3-butanedione, from about 0.5 to about 6% phenol, from about 4 to about 20% pine oil, from about 5 to about 55% turpentinel from about 2 to about 50% propylene glycol, and from about 1 to about 8% surfactant. More preferred is a composition comprising from about 10 to about 25% 2,3-butanedione, from about 3 to about 5% phenol, from about 6 to about 14% pine oil, from about 20 to about 40% turpentine, from about 20 to about 40% propylene glycol, and from about 3 to about 15% surfactant. Most preferred is a broad-spectrum deodorant having the nominal composition of about 16.7% 2,3-butanedione, about 3.7% phenol, about 9.3% pine oil, about 33.3% turpentine, about 33.3% propylene glycol and about 3.7% sufactant.
The broad-spectrum compositions may advantageously be prepared as aqueous concentrates by dilution with water in the range of up to about 3:1 to 5:1 water to deodorant.
For application, the concentrate may be further diluted up to about 50:1 or more with water depending upon the nature of the prec1se odor to be treated. The selection of an appro-priate solvent level is within the skill o~ the art and, ~233~Z~

guided by the principles set forth herein, the skilled artisan should have no difficulty in deciding upon a suitable dilution to meet the requirements at hand.
~'he foregoing formulations relate to a broad-spectrum, germicidally-activé deodori~.ing composition. That compositio~
of broad utility may be readily tailored to yield one for specific-source odor treatment by the addition of other constituents.
Metallic ions, as a class, have a marked influence on the deodorizing efficacy of the compositions of the present invention. Some metallic ions are more effective than others, both in general and as respects interaction with the specific constituents of the odorant. Those determined to be most effective include the ions of aluminum, barium, bisrnuth,':
cobalt, chromium, copper, iron, magnesium, manganese, nickel, potassium, titanium and zinc. The copper ion is generally most preferred, and especially where sulfur-based odors are to be combatted, while those of aluminum and zinc will be found highly effective in treating odors associated with organic acids such as the degenerative products of fatty acids. Depending upon the specific odor source, one or another of the enumerated ions may be found more beneficial -than others.
Turning from the general to the specific, the odor associated with animal feedlots, poultry areas, and processing plants are complex. The degeneration of organic materials whether the same be offal or fecal in nature, typically include (and approximately in order of descending concentrations) ammonia, n-amy'lamine, n-butyl-amine, secondary 3a butylamine, tertiary buty:Lamine, diethylamine, hydrogen sulide, trirnethylamine, skatole, ethylamine, methylamine, 31 ;~33~

methylmercaptan, n-butylmercaptan, sulfides, disulfides, C-4 and C-7 aldehydes, arnines, dimethylpyrazine, and C-3 and c-6 acids. Where poultry wastes or waste by-products are of concernl to varying extents each of the aforementioned will contribute to perceptible malodor. It has been determined that the broad-spectrum composition described above, and particularly that which includes the preferred characterizing agents of pine oil and turpentine, along with propylene glycol and a surfactant, may be easily tailored to meet the requirements of an effecti~e deodorant for these sources.
For treatment of poultry wastes, it is preferred to lnclude a water-soluble copper compound, preferably one selected from the group consisting of copper acetate (Cu(C H )2 CuO 6H20 or Cu(C2H302)2 H2 )~
dichloride (Cu(NH3)6Cl2), copper tetraamine dithionate ([Cu(NH3)4]S206), copper tetraamine nitrate ([Cu(NH3)43(N03)2), copper amine nitrate ([Cu(NH3)4](N02)2), copper tetraamine s~lfate ([Cu(NH3)4]S04-H2o), copper benzoate (Cu(C7H502)2 2H20), copper metaborate (Cu(B02)2), copper bromate (Cu(BrO3)2 6H20), copper bromide (CuBr2), copper chlorate (Cu(C103)~
6H20), copper perchlorate (Cu(C104)2 or hydrate Cu(Cl04)2~
6H20), copper chloride (CuCl2 or hydrate CuCl2~2H20), copper chloride thioureate (CuCl 3~CS(NH2)2]), copper dichromate (CuCr207~2H20), copper fluoride (CuF2 or hydrate CuF2-2H20), Z5 copper fluosilicate (CuSiF64H20 or CuSiF6~6H20), copper 2)2 or hydrate Cu(CH02)2a4H 0) coppe (Cu(C3H503)2~2H20), copper nitrate (Cu(N03)2 3H20 or Cu(N03) 6H20), copper clipyridine clichloride (Cu(C6H5N)2C12), copper salicylate (CU(C7H$03)2~4H20), copper selenate (CuSeO~5H20), copper sulfate (CuS04 or hydrates CuS04~H20 or CuS04~';H20);
and the amino salts of copper gluconate (Cu[CH20H(CH0}-l)4C02]

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H20 or Cu(H2~CH2C00)24H20 or Cu(H2NCH2C00)2-2H20). The preferred eopper compounds are the acetate, chloride, nitrate and sulfate forms. The most preferred copper compounds are the copper sulEates, and particularly the anhydrous form thereof.
It has also been determined that the addition of an acid, preferably a volatile acid capable of tracking a volitile odorant, materially enhances the deodorizing effectiveness of the composition. A highly preferred acid is hydrochlorie acid as respects poultry waste odors; inhibiting as well the breakdown of valuable nitrogen constituents.
A preferred poultry waste deodorant composition is comprised of from about 1 to about 99% of the broad-spectrum composition described above, from about .01 to about 20%
of a water soluble copper compound and preferably copper sulfate, from about .01 to about 10% hydrochloric acid, and up to about 98.98% water. More preferred is a composition comprised of from~about 20 to about 40% of the broad-spectrum composition, from about 1 to about 5% copper sulfate ~or equivalent), from about 2 to about 6% hydrochloric acid, and up to about 77% water. Most preferred is a composition with a nominal formula of about 20.3% broad-spectrum deodorant, about 1.7% copper sulfate, about 2.9% hydrochloric acid, balance water. This poultry-waste deodorant may then be diluted further with water up to about 50 to 1 parts water to deodorant and applied directly to poultry waste for an effective deodorizing treatment thereof.
Another, and closely related deodorant composition useful in the treatment oE poultry wastes, as a spray which may be applied to raw poultry waste in a chicken house or in a field, is comprised oE from about 40 to about 75% of the broad-spectrum deodorant composition, from about G, to about 1~,% hydrochloric acid, from about 2 to about 9% of ~33~

a water soluble copper compound, and preferably copper sulfate, and up to about 40~ of a nonionic surfactant. This may then cut up to about 5:1 with water to form a spray.
More preferred is a composition comprised of from about 50 to about 70% of the broad-spectrum deodorant composition, from about 6 to about 12% hydrochloric acid, from about

4 to about 7% copper sulfate, and up to about 30% of the nonionic surfactant; cut up to about 4:1 with water before application. Most preferred is a composition comprising about 65% of the broad-spectrum deodorant composition, about 9% hydrochloric acid, about 6% copper sulfate, and about 20% nonionic surfactanti that being cut 3:1 with water for spray application directly on raw poultry waste.
The poultry-waste deodorants described above have also been determined to be highly effective for the cleansing treatment of clothing worn by workers in food processing plants, and particularly the footwear of such workers, by further dilution with water and the further add~tion of about 0.5 to about 2.0% of a detergent and, preferably, a surfactant compatible with the emulsifier of the basic composition; and most preferably the same surfactant as was used in the formulation of the broad-spectrum composition to insure complete compatibility. These compositions may be used in conjunction with the present inventor's "Shoe Cleaner" which is the subject of U.S. Patent No. 4,425,677, issued January 17, 1984.
I~ore particularly, a preferred composition for use in the aforementioned shoe cleaner, for effec-ting both a cleaning and a deodorizing of the soles oE footwear, :is comprised of about 2 to abou-t 98~ of the broad-spec-trum deodorant (i.e., one including characterizing agent, carrier ! - 19 -3L233~

and surfactant), from about .05 to about 20% of a water soluble copper compound such as one seleeted from the group of copper compounds set forth above, and preferably copper sulfate, and from about .05 to about 5% hydrochloric acid, which composition is then diluted with water up to about 20:1 and to which is then added from about .5 to about 2.0%
of additional surfactant based on the diluted volume. More preferred is a composition comprising from about 20 to about 40% of the broad-spectrum deodorant, from about 1 to about

5% copper sulfate (or equivalent) from about 2 to about 4% hydrochloric acid, balance water, then cut up to about 15:1 with water tpredominating) and to which is added from about .5 to about 1.5% additional surfactant. The most preferred eomposition for this purpose of eleaning and deodorizing footwear is one having the nominal formulation of about 20.3% broad-spectrum deodorant, about 1.7% copper sulfate, about 2.9% hydrochloric acid, about 75% water, then cut up to about 12:1 with additional water to dilute, and further comprising about 1% surfactant.
Another closely related variation and highly preferred for use in the present inventor's shoe cleaner apparatus is a composition comprising of from about 50 to ~bout 90%
of the broad-spectrum deodorant, from about 5 to about 20%
hydrochloric acid, from about 2 to about 12% water soluble copper compound, preferably copper sulfate, and up to about 5% of a nonionic surfactant, which is then cut with water in the ratio of up to about 35:1, water predominating. More preferred is a composition comprising of from about 70 to 90~' of the broad-spec-trum deodorant, from about 8 to about 15% hydrochloric acicl, from about S to about 10% copper sulfate, and up to about 3% surfactant; that cornposition ~233~

then being cut up to about 30:1 with water. Most preferred for this variant is a composition comprising about 80% of the broad-spectrum deodorant, about 12% hydrochloric acid, about 7% copper sulfate, about 1% surfactant, and cut then with water in the ratio of 19:1. These compositi.ons, when employed in the present inventor's aforementioned shoe cleaner, are very effective in removing stubborn organic deposits from the soles of footwear and provide a good deodorizing treatment thereof~
It has been determined tha-t poultry was-te may be processed advantageously to form fertilizer materials due to the copious quantities of available nitrogen contained therein. However, further processing of raw poultry waste is oftentimes accompanied by considerable odor as may subsequent use of the processed material. The basic, broad-spectrum composition of the present invention is readily adaptable to provide a deodorizing composition for pre-treatment of poultry waste to minimize these noxious odors during and after such processing.
For a deodorant capable of treating poultry wastes to produce fertilizer or like products, the broad-spectrum composition, including the characterizing agents of pine oil and turpentine, a carrier/absorbent of propylene glycol and emulsifying surfactant, is modified by addition of a water-soluble copper compound which may be any of the afore-mentioned, but particularly copper sulfate, and acetic acid.
Preferably, this poultry-waste trea-tment composition is comprised of from about 2 to about 90% of the broad-spectrum composition, from about .2 to about 15% copper sulfate (or equivalent), from about .2 to about 15% acetic acid, and up to about 97.6% water to form a concentrate; which concentrate -21~

~;~33~

may then be further diluted up to about 50:1 with water ~predominating). More preferably, the compos:ition is comprised of from about 2 to about 8% broad-spectrum deodorant, from about .2 to about 1% copper sulfate (or equivalent), from about .2 to about 1% acetic acid ? and up to about 97.6%
water. Most preferably, this poultry-waste treatment composition i5 comprised of about 5% of the broad-spectrum deodorant, about .5Y0 each of copper sulfate and acetic acid, and about 94% water. This deodorizing composition may then be cut with water up to about 50:1 for treatment of the poultry waste in preparation for or during further processing thereof.
Septic systems pose some unique odor environments, particularly where the effluent residue is comprised of sewage and trap grease. A composition particularly well adapted for the treatment of septic systems, including those where trap grease is a problem, is one where the basic, broad-spectrum deodorant aforesaid includes a water-soluble copper compound such as one from the group set forth above and dichlorobenzene. The preferred copper compound is copper sulfate and the preferred dichlorobenzene is the ortho form.
The otho-dichlorobenzene constituent augments the basic deodorizing efficacy of the composition, contributing its own deodorizing properties, insecticidal activity, and solvent capabilities for grease. Preferably, the septic tank deodorizing composition is one comprising from about .1 to about 98%
of the basic broad--spectrum deodorant, including the character-izing agents, carrier and surfactant, from about .05 to abo~t 20% copper sulfate, from about .05 to about 10% ortho-dichlorobenzene, and up to about 99.8% water. More preferred is a composition comprising from about 20 to about 40% of the broad-spectrurn deodorant, from about l to about 5% copper ~;~33~

s~lfate (or equivalent) from about 2 to about 6% ortho-dichlorobenzene, up to ahout 77% water and preferably from about 50 to about 70% water. The most preferred septic tank composition is comprised of about 27.1% of the broad-spectrum deodorant; about 2.3% copper sulfate about 3.8% ortho-dichlorobenzene, balance water. This composition may be diluted further from that concentrate form by addition of .water in the range of from about 40:1 to about 50:1, water predominating. In some instances, it may not be necessary or desirable to include the dichlorobenzene constituent in the composition. In such a case, it has been determined that a highly active deodorant for treating septic systems may be comprised of from about 20 to about 70% of the broad-spectrum deodorant, from about 20 to about 60% of a water . 15 soluble copper compound, preferably copper sulfate, and up to about 30% of a nonionic surfactant; which concentrate lS then cut in the ratio of up to 30:1 with water (pre-dominating). More preferable is a composition comprised of from about 30 to about 50% of the broad-spectrum deodorant t from about 25 to about 40% copper sulfate, up to about 20%
nonionic surfactant; which composition is then cut up to about 20:1 with water. The most preferred composition within this variation is comprised of about 46% of the broad-spectrum deodorant, 32% copper sulfate, about 18% surfactant, cut at about 10:1 with water; to yield a final deodorant (which may be placed directly within the septic system) having a nominal composition of about 4.5% broad-spectrum deodorant, about 2.91% copper sulfate, about 2.02% surfactant, balance water. These cornpositions have been determined to be deodorizing effective in treating septic -tank wastes while also breaking down trap grease without interfering with the normal organic ~2333.~3 degradation within the septic system.
Kennel wastes can pose a significant source of malodor. The basic composition for the broad-spectrum deodorant is readily adaptable to meet the requirements for deodorizing efficiency in the treatment of kennel wastes.
A preferred composition for this purpose of treating kennel wastes is comprised of from about .01 to about 90%
of the broad-spectrum deodorant cornposition, including the characterizing agents, carrier and emulsifier, from about .01 to about 10% arnyl acetate, from about .05 to about 20%
of a water soluble copper compound such as one from the group set forth above (preferably copper sulfate), from about .05 to 40% additional propylene glycol (over the amount already present in the broad-spectrum composition), from about .01 to about 10% additional pine oil, and up to about 99.87% water. More preferred is a kennel-waste deodorant comprised of from abou-t .1 to about 5% of the broad-spectrum deodorant, from about .l to about 5% amyl acetate, from about .5 to about 15% copper sulfate (or equivalent), from about 1 to about 25% additional propylene glycol, from about .S to about 5% additional pine oil, and up to about 97.8%
water. A highly preferred kennel waste deodorant is comprised of about 10% broad-spectrum deodorant, about 1% amyl acetate, about 5% copper sulfate, about 10% additional propylene glycol, about 2.5% additional pine oil, and up to about 80.5% water. Another related kennel waste deodorant, but one which omits the amyl acetate constituent in favor of acidic deodorant constituents, is pre~erably comprised of frorn about 30 to about 70% of the broad-spectrum deodorclnt, from about 3 to about 12% hydrochloric acid, from about 5 to about ~Q% of a water soluble copper compound, preferabl ~;~33~

copper sulfate, from about 2 to about 8% additional propylene glycol from about 2 to about 8% acetic acid, from about 2 to about 8% additional pine oil, and up to about 20% of a nonionic surfactant; which concentrate is then cut in the ratio of up to about 30:1 with water, where water pre-dominates. More preferable is a composition comprising from about 40 to about 60% of the broad-spectrum deodorant, from about 5 to about 10% hydrochloric acid, from about 8 to about 15% copper sulfate, from about 2 to about 6% additional propylene glycol, from about 2 to about 6% acetic acid, from about 2 to about 6% additional pine oil, and up to about 20% nonionic surfactant; which concentrate is then cut up to about 20:1 with water. Most preferred for this variation is a composition comprised of about 54% of the broad-spectrum deodorant, about 7% hydrochloric acid, about 11% copper sulfate, about 4% additional propylene glycol, about 4% acetic acid, about 4% additional pine oil, and about 16% surfactant; cut at about lS:1 with water. These kennel wastes deodorants, in an appropriately dilute concen-tration, may be sprayed within a kennel area and effectivelyreduce the noisome odors emanating therefrom.
In order to exemplify the most preferred compo-sitional ranges and formulations for deodorant compositions within the scope of the present invention, the following examples will be given.
EXAMPLE A
Both -the base and the broad-spectrum deodoriziny compositions of the present invention include 2,3-butanedione as a deodoriziny agent. l`his component may be obtained com-mercially in either the diacetyl or biacetyl form. If acommercial yrade 2,3-butanedione is selected for compounding 3~
the deodorants of the present invention, it is prefer~ably acidified slightly with sulfuric acid, in the range of from about 1 to about 2%. However, it is more preferred that the 2,3-butanedione used in conjunctiorl with the present invention be formulated in accordance with the following technique; since it has been determined that the efficiencies of the compositions of the instant invention are enhanced when this technique for formulation is utilized as opposed to procurement of commercial 2,3-butanedione. Indeed, when formulated as set forth below, this constituent alone functions extremely well as a broad-spectrum deodorant without the need to include phenol.
The 2,3-butanedione of the present invention is preferably the reaction produc-t of about 61 parts methyl-ethylketone, about 4 parts nitric acid, about 4 parts sulfuric acid, about 6 parts hydrochloric acid, and about 25 parts of a mixture of about 5 parts of a saturated aqueous solution of sodium nitrate and about 3 parts formaldehyde. The procedure for formulation is as follows.

First, a base mixture of saturated sodium nitrate and formaldehyde is prepared by saturating about 5 gallons of water with technical grade sodium nitrate, to which is then added 3 gallons of formaldehyde (37% conc.).

To 10 gallons of methylethylketone are added .625 gallons each of nitric and sulfuric acids (42Be and 56Be, respectively) and this mixture is allowed to stand for up to about one day. Next, about 0.083 gallons of the sodium nitrate/formaldehyde mixture are added a-t the rate of about 5 milliliters per minute. Additions of the sodium nitracte/

formaldehyde mixture must be regulated very closely to avoid explosive conditions. Water coo]in~ of the react:ion vessel :Ls hiyhly desirable in conducting this process for tha-t reason. The reac-tion m:ixture is allowed to stand for up to about one day after the initial reaction, and a subsequent -~6-~L233~

addition of about 0.125 gallons of the sodium nitrate/
formaldehyde mixture is again made at the rate of about 5 milliliters per minute following the same precautions.
This mixture is again allowed to stand for up to about one day, and another 0.75 gallons of the sodium nitrate/formaldehyde mixture is added at the raté of about 5 milliliters per minute. Following another rest period of up to about one day, about 3.042 gallons of the sodium nitrate~formaldehyde mixture is again added at the rate of about 5 milliliters per minute, and the mixture is permitted to stand for up to about one day. Last, about 1 gallon of hydrochloric acid (20Be) is added at the rate of about 500 milliliters per minute and the product again allowed to rest for about one day. The resultant product is a 2,3-butanedione (C4H602) which has been determined to provide a bet-ter deodorizing effect in use with the other components of the present invention than commercially-available product; albeit, commercially-available 2,3-butanedione can be used.
EXAMPLE _ A basel germicidally-active deodorant composition is prepared by mixing about 9 parts of the composition produced in Example A with about 2 parts of carbolic acid. This admixture is then diluted with wa-ter in the ratio of about 10:1.
_XAMPLE C
A broad-spectrum, germicidally-active deodorant composition is prepared by rnixing 9 parts of the 2,3-butane-dione of Example A with 2 parts phenol, about 5 parts pine o-il, about 18 parts turpentine, about 18 propylene glycol, and about 2 parts of a nonionic surfactant.
A first portion of this formulation is set aside for further additions. The remainder is dilutecl with water ~L233~

in the ratio of about 30 parts water to deodorant to yield a solution of application to feedlot waste. The deodorant is completely effective for eliminating the noxious odor perception associa-ted with the source.
EXAMPLE D
A deodorant for poultry waste was prepared by first taking 35 parts of the.withheld portion of the deodorant prepared in Example C. To this was added 5 parts of hydrochloric acid and about 3 parts of coppe.r sulfate in the form of a satura-ted aqueous solution thereof.
This composition was then diluted 3 to 1 wi-th water to concentrate same. That concentrated solution was then further diluted 40 to 1 with water and sprayed on poultry waste. Within about 1 minute the offensive odors formerly emanating from the poultry waste were dissipated and within 10 minutes the odor was suppressed by 98%.
EXAMPLE E
A solvent and deodorant ~omposition useful for cleaning and deodorizinq the clothing worn by workers in a food processing plant, and particularly the soles of footwear, is prepared by taking 1 gallon of the concentrated deodorant composition of ~xample D, diluting that composition with 4 gallons of water and adding about 6.5 ounces of an anionic surfactant.
About 1 gal.lon of this composition was then added to the "Shoe Cleaner" disclosed and claimed in the present inventor's U.S. Patent No. 4,425,677. It was determined that th.is compos.ition was entirely effective :in the removal of stu~born organic deposits on the soles of foo-twear when used in that apparatus and also accomplished a deodorizing treatment of the footwear.

~33~Z(~

EXAMPLE F
-A deodorizing composition useful for the treatment of septic systems, and particularly those where trap grease is a component of the sludge~ is prepared by mixing parts of the composition of Example C with 5 parts of ortho-dichloro-benzene and 3 parts of a saturated aqueous solution of copper s~lfate. This admixture was first diluted with 20 parts of water to form a concentrate. The concentrated solution is then cut with additional water in the ratio of a~out - 10 40 to 1 and introduced to a septic system through a trap in the plumbing. This composition will deodorize the system and break down the trap grease without otherwise interfering with the normal operatio~al characteristics of the septic system.
Exam~e G
Another deodorizing composition useful for the treatment of septic systems and effective in breaking down trap grease is prepared by mixing 23 parts of the composition of Example C with 16 parts of a saturated aqueous solution of copper sulfate and 9 parts of a nonionic surfactant in the form of liquid soap. This mixture is then diluted with water by mixing same in the ratio of 5 parts water to 1 part deodorant and that diluted solution is then introduced to a septic system for deodorizing the same.
EXAMPLE H
A deodorizing composition useful for -treating kennel areas is prepared by admixing 2 parts of the deodorant composition of Example C with 2 parts of amyl acetate, ~.0 parts of a saturated aqueous solut-lon of copper sulfa-te, .30 20 parts of propylene glycol, and 5 parts of a water-soluble pine oil marketed under the name "Pine Sol." ~his admixture -29- -~

33~LZ~

is cut by the addition of 156 parts of water (that being in the ratio of 4 to l) to yield a kennel waste deodorant which may be sprayed within a kennel area to eliminate the noxious odors thereof.
Example I
S Another deodorizing composition useful for treating kennel wastes is-prepared by admixing 54 parts of the deodorant composition of Example C with 7 parts hydrochloric acid, 11 parts of a saturated aqueous solution of copper sulfate, and 4 parts each of propylene glycol, glacial acetic acid, and pine oil. To this is added 16 parts of a nonionic sur-factant in the form of liquid soap and that mixture is then diluted with water in the ratio of 15 parts water to one part deodorant. This deodorant is then sprayed in a kennel area to combat the odors emanating therefrom.

Each of the foregoing deodorant formulations, whether it be general or specific in terms of its applicability to the task at hand, is delivered to the odor source as a solutionO In many cases, it is desirable to utilize a carrier for the deodorant in order to deliver the active constituents in a paste, semi-solid, gelatinous, or somewhat more rigid pellet form. Likewise, slow or time-release character-istics are desirable and these are more easily achieved by application in, e.g., gel form than in the case of pre-dominantly liquid deodorant solutions. Accordingly, it is envisioned within the broad scope of the present invention to provide a carrier system adaptable for deli.vering the active ~eodoran-t constituents i.n a paste, semi-solid, gel, or pellet-like state.
In this aspect of the present invention, the carriers -~50- ' ~233~

are preferably organic, gel-forming compouncls as opposed to inorganic compositions such as thickeners or extenders;
albeit, clay or the like might find a suitable role under certain circumstances. Those gelling agents deemed preferable for this purpose are acacia gum, agar, alginate, amylopectin, gum arabic, carrageenan, chitosan, dextrin, fucoidan, gum ghatti, guar gum~ locust bean gum, methyl cellulose, gum tragachanth and xanthan gum. Most preferable is alginate in any of its various forms.
Certain of the aforementioned carriers or gelling agents exhibit~ to varying degrees, a sensi-tivity to metallic ions which causes an undesirable cross-linking or type of cross-linking reaction rendering the carrier either less effective or, in the extreme, totally ineffective for delivery of the desirable deodorant composition. Indeed, the most preferred alginate carriers eY~hibit this metal sensitivity;
setting into a rather intractable mass. In those cases, it thus becomes important, if not essential, to include a "blocking agent" which will interfere with this tendency toward the formation of an insoluble vice soluble gel, thereby effectively overcome the metal sensitivity, but nonetheless leave the metallic ions available for deodorizing. As used herein, therefore, this term "blocking agent" is meant -to connote one which is effective to prevent the unwanted transition to insolublization but is otherwise benign as respects the deodorizing efficiency of the metallic ions.

The blocking agents may come from quite a wide range of classes of compositions. They may be a permanen-t or indigenous component of the overall composition or may be a transien-t one which, e.g., volatilizes upor, use. Arlother or alternative characteristic for selection of suitable ' 31-1~2333L~

blocking agents is the ability to buffer the composition and maintain a pH in a fairly neutral range thereby precluding the irreversible cross-linking irrespective of the presence of a sensitizing metallic cation.
With the functional objectives noted above borne in mind, suitable volatile blocking agents include volatile amines such as, for example, trimethylamine or methylamine.
Related thereto is also ammonia, a highly preferred volatile blocking agent when alginate is the metal-sensitive gelling carrier and copper is the deodorizing-active metallic cation.
The volatile blocking agent will be compounded initially with the carrier, e.g. alginate, prior to introduction of the active deodorant constituents which include the sensitizing cation, e.g. copper. A paste or gel will thus form and be preserved in that state for purposes of packaging prior to use. However, when the deodorant composition is then applied to a surface within a space to be deodorized, the volatile agent will dissipate allowing the gel or paste to set. Notwithstanding the transition to an insoluble form, the metal ions responsible for that will nonetheless remain available for deodorizing efficiency since the reaction between the odor to be combatted and the metallic ion is a more compelling one than that responsible for the chemical linking of the gel across the metallic ion. Accordingly, and particularly when treating acidic vapors (a predominant characteristic of many odorants), the deodoran-t composition will then again undergo a transformation akin to depolymer-ization.
To illustrate this aspect of the invention somewhat more specifically, a paste of alginate, water, and aMmonia of -the desired consistency may first be prepared. A composition ~2333L;2~3 such as that described in Example D is then blended into the paste. Normally, the copper ions present would cause the alginate to undergo a transition from the soluble to the insoluble form and yield an intractable mass within a very short amount of time. This, obviously, limits the applicability of the composition~ However, the ammonia con-stituent initially added will interfere with that tendency and effectively overcome the copper sensitivity of the alginate.
The paste can be stored for prolonged periods while still in a free-flowing form (i.e., in the sense that it remains plactically deformable). For example~ the paste might be disposed within a tube from which it can be e~truded or -exuded for application and retain the necessary physical characteristics to permit such operations when application is desired.
At the time of application, a bead of this paste can be applied to a surface in a space to be deodorized.
When exposed to the ambient, the ammonia blocking agent will evaporate thereby permitting the alginate carrier to exhibit its metal sensitivity. Copper ions will bridge alginate molecules and an insoluble gel will be realized once vola-tization of the ammonia proceeds. However, when acidic vapors in an odor source contact the gel, the reaction between the copper constituent and the odor is a more compelling one (from the point of view of the free energy of reaction) than the bond strength across the cation. Accordingly, the metallic constituent remains free for deodoriæing efficiency and, by virtue o~ the reaction, is robbed from its linlcing role and a type of depolymerization in the solicl maSC; then occurs.
The other preerred classes of bloc}cing alents 333L~

noted above remain as an indigenous component of the overall composition. Accordingly, the paste, gel, etc. will retain its physical attributes upon use. In some cases, the metal sensitivity of the carrier (a function of both the specific carrier and specific ion) can be overridden by pH reglllation.
These gels tend to be most stable in a pH range of from about 5 to about 9. Stability can be maintained by including a base, such as sodium hydroxide, or any suitable buffer capable of maintaining and/or regulating the pH of the gel within that range. In fact, some of the formulations for deodorants in accordance with the present invention which do not include metalllc cations may nonetheless exhibit st~ acidic a pH that this type of buffering and/or regulation will still be essential irrespective of the presence of such cations. Consequently, there may be isolated circumstances where the same undesirable insolublization becomes a consid-eration apart from the more predominant cause due to the presence of metallic cation(s).
A particularly preferred blocking agent, which to a certain extent is capable of pH regulation but which exhibits markedly better results than, e.g., sodium hydroxide, is sodium hexametaphosphate. Relatively slight additions of sodium hexametaphosphate have been found to prevent the undesirable insolublization of alginate gels, and particularly where copper ion is the cation employed in the deodorant.
This leads to another entire class of suitable blocking agents, those being chelating agen-ts capable of ligancy with the metallic cation sufficient to overcome its tendencies -toward insolubliY.ation of the carrier but none-theless leaviny the cation available for its deodorizing task. Exemplary of the preferred blocking ayents in this ~333~

class are the condensed phosphates, citric, oxalic and tartaric acids, gluconates, citrakes, ethylenediaminetetraacetic acid, nitrilotriacetic acid, and diethylenetriaminepentaacetic acid. These blocking agents will be compounded into the overall composition in the same way as described generally above as respects the ammonia or related volatile agents;
being blending initially with the susceptible carrier prior to introduction of the sensitizing constituents.
The formulations for the liquid deodorants will normally be modified slightly when it is desired to utilize the gel carrier. For example, the surfactant component becomes a highly optional one, and in most cases the option of exclusion will be exercised. Likewise, many of the liquid formulations include propylene glycol. To a certain extent, the propylene glycol might be retained to retard or control evaporation in order to provide a more even dispersion; but again this constituent becomes highly optional. Emulsifiers, generally necessary to maintain the oily constituents in uniform dis-persion throughout the liquid formulations, may be dispensed with; except where the blending of a specific composition with the initial carrier paste is made easier by the inclusion of those components.
The delivery of the active deodorizing formulations of the present invention may also be made by way of pellets.
z5 Srnall pellets, perhaps viewed more closely akin to large-sized granules, can be sprayed in that solid form over an odor source or be admixed therein. These small pellets could also find good utility in cat litter boxes by mixing a suitable percentage thereof with normal li-tter material. On the other hand, relatively large-sized pellets can be prepared for depositing the deodorant compositions in solid form with:in a liquid odor source, such as a sewage holding tank or the like.
One approach to pelletizing is simply an impregnation of clay or like pellet materials with a liquid deodorant by absorbing the latter into the former. However~ the concen-tration of active constituents is generally limited by that approach. Far preferable is the transformation of an initial paste or gel into a pellet since higher deodorant concentrations can be accepted in that way.
While the insoluhlization of the gel carrier is noted above to be a drawback, as regards the maintenance of a plastically-deformable deodorant material, those tendencies can be used to good advantage for pelletizing. However, most o the metal ions enjoying deodorizing utility do not exhibit suitable tendencies for the fabrication of a harder pellet. In other words, the metal sensitivity to the deodorizing ions by the carrier material is just good enough to interfere with desirable gel applications but not good enough to yield a solid pellet. Accordingly, it is generally preferred to use a more powerful gelling agent such as, for example, calcium ions, adipic acid, or other known agents which will serve to solidify the carrier into a homogeneous solid shape.
In situations where the carrier is not metal sensitive or in situations where no metallic cation is included as an active constituent, the pelle-ts can be formed quite simply by admixture of the carrier with the active deodorizing constituents and then treatment with the solidifying or pelletizing agent. But, where the metal sensitivity is to be expected due to the selection of either or both of the carrier and deodorant compos:ition, the process :Ls slightly more complica-ted. In such a case, the paste or gel is E`ormed ~Z33~Z~3 as aforesaid, where a blockir?g agent such as sodium hexameta-phophate is included. Otherwise, admixture o the carrier and deodorant would begin the insolublization process pre-maturely. With a stable gel form, then the pelletizing process can continue in normal course with due regard for the fact that perhaps added concentrations of pelletizing agent (e.g., calcium ions or adipic acid) will be required.
Depending upon the desired consistency of either the plastically-deformable carrier or the structure of the solid pellet, the amount o* carrier will vary over fairly ~ wide ranges. In virtually all cases, the carrier will be present up to about 2% by wei~ht. Additions of about 0.1-0.5%
by weight will yield a thick but flowable mass. Increasing the concentration to about 1% by weight will progressively give thicker viscosities up to paste-like consistencies.
Gels are best formed with additions in the range of about 0.8-1.5%, but in some cases may require up to about 2% carrier.
These higher concentrations may also be found more desirable for conversion of the plastically-deformable form into the pellet form.
In order to illustrate more specifically these various carrier systems, the following exemplary formulations are provided.
EXAMPLE J
A broad-spectrum deodorant like that of Example C is prepared, omitting the propylene glycol, surfactant, and water components. Approximately 1.5 grams of alginate is dissolved in 150 grams of water and allowed to rest to insure complete and uniform di.ssolution~ To this is added 3 grams of sodium hydroxide to counteract the rather acidic pH of the active deodorant components. This yields a relatively ~233~

viscous mass. Next, 800 grams of the active deodorant is blended and the mixture is allowed to stand. A thickened deodorant is achieved, but one which has flowing characteristics.
EXAMPLE K
The procedure of Example J is repeated, but about 13 grams of alginate i5 used to increase the viscosity from a flowable paste to a gel. In this case, initial difficulty in-complete acceptance of the alginate by the water is en-countered, but subsequent addition of the liquid deodorant 1~ component provides sufficient fluid. Upon setting, a pliable gel is achieved which can be applied by extrusion through a nozzle in order to form a bead of active deodorant.
EXAMPLE L
The procedur~ of Example K is reproduced with the addition of about 3 grams of borax. In this case, the borax forms a much tougher gel which is somewhat more adherent than that of the previous example.
EXAMPLE M
A deodorant like that prepared in Example D is formulated, but without the added aqueous components (save that for dissolution of the copper sulfate), surfactant, and propylene glycol. About 3 grams of sodium hexametaphosphate and about 3 grams of sodium hydroxide are each dissolved in about lSO grams of water. To that is added about 10 grams of alginate to form a very stiff mass. 800 grams of the deodorant composition, now including copper sulfate, is blended into the carrier and the mixture is allowed to set to a fairly -tough gel. Several aliquot portions oE this gel are ~et aside for pelleti~ing as a subsequent procedure.
EXAMPLE N
One of the portions oE the gel of Example M :is -~ -38-~233~

subdivided and treated with adipic acid in excess. The gel solidifies to a homogeneous solid form.

Calcium carbonate is added to an aliquot portion S of the gel of Example M. After thorough blending, the gel is dropped into an acidic bath. Reaction between the acid and calcium carbonate releases free carbon dioxide and calcium ion. The calcium ion effectuates a solidification of the gel into a solid pellet while the carbon dioxide causes 0 a slight expansion in the structure thereof.
EXAMPLE P
1he paste of Example J, which has a somewhat flowing consistency, is dripped into a calcium bath. As the paste droplets strike and move through the bath, free calcium ion causes a solidification of the paste into a generally rigid pellet structure.

* * *
While the invention has now been described with reference to certain preferred embodiments thereof, and exemplified in respect thereto, those skilled in the art will appreciate that various substitutions, modifications, omissions, and changes may be made without departing from the spirit thereof. Accordingly, it is intended that the scope of the present invention be limited solely by that of the claims granted herein.

Claims (86)

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:-

1. A broad-spectrum, germicidally-active deodorant composition comprising a germicidal-effective amount of a phenol and a deodorizing-effective amount of 2,3-butanedione.

2. The deodorant composition of claim 1, further comprising a characterizing agent.

3. The deodorant composition of claim 2, wherein said characterizing agent is selected from the group consisting of Siberian fir needle oil, anise oil, balsam tolu oil, bay oil, bergamot oil, cassia oil, cedar wood oil, citronella oil, clove oil, methyl salicylate, ocotea oil, pennyroyal oil, pine oil, pine needle oil, sassafras oil, thyme oil, turpentine and mixtures thereof.

4. The deodorant composition of claim 3, wherein said characterizing agent is a mixture of pine oil and tur-pentine.

5. The deodorant composition of claims 2, further comprising a propylene glycol carrier.

6. The deodorant composition of claim 5, further comprising an emulsifying agent.

7. The deodorant composition of claim 6, wherein said emulsifying agent is nonionic surfactant.

8. The deodorant composition of claim 1 wherein the ratio of the volumetric quantities of said 2,3-butanedione to said phenol is from about 3:1 to about 6:1.

9. The deodorant composition of claim 8, wherein said ratio is from about 4:1 to about 5:1.

10. The deodorant composition of claim 9, wherein said ratio is about 9:2.

11. A broad-spectrum, germicidally-active deodorant composition comprising from about 6 to about 18 parts of 2,3-butanedione and from about 1 to about 6 parts of a phenol.

12. The deodorant composition of claim 11, comprising from about 6 to about 16 parts of said 2,3-butanedione and from about 1 to about 3 parts of said phenol.

13. The deodorant composition of claim 12, comprising about 9 parts of said 2,3-butanedione and about 2 parts of said phenol.

14. A broad-spectrum, germicidally-active deodorant composition comprising from about 5 to about 40% 2,3-butane-dione, from about .5 to about 6% phenol, from about 4 to about 20% pine oil, from about 5 to about 55% turpentine, from about 2 to about 50% propylene glycol and up to about 8% surfactant.

15. The deodorant composition of claim 14, comprising from about 10 to about 25% 2,3-butanedione, from about 3 to about 5% phenol, from about 6 to about 14% pine oil, from about 20 to about 40% turpentine, from about 20 to about 40% propylene glycol, and up to about 5% surfactant.

16. The deodorant composition of claim 15, comprising about 16.7% 2,3-butanedione, about 3.7% phenol, about 903%
pine oil, about 33.3% turpentine, about 33.3% propylene glycol and about 3.7% surfactant.

17. The deodorant composition of claims 14, 15 or 16, diluted with water in the range of up to about 50:1 water to deodorant.

18. A deodorant composition, comprising from about 1 to about 99% of the broad-spectrum deodorant composition of claim 14, from about .01 to about 20% of a water soluble copper compound, from about .01 to about 10%
hydrochloric acid, and up to about 98.98% water.

19. The deodorant composition of claim 18, wherein said water soluble copper compound is selected from the group consisting of copper acetate, copper hexaminedichloride, copper tetraamine dithionate, copper tetraamine nitrate, copper amine nitrate, copper tetraamine sulfate, copper benzoate, copper metaborate, copper bromate, copper bromide, copper chlorate, copper perchlorate, copper chloride, copper chloride thioureate, copper dichromate, copper fluoride, copper fluosilicate, copper formate, copper lactate, copper nitrate, copper dipyridine dichloride, copper salicylate, copper selenate, copper sulfate, and the amino salts of copper gluconate.

20. The deodorant composition of claim 18, comprising from about 20 to about 40% of said broad-spectrum deodorant, from about 1 to about 5% of a copper compound selected from the group consisting of copper acetate, copper chloride, copper nitrate and copper sulfate, from about 2 to about 6% hydrochloride acid, and up to about 77% water.

21. The deodorant composition of claim 20, comprising about 20.3% of said broad-spectrum deodorant, about 1.7%
copper sulfate, about 2.9% hydrochloride acid, and up to about 75.1% water.

22. The deodorant composition of claim 18, diluted with water in the range of up to about 50:1 water to deodorant.

23. The deodorant composition of claim 19, diluted with water in the range of up to about 50:1 water to deodorant.

24. The deodorant composition of claim 20, diluted with water in the range of up to about 50:1 water to deodorant.

25. The deodorant composition of claim 21, diluted with water in the range of up to about 50:1 water to deodorant.

26. The deodorant composition of claim 22, further comprising up to about 2% surfactant based on the diluted volume of said deodorant.

27. The deodorant composition of claim 23, further comprising up to about 2% surfactant based on the diluted volume of said deodorant.

28. The deodorant composition of claim 24, further comprising up to about 2% surfactant based on the diluted volume of said deodorant.

29. The deodorant composition of claim 25, further comprising up to about 2% surfactant based on the diluted volume of said deodorant.

30. A deodorant composition, comprising from about 2 to about 98% of the broad-spectrum deodorant composition of claim 14, from about .2 to about 15% acetic acid, from about .2 to about 15% of a water soluble copper compound, and up to about 97.6% water.

31. The deodorant composition of claim 30, wherein said copper compound is selected from the group consisting of copper acetate, copper hexaminedichloride, copper tetraamine dithionate, copper tetraamine nitrate, copper amine nitrate, copper tetraamine sulfate, copper benzoate, copper metaborate, copper bromate, copper bromide, copper chlorate, copper perchlorate, copper chloride, copper chloride thioureate, copper dichromate, copper fluoride, copper fluosilicate, copper formate, copper lactate, copper nitrate, copper di-pyridine dichloride, copper salicylate, copper selenate, copper sulfate, and the amino salts of copper gluconate.

32. The deodorant composition of claim 30, comprising from about 2 to about 8% of said broad-spectrum deodorant, from about .2 to about 1% of a copper compound selected from the group consisting of acetate, copper chloride, copper nitrate and copper sulfate, from about .2 to about 1% acetic acid, and up to about 97.6% water.

33. The deodorant composition of claim 32, comprising about 5% of said broad-spectrum deodorant, about .5% copper sulfate, about .5% acetic acid, and up to about 94% water.

34. The deodorant composition of claim 30, diluted with water in the range of up to about 50:1 water to deodorant.

35. The deodorant composition of claim 31, diluted with water in the range of up to about 50:1 water to deodorant.

36. The deodorant composition of claim 32, diluted with water in the range of up to about 50:1 water to deodorant.

37. The deodorant composition of claim 33, diluted with water in the range of up to about 50:1 water to deodorant.

38. A deodorant composition, comprising from about 2 to about 98% of the broad-spectrum deodorant composition of claim 14, from about .05 to about 20% of a water soluble copper compound, from about .05 to about 5%
hydrochloric acid, up to about 97.4% water; diluted with water in the range of up to about 50:1 water to deodorant;
said composition further comprising from .5 to about 2%
surfactant based on the diluted volume.

39. The deodorant composition of claim 38, wherein said water soluble copper compound is selected from the group consisting of copper acetate, copper hexaminedichloride, copper tetraamine dithionate, copper tetraamine nitrate, copper amine nitrate, copper tetraamine sulfate, copper benzoate, copper metaborate, copper bromate, copper bromide, copper chlorate, copper perchlorate, copper chloride, copper chloride thioureate, copper dichromate, copper fluoride, copper fluosilicate, copper formate, copper lactate, copper nitrate, copper dipyridine dichloride, copper salicylate, copper selenate, copper sulfate, and the amino salts of copper gluconate.

40. The deodorant composition of claim 38, comprising from about 20 to about 40% of said broad-spectrum deodorant, from about 1 to about 5% of a copper compound selected from the group consisting of copper acetate, copper chloride, copper nitrate and copper sulfate, from about 2 to about 4% hydrochloride acid, and up to about 77% water; diluted with water in the range of up to about 50:1 water to deodorant; said composition further comprising from about .5 to about 1.5% surfactant based on the diluted volume.

41. A deodorant composition, comprising from about .1 to about 98% of the broad-spectrum deodorant composition of claim 14, from about .05 to about 10% dichlorobenzene, from .05 to about 20% of a water soluble copper compound, and up to about 99.8% water.

42. The deodorant composition of claim 41, wherein said dichlorobenzene is ortho-dichlorobenzene and said copper compound is selected from the group consisting of copper acetate, copper hexaminedichloride, copper tetraamine dithionate copper tetraamine nitrate, copper amine nitrate, copper tetraamine sulfate, copper benzoate, copper metaborate, copper bromate, copper bromide, copper chlorate, copper perchlorate, copper hydrate, copper chloride, copper chloride thioureate, copper dichromate, copper fluoride, copper fluo-silicate, copper formate, copper lactate, copper nitrate, copper dipyridine dichloride, copper salicylate, copper selenate, copper sulfate, and the amino salts of copper gluconate.

43. The deodorant composition of claim 41, comprising from about 20 to about 40% of said broad-spectrum deodorant, from about 2 to about 6% of ortho-dichlorobenzene, from about 1 to about 5% of a copper compound selected from the group consisting of copper acetate, copper chloride, copper nitrate and copper sulfate, from up to about 77% water.

44. The deodorant composition of claim 43, comprising about 27.1% of said broad-spectrum deodorant, about 3.8%
ortho-dichlorobenzene, about 2.3% copper sulfate, and up to about 66.8% water.

45. The deodorant composition of claim 41, diluted with water in the range of up to about 50:1 water to deodorant.

46. The deodorant composition of claim 42, diluted with water in the range of up to about 50:1 water to deodorant.

47. The deodorant composition of claim 43, diluted with water in the range of up to about 50:1 water to deodorant.

48. The deodorant composition of claim 44, diluted with water in the range of up to about 50:1 water to deodorant.

49. A deodorant composition, comprising from about .01 to about 90% of the broad-spectrum deodorant composition of claim 14, from .01 to about 10% amyl acetate, from about .05 to about 20% of a water soluble copper compound, from about .05 to about 40% additional propylene glycol, from about .01 to about 10% additional pine oil, and up to about 99.87 water.

50. The deodorant composition of claim 49, wherein said copper compound is selected from the group consisting of copper acetate, copper hexaminedichloride, copper tetraamine dithionate, copper tetraamine nitrate, copper amine nitrate, copper tetraamine sulfate, copper benzoate, copper metaborate, copper bromate, copper bromide, copper chlorate, copper perchlorate, copper hydrate, copper chloride, copper chloride thioureate, copper dichromate, copper fluoride, copper fluo-silicate, copper formate, copper lactate, copper nitrate, copper dipyridine dichloride, copper salicylate, copper selenate, copper sulfate, and the amino salts of copper gluconate.

51. The deodorant composition of claim 49, comprising from about .1 to about 5% of said broad-spectrum deodorant, from about .1 to about 5% amyl acetate, from about .5 to about 15% of a copper compound selected from the group consist-ing of copper acetate, copper chloride, copper nitrate and copper sulfate, from about 1 to about 25% additional propylene glycol, from about 5 to about 5% additional pine oil, and up to about 97.8% water.

52. The deodorant composition of claim 51, comprising about 1% to said broad-spectrum deodorant, about 1% amyl acetate, about 5% copper sulfate about 10% additional propylene glycol, about 2.5% additional pine oil and up to about 80.5%
water.

53. The composition of claim 49, diluted with water in the range of up to about 20:1 water to non-aqueous constituents thereof.

54. The composition of claim 50, diluted with water in the range of up to about 20:1 water to non-aqueous constituents thereof.

55. The composition of claim 51, diluted with water in the range of up to about 20:1 water to non-aqueous constituents thereof.

56. The composition of claim 52, diluted with water in the range of up to about 20:1 water to non-aqueous constituents thereof.

57. A deodorant composition comprising from about 20 to about 70% of the broad-spectrum deodorant composition of claims 14, from about 20 to about 60% of a water-soluble copper compound and up to about 30% of a sur-factant.

58. The deodorant composition of claim 57, comprising from 30 to about 50% of said broad spectrum deodorant compo-sition, from about 25 to about 40% of a copper compound selected from the group consisting of copper acetate, copper chloride, copper nitrate and copper sulfate, and up to about 20% of a nonionic surfactant.

59. The deodorant composition of claim 58, comprising about 46% of said broad-spectrum deodorant composition, about 32% copper sulfate and about 18% of said surfactant.

60. A deodorant composition comprising from about 30 to about 70% of the broad-spectrum deodorant of claims 14, from about 5 to about 20% of a water-soluble copper compound, from about 2 to about 8% additional propylene glycol, from about 2 to about 8% additional pine oil, from about 3 to about 12% hydrochloric acid, from about 2 to about 8% acetic acid, and up to about 20% of a surfactant.

61. The deodorant composition of claim 60, comprising from about 40 to about 60% of said broad-spectrum deodorant, from about 8 to about 15% of a copper compound selected from the group consisting of copper acetate, copper chloride, copper nitrate and copper sulfate, from about 2 to about 6% of said propylene glycol, from about 2 to about 6% of said pine oil, from about 5 to about 10% of said hydrochloric acid, from about 2 to about 6% of said acetic acid, and up to about 20% of a nonionic surfactant.

62. The deodorant composition of claim 61, comprising about 54% of said broad-spectrum deodorant, about 11% copper sulfate, about 4% of said propylene glycol, about 4% of said pine oil, about 7% of said hydrochloric acid, about 4% of said acetic acid and about 16% of said surfactant.

63. The deodorant composition of claim 1, further comprising a deodorizing-effective metallic ion selected from the group consisting of aluminum, barium, bismuth, cobalt, chromium, copper, iron, magnesium, manganese, nickel, potassium, titatium and zinc.

64. The deodorant composition of claim 63, further comprising an organic, gel-forming carrier.

65. The deodorant composition of claim 64, wherein said carrier is selected from the group consisting of acacia gum, agar, alginate, amylopectin, gum arabic, carrageenan, chitosan, dextrin, fucoidan, gum ghatti, guar gum, locust bean gum, methyl cellulose, gum tragacanth, and xanthan gum.

66. The deodorant composition of claim 65, further comprising a blocking agent for preventing said metallic ion from cross-linking said carrier into an insoluble gel.

67. The deodorant composition of claim 66, wherein said blocking agent is a volatile amine.

68. The deodorant composition of claim 66, wherein said blocking agent is ammonia.

69. T-he deodorant composition of claim 66, wherein said blocking agent is sodium hexametaphosphate.

70. The deodorant composition of claim 66, wherein said blocking agent is a chelating agent selected from the group consisting of condensed phosphates, citric acid, oxalic acid, tartaric acid, gluconates, citrates, ethylene-diaminetetraacetic acid, nitrilotriacetic acid and diethylene-triaminepentaacetic acid.

71. The deodorant composition of claim 66, wherein said blocking agent is a buffering agent for maintaining the pH of said composition in the range of from about 5 to about 9.

72. The deodorant composition of claim 65, further comprising a pelletizing agent to cross-link said carrier and yield a shape-sustaining mass.

73 The deodorant composition of claim 65, wherein said carrier is alginate.

74. The deodorant composition of claim 73, wherein said metallic ion is copper.

75. The deodorant composition of claim 73, further comprising a blocking agent, for preventing said ion from cross-linking said alginate into an insoluble gel, selected from the group consisting of ammonia and sodium hexameta-phosphate.

76. A deodorant composition according to claim 1 com-prising a gel carrier therefor selected from the group consisting of acacia gum, agar, alginate, amylopectin, gum arabic, carrageenan, chitosan, dextrin, fucoidan, gum ghatti, guar gum, locust bean gum, methyl cellulose, gum tragacanth and xanthan gum.

77. The deodorizing composition of claim 76, wherein said carrier is alginate.

78. The deodorizing composition of claim 76, wherein said deodorant includes a deodorizing-effective metallic ion selected from the group consisting of aluminum, barium, bismuth, cobalt, chromium, copper, iron, magnesium, manganese, nickel, potassium, titanium and zinc.

79. The deodorizing composition of claim 78, further comprising a blocking agent for said carrier to prevent same from an insolublization transformation.

80. The deodorizing composition of claim 79, wherein said blocking agent is a volatile amine.

81. The deodorizing composition of claim 79, wherein said blocking agent is ammonia.

82. The deodorizing composition of claim 79, wherein said blocking agent is sodium hexametaphosphate.

85. The deodorizing composition of claim 79, wherein said blocking agent is a chelating agent selected from the group consisting of condensed phosphates, citric acid, oxalic acid, tartaric acid, gluconates, citrates, ethylenediamine-tretraacetic acid, nitrilotriacetic acid and diethylene-triaminepentaacetic acid.

84. The deodorizing composition of claim 79, wherein said blocking agent is a buffering agent for maintaining the pH of said composition in the range of from about 5 to about 9.

85. The deodorizing composition of claim 78, further comprising a pelletizing agent to cross-link said carrier and yield a shape-sustaining mass.

86. The deodorizing composition of claim 79, further comprising a pelletizing agent to cross-link said carrier to yield a shape-sustaining mass.