# Patent

## Title
Methods of treating manure

## Abstract

A method of treating animal manure solids comprises contacting the solids with a treatment composition comprising AlCl3.nH2O or Al(NO3)3.mH2O, or the residue of AlCl3.nH2O or Al(NO3)3.mH2O, to form a treated waste product, wherein n is from 0 to 10, and m is from 0 to 12. The treatment amount can be effective to reduce phosphorus solubility in the manure; reduce phosphorus runoff and/or phosphorus leaching from fields fertilized with manure; inhibit ammonia volatilization from the manure; flocculate solids in the manure; reduce pathogens in the manure; increase the nitrogen content in the manure; and/or reduce acid rain and PM-10s associated with the manure.

## Background
RELATED APPLICATIONS
This application is a continuation-in-part application of copending U.S. application Ser. No. 09/177,095, filed Oct. 22, 1998 now U.S. Pat. No. 6,346,240, which is incorporated by reference in its entirety.


FIELD OF THE INVENTION
This invention relates to the treatment of animal waste to reduce harmful phosphorus runoff from fields to which the animal wastes are applied, and to the reduction of ammonia emitted from such animal wastes. The invention is particularly applicable to treating poultry litter, and liquid slurries of animal waste that are generated during the rearing of livestock in controlled rearing facilities.
BACKGROUND OF THE INVENTION
Swine, poultry and other livestock are commonly reared in facilities that are specially designed to manage manure and liquid waste generated by such livestock. For example, poultry are typically raised on beds of litter that contain a filler such as wood shavings or saw dust, spilled food, feathers, and manure. After a growout on the bed of litter, and during successive growouts, the litter is predominantly manure, and is eventually replaced by fresh bedding.
Some swine rearing facilities have slatted floors on which the swine are raised. Beneath the floors are pits for receiving swine manure and urine that pass through the slatted floor. These pits contain water that is occasionally drained to remove the livestock waste. Other facilities raise swine on a hard slanted floor, and periodically wash accumulated manure and urine from the slanted floor. Still other facilities use a combined approach, and have slatted floors on which the swine are raised, and a slanted floor underneath that is periodically washed to remove accumulated manure and urine. Water that is used to flush manure in these facilities is often pumped into large tanks that can be quickly discharged to rapidly flush manure from the facility.
Dairy cows are also often raised in facilities that must periodically be washed of animal manure and urine. The dairy cows are often fed in a sheltered pen that has a hard concrete floor that is periodically washed.
Farmers manage the manure and waste water from livestock rearing facilities in several manners. Almost all farmers attempt to apply the manure and waste water onto agricultural fields. Some farmers spread the manure and waste water from the facilities directly onto their fields. When managing waste water, some farmers first send the waste water to a holding pond or lagoon before spreading the waste water onto their fields. Because solids tend to separate from the water in the center of the holding pond or lagoon, some farmers withdraw water from the center of the pond or lagoon and reuse it in their facilities to wash away excess manure.
Manure excreted by the poultry and other livestock generate ammonia that contributes to the offensive odor in many rearing facilities. Ammonia volatilization is especially acute in poultry facilities during the winter, when ventilation must be minimized to reduce heating costs. Ammonia volatilization is also acute in facilities that are flushed with recycled water from an anaerobic lagoon or holding pond. Nitrogen in swine lagoon effluent is mostly in the form of NH4, with little NO3 present. Indeed, ammonia concentrations of 350 mg/l and greater are common in lagoon effluent. In addition, because swine lagoon effluent is typically alkaline (pH>7.0), ammonia is favored over ammonium, resulting in conditions favorable for ammonia volatilization. When high pH water from swine lagoons is used for flush water, large quantities of ammonia are volatilized, causing even further elevated levels of ammonia gas inside and outside the rearing facility.
High atmospheric ammonia levels in swine rearing facilities have been shown to have a significant negative effect on feed consumption, feed conversion and daily weight gain in pigs. High levels of atmospheric ammonia in swine rearing facilities also increase the susceptibility of swine to micro-organisms responsible for respiratory problems, such as P. multocida. Ammonia also increases the susceptibility of four week old pigs to conchal atrophy. Likewise, high ammonia levels in swine facilities may play a significant role in the development of atrophic rhinitis. Similar problems are reported in poultry houses.
Another detrimental aspect of NH3 volatilization from poultry and hog manure is the effect on acid rain. The reportedly dominant source of atmospheric NH3 in Europe is livestock waste, with long term trends showing a 50% increase in NH3 emissions in Europe from 1950 to 1980. Ammonia raises the pH of rainwater, which allows more SO2 to dissolve in it. Ammonium sulfate then forms, which oxidizes in the soil, releasing nitric and sulfuric acid. This produces two to five times the acid input to soils previously described for acid atmospheric deposition, resulting in extremely low pH values (2.8–3.5) and high levels of dissolved aluminum in non-calcareous soils. Ammonia volatilization can also contribute to eutrophication. Reports show that nitrogen deposited via wet fallout tripled in Denmark from 1955 to 1980, corresponding to increases in nitrogen losses from agricultural operations during this period. The rising levels of nitrogen in the fallout have also been linked to the NH3 content in Danish streams.
Atmospheric ammonia can also result in the formation of ammonium nitrate particles in the air. These particles, which are usually less than 2 microns in size, contribute greatly to small airborne particles referred to as PM-10's (particulate matter less than 10 microns).
Poultry and swine (Sus scrofa domesticus) production is currently on the rise in the United States. As the poultry and swine industry moves into watersheds susceptible to eutrophication, various groups have voiced concern over water pollution. Modern poultry and swine rearing facilities often have large numbers of animals and a relatively limited land base to apply the manure. This leads to excessive application of nutrients, especially phosphorus, to the land. Phosphorus is considered to be the primary cause of eutrophication of freshwater systems. The threat of eutrophication due to phosphorus runoff has already resulted in limits being placed on the amount of animal units produced per area of land in The Netherlands.
SUMMARY OF THE INVENTION
Aluminum sulfate has previously been used to reduce phosphorus solubility and to inhibit ammonia volatilization from poultry litter, with tremendous success. U.S. Pat. No. 5,622,697 to Moore. However, when aluminum sulfate is added to a manure slurry, it can generate off-gasses that compound the odor problems associated with controlled livestock operations. It has unexpectedly been discovered that aluminum chloride and aluminum nitrate, when contacted with poultry litter, can reduce the harmful environmental effects of the manure, such as ammonia volatilization and phosphorus solubilization.
It has also unexpectedly been discovered that aluminum chloride and aluminum nitrate, when contacted with manure slurries from livestock, can reduce such harmful environmental effects. For example, aluminum chloride and aluminum nitrate can reduce ammonia volatilization and phosphorus solubilization without generating other off-gasses when applied to liquid slurries.
Accordingly, this invention, in one aspect, relates to a method of treating animal manure comprising contacting animal manure solids with a composition comprising AlCl3.nH2O or Al(NO3)3.mH2O, or the residue of AlCl3.nH2O or Al(NO3)3.mH2O, to O, to form a treated waste product, wherein n is from 0 to 10, and m is from 0 to 12.
Additional aspects and advantages of the invention will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. The advantages of the invention will be realized and attained by means of the elements and combinations particularly pointed out in the appended claims. It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the invention, as claimed.



BRIEF DESCRIPTION OF THE DRAWINGS
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate several embodiments of the invention and together with the description, serve to explain the principles of the invention.
FIG. 1 is a graph showing the relationship between the pH of swine lagoon water and the amount of aluminum chloride added to the swine lagoon water.
FIGS. 2A and 2B are graphs showing the effect of varying concentrations of alum and aluminum chloride on (A) soluble reactive phosphorus, and (B) pH, of liquid swine manure.
FIGS. 3A and 3B are bar graphs showing (A) soluble reactive phosphorus, and (B) pH, of 100 ml. of liquid swine manure to which has been added 10 ml. of 10% alum or aluminum chloride.



DESCRIPTION OF PREFERRED EMBODIMENTS OF THE INVENTION
The present invention may be understood more readily by reference to the following detailed description of the invention and the Examples included therein and to the Figures and their previous and following description. Before the present compounds, compositions and methods are disclosed and described, it is to be understood that this invention is not limited to specific methods, or to particular formulations, as such may, of course, vary. It is also to be understood that the terminology used herein is for the purpose of describing particular embodiments only and, unless the context dictates otherwise, is not intended to be limiting.
Use of Terms
It must be noted that, as used in the specification and the appended claims, the singular forms “a,” “an” and “the” include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to “an aromatic compound” includes mixtures of aromatic compounds, reference to “a treatment composition” includes mixtures of two or more such treatment compositions, and the like.
Ranges are often expressed herein as from “about” one particular value, and/or to “about” another particular value. When such a range is expressed, another embodiment includes from the one particular value and/or to the other particular value. Similarly, when values are expressed as approximations, by use of the antecedent “about,” it will be understood that the particular value forms another embodiment.
Definitions
In this specification and in the claims which follow, reference will be made to a number of terms which shall be defined to have the following meanings:
Parts by weight, of a particular element or component in a composition or article, denotes the weight relationship between the element or component and any other elements or components in the composition or article for which a part by weight is expressed. Thus, in a compound containing 2 parts by weight of component X and 5 parts by weight component Y, X and Y are present at a weight ratio of 2:5, and are present in such ratio regardless of whether additional components are contained in the compound.
A weight percent of a component, unless specifically stated to the contrary, is based on the total weight of the formulation or composition in which the component is included.
A residue of a chemical species, as used in the specification and concluding claims, refers to the moiety that is the resulting product of the chemical species in a particular reaction scheme or subsequent formulation or chemical product, regardless of whether the moiety is actually obtained from the chemical species. Thus, an ethylene glycol residue in a polyester refers to one or more —OCH2CH2O— units in the polyester, regardless of whether ethylene glycol was used to prepare the polyester. Similarly, an aluminum chloride hexahydrate residue in solution refers to the aluminum and chloride ions and H2O molecules that are obtained by dissolving aluminum chloride hexahydrate in solution, as well as the Al(OH)3 that is also generated, regardless of whether the ions and molecules are obtained by dissolving aluminum chloride hexahydrate in solution. Thus, the solution residue of aluminum chloride hexahydrate could be obtained by dissolving anhydrous aluminum chloride in water, as long as at least six moles of water are present per mole of aluminum chloride. A “slurry residue” is the resulting product of the chemical species in a slurry.
“Optional” or “optionally” means that the subsequently described event or circumstance may or may not occur, and that the description includes instances in which said event or circumstance occurs and instances where it does not. For example, the phrase “optionally comprising a defoaming agent” means that the composition may or may not contain a defoaming agent and that this description includes compositions that contain and do not contain a foaming agent.
By the term “effective amount” of a compound or property as provided herein is meant such amount as is capable of performing the function of the compound or property for which an effective amount is expressed. As will be pointed out below, the exact amount required will vary from process to process, depending on recognized variables such as the compounds employed and the processing conditions observed. Thus, it is not possible to specify an exact “effective amount.” However, an appropriate effective amount may be determined by one of ordinary skill in the art using only routine experimentation.
Animal manure solids refer to manure solids that are present in a composition, such as poultry litter or an animal waste slurry, that contains manure. Solids content refers to the amount of solids present in a composition that remain after water from the liquid is evaporated.
Poultry litter refers to the bed of material on which poultry are raised in commercial poultry rearing facilities. The litter contains a filler/bedding material such as sawdust or wood shavings, poultry manure, spilled food and feathers. Because the same bed of litter is often used in successive growouts of poultry, the litter varies over time with the addition of manure to the litter, the addition of bedding or amendments between growouts, and efforts to clean the litter between growouts.
A manure slurry refers to a mixture of manure and a liquid, e.g., urine and/or water. Thus, a manure slurry is formed when animal manure and urine are contacted, or when manure is mixed with water from an external source.
Aluminum chloride includes hydrated or anhydrous aluminum chloride when present as a solid. Aluminum chloride can be used in this invention in solid or liquid form, and thus discussions of aluminum chloride include both solid aluminum chloride and aluminum chloride solutions (in which aluminum chloride is present as a solution residue). Preferred aluminum chloride for practicing this invention is AlCl3.nH2O, wherein n is from 0 to 10, and even more preferred aluminum chloride is AlCl3.nH2O, wherein n is from 4 to 8. Aluminum chloride hexahydrate is most preferred.
Aluminum nitrate includes hydrated or anhydrous aluminum nitrate when present as a solid. Aluminum nitrate can be used in this invention in solid or liquid form, and thus discussions of aluminum nitrate include both solid aluminum nitrate and aluminum nitrate solutions (in which aluminum nitrate is present as a solution residue). Preferred aluminum nitrate for practicing this invention is Al(NO3)3.mH2O, wherein m is from 0 to 12, and even more preferred aluminum nitrate is Al(NO3)3.mH2O, wherein m is from 7 to 11. Aluminum nitrate nonahydrate is most preferred.
The alum or aluminum sulfate referred to in this specification includes Al2(SO4)3.nH2O, wherein n is generally from 14 to 18.
A sample refers to a portion of a composition, of any size. Thus, a composition has a sample that has a pH below 6.5 if any portion of the composition exhibits a pH below 6.5.
A controlled animal rearing facility refers to any facility in which animals are gathered, and in which live stock manure is collected and managed.
Discussion
This invention includes a method of treating animal manure solids comprising contacting the solids with a treatment composition includes AlCl3.nH2O or Al(NO3)3.mH2O, or the residue of AlCl3.nH2O or Al(NO3)3.mH2O, wherein n is from 0 to 10, and m is from 0 to 12. In one embodiment the treatment composition includes a AlCl3.nH2O or the residue of AlCl3.nH2O, and n is from about 4 to about 8. In a more preferred embodiment the treatment composition includes aluminum chloride hexahydrate, or the residue thereof.
In another embodiment the treatment composition includes Al(NO3)3.mH2O or the residue of Al(NO3)3.mH2O, and m is from about 7 to about 11. In one example of this embodiment, the treatment composition comprises aluminum nitrate nonahydrate, or the residue thereof.
The treatment compositions are employed in amounts effective to provide a treated waste product having at least one improved environmental, health and/or animal performance property as compared to a waste product that is not treated with the treatment composition.
For example, the methods of this invention can be effective in reducing phosphorus solubility in the manure, reducing phosphorus runoff and/or phosphorus leaching from fields fertilized with manure, inhibiting ammonia volatilization from the manure, flocculating at least a portion of the solids in the manure, reducing at least one pathogen in the manure, increasing the nitrogen content in the manure, reducing acid rain, atmospheric nitrogen loading, and PM-10s (particulate matter<10 microns), associated with the manure, reducing energy use in an animal rearing facility (by reducing ventilation requirements), improving animal performance (such as weight gain, feed conversion, and/or disease resistance of animals).
When aluminum chloride is contacted with manure to form a treated waste product, it can lower the pH of the manure, and converts ammonia to ammonium, which keeps the inorganic nitrogen from volatilizing. Thus, this process increases the fertilizer value of the manure, while inhibiting ammonia volatilization inside the animal rearing facility and to the atmosphere, for the benefit of both animals and humans alike.
The methods of this invention are effective for treating any livestock manure, and especially poultry litter and livestock manures that are combined in liquid slurries in controlled livestock rearing operations. Animals commonly reared in such operations include sheep, swine, poultry, goats, cattle, dairy cows, ducks, and geese. The invention is especially applicable to poultry rearing, swine rearing and dairy cow rearing operations.
The amount of AlCl3.nH2O or Al(NO3)3.mH2O (or residues thereof) that is contacted with the animal manure solids generally depends upon the amount of solids in need of treatment. In slurry operations, the solids are from two sources in slurry operations: (1) fresh manure from the livestock, and (2) if water is recycled from the holding pond, the amount of manure solids present in the recycled water. AlCl3.nH2O or Al(NO3)3.mH2O is also from two sources: (1) fresh AlCl3.nH2O or Al(NO3)3.mH2O (or residues thereof), and (2) if water is recycled from the holding pond, the amount of AlCl3.nH2O or Al(NO3)3.mH2O (or residues thereof) present in the recycled water. In poultry litter the source of aluminum chloride or aluminum nitrate includes material from prior and ongoing applications. The amount of aluminum chloride or aluminum nitrate used may also depend on the phosphorus content and/or the alkalinity of the animal waste; both of which are normally related to the solids contents.
In a preferred embodiment, which can be particularly effective for reducing phosphorus solubility and inhibiting ammonia volatilization, and the resulting waste product comprises from about 0.001 to about 50 parts by weight of the waste product residue of AlCl3.nH2O or Al(NO3)3.mH2O, and about 99.999 to about 50 parts by weight manure solids. These components of the waste product can generally be present at any ratio or range of ratios within the above endpoints. The ratio of the waste product residue of AlCl3.nH2O or Al(NO3)3.mH2O to manure solids can be greater than the smallest ratio (0.001:99.999), and/or less than the greatest ratio (50:50). Thus, the weight ratio of the waste product residue of AlCl3.nH2O or Al(NO3)3.mH2O to manure solids can be greater than 0.001:99.999; 0.005:99.995; 0.01:99.99; 0.05:99.95; 0.1:99.9; 0.5:99.5; 1:99; 2:98; 5:95; or 10:90, and/or less than 50:50; 40:60; 30:70; 25:75; 20:80; 15:85; 10:90; 5:95; or 1:99, in any overlapping range that is mathematically possible.
In slurry treatments, the amount of AlCl3.nH2O or Al(NO3)3.mH2O (or residue thereof) that is effective to reduce phosphorus solubility or to inhibit ammonia volatilization can also be expressed as grams of the waste product residue of AlCl3.nH2O or Al(NO3)3.mH2O per liter of resulting waste product. The liquids in the slurry are mostly from the flush water in slanted floor systems, the pit water in pit systems, and livestock urine. Water spilled by the livestock, and water used to rinse the facility, also contributes to the slurry liquids. The flush water or pit water can be fresh water or recycled holding pond water. The effective amounts will, therefore, vary depending upon whether the treatment composition also comprises recycled holding pond water. If the treatment composition does not comprise recycled holding pond water, then the resulting slurry preferably comprises from about 0.001 to about 100, and more preferably the resulting slurry comprises from about 0.1 to about 10 grams of the slurry residue of AlCl3.nH2O or Al(NO3)3.mH2O per liter of slurry. If the treatment composition does comprise recycled holding pond water, then the resulting slurry preferably comprises from about 0.001 to about 200, and more preferably the resulting slurry comprises from about 0.1 to about 20 grams of the slurry residue of AlCl3.nH2O or Al(NO3)3.mH2O per liter of slurry.
In situations in which the liquid flush water or pit water is the treatment composition, the amount of AlCl3.nH2O or Al(NO3)3.mH2O (or residue thereof) that is effective to reduce phosphorus solubility or to inhibit ammonia volatilization can also be expressed as grams of the composition residue of AlCl3.nH2O or Al(NO3)3.mH2O per liter of composition. Again, the effective amounts will vary depending upon whether the flush water also comprises recycled holding pond water. If the treatment composition does not comprise recycled holding pond water, then the treatment composition preferably comprises from about 0.001 to about 100, and more preferably from about 0.1 to about 10 grams of the composition residue of AlCl3.nH2O or Al(NO3)3.mH2O per liter of treatment composition. If the treatment composition does comprise recycled holding pond water, then the treatment composition preferably comprises from about 0.001 to about 200, and more preferably from about 0.1 to about 20, grams of the composition residue of AlCl3.nH2O or Al(NO3)3.mH2O per liter of treatment composition.
The amount of AlCl3.nH2O or Al(NO3)3.mH2O (or residue thereof) that is effective to inhibit ammonia volatilization can also be expressed as the amount that results in a preferred pH of the treatment composition and/or of a sample of the resulting waste product. Thus, in a preferred embodiment the resulting waste product comprises a sample that has a pH of about 7.5 or below, more preferably 7.0 or below, and even more preferably 6.5 or below. In a more preferred embodiment, the pH of the sample remains at or below the above recited pH values for at least 4 hours, and more preferably for at least 24 hours. In another embodiment the treatment composition has a pH of about 7.5 or below, more preferably 7.0 or below, and even more preferably 6.5 or below. The pH of the treatment composition can be selected based upon the level of ammonia volatilization and/or phosphorus control.
In another embodiment, especially applicable when treating poultry litter with liquid aluminum chloride or aluminum nitrate, the resultant waste product comprises from about 10 to 90 wt. % moisture, and more preferably from about 15–50%. The aluminum to phosphorus mole ratio (Al:P mole ratio) in the resultant waste product should be from about 0.05 to 5.0, and more preferably from about 0.25 to 1.5.
Another method of obtaining a treatment composition that has a pH at or below the above-described pH values would be to add the aluminum chloride to water used to flush the houses. In this system, a large tank of liquid aluminum chloride would be prepared by adding to water a concentrated liquid aluminum chloride (preferably about 27.8 wt. % of the solution residue of anhydrous aluminum chloride) to periodically flush manure from the facility. Thus, if manure is received onto a concrete floor, the tank containing water and liquid aluminum chloride can flush the surface of the floor at any desired frequency. If manure is collected in a confined liquid pit beneath slatted floors, then the contents of the large tank could be used to refill the pit when the pit is periodically drained.
The amount of aluminum chloride needed for a tank of liquid aluminum chloride can be determined principally by the amount of liquid in the tank, and by the alkalinity of the water in the tank. To determine the amount of aluminum chloride needed per liter of water in the tank, the following procedure may be used:
Obtain 1000 ml of the water to be used for flushing. While stirring, slowly add aluminum chloride and measure the pH of the water as subsequent aluminum chloride additions are made. Note the amount of aluminum chloride needed to decrease the pH to 7.5, 7.0, 6.5, 6.0, etc. This is basically an acid-base titration, with the aluminum chloride being the acid. An example of the results from a titration of swine lagoon effluent with a 10% aluminum chloride solution is shown in FIG. 1. After this has been determined, the amount of aluminum chloride needed per flush can be calculated using the volume of water held by the flush tank, by simply multiplying the number of liters contained in the tank by the amount of aluminum chloride required to reduce the pH to the desired level. The foregoing method can also be used to determine the amount of aluminum chloride needed to achieve a desired pH in the resulting waste product, except that a 1000 ml sample of the resulting waste product without aluminum chloride would be analyzed instead.
Take a large bulk litter sample from the house and mix in a suitable container, e.g., a plastic bucket. If interested in pH reduction, then add twenty grams of litter to ten centrifuge tubes. Then add 0, 0.1, 0.2, 0.4, 0.6, 0.8, 1.0, 1.5, 2.0 and 4.0 grams of liquid aluminum chloride to the litter. Afterwards, add 100 ml of D.I. water to each, shake for a suitable period of time, e.g., two hours, and measure the pH of solution.
The application system for slurry treatments could be of two basic designs; depending on the type of rearing facility. In a facility with concrete floors, the aluminum chloride would typically be added to the flush tanks, as described above. In a house with a pit beneath slatted flooring, aluminum chloride could be added to the flush tanks or directly to the liquid pit beneath the flooring.
In some instances, particularly when aluminum chloride or aluminum nitrate react with recycled holding pond effluent, lagoon effluent or liquid manures, a foam is formed. This foam is probably the result of solid phase calcium carbonates (or calcium-magnesium carbonates) dissolving as the pH of the liquid is lowered. The foam can be very beneficial from the point of view of ammonia control, as well as odor control, since it can act as a physical barrier for diffusion from at the liquid/air interface.
The treatment composition is preferably added in the amount to provide a foam depth of about 0.001 to 50 cm, more preferably about 0.5 to 5.0 cm.
Experimental
The following examples are put forth so as to provide those of ordinary skill in the art with a complete disclosure and description of how the compounds claimed herein are made and evaluated, and are intended to be purely exemplary of the invention and are not intended to limit the scope of what the inventors regard as their invention. Efforts have been made to ensure accuracy with respect to numbers (e.g., amounts, temperature, etc.) but some errors and deviations should be accounted for. Unless indicated otherwise, parts are parts by weight, temperature is in °C. or is at room temperature, and pressure is at or near atmospheric.
EXAMPLE 1
The following experiment was conducted to determine the effect of aluminum chloride and alum on phosphorus solubility from swine lagoon effluent. About 20 liters of a manure slurry from a swine rearing facility were collected and homogenized in a blender. The manure slurry contained manure, urine, and flush water. The flush water was recycled holding pond effluent removed at the center of the water column in the holding pond, combined with the aluminum chloride or alum treatment. The holding pond water had never before been treated with aluminum chloride or any other phosphorus control agent. Soluble phosphhorus reductions from the aluminum chloride and alum treatments were determined by APHA (American Public Health Association) method 424-G.
One hundred ml of the slurry were added to 45 250-ml polycarbonate centrifuge tubes. There were 8 alum treatments and 8 aluminum chloride treatments with 3 replications per treatment. The treatments were 0, 0.1, 0.25 0.5, 1.0, 2.0, 5.0 and 10 ml of 10% alum and aluminum chloride (10 wt. % solution of each). After adding the treatments, the tubes were put on a shaker and shaken for 5 minutes, then pH was measured. The samples were then incubated in the dark at 25° C. for three days. At this time the tubes were centrifuged at 9,000 rpm for 30 minutes and the supernatant was filtered through 0.45 um filters. The samples were then acidified to pH 2.0 with HCl and frozen until analyzed. Soluble reactive phosphorus (SRP) was determined using the Murphy-Riley method on a Technicon Auto-analyzer. Soluble metals were analyzed using ICAP. Unfiltered samples were analyzed for pH, EC and alkalinity.
The results of this experiment are shown in FIG. 2. Aluminum chloride decreased the amount of soluble phosphorus, as did aluminum sulfate. However, the aluminum chloride did not result in hydrogen sulfide gas formation. Both chemicals also reduced the pH, which would inhibit ammonia volatilization.
EXAMPLE 2
Although the experiment described above resulted in good reductions in soluble phosphorus, the manure used was not fresh and had been sitting in the laboratory for several weeks prior to the experiment. This may have affected the results, so another study was conducted with liquid swine waste. A manure slurry was collected as described above and returned to the laboratory where is was homogenized in a blender. One hundred ml of the slurry were added to 9 250-ml polycarbonate centrifuge tubes. There were three treatments; a control, 10 ml of 10% alum and 10 ml of 10% aluminum chloride. After adding these, the tubes were put on a shaker and shaken for 5 minutes, then pH was measured. The samples were then incubated in the dark at 25° C. for three days. At this time the tubes were centrifuged at 9,000 rpm for 30 minutes and the supernatant was filtered through 0.45 um filters. The samples were then acidified to pH 2.0 with HCl and frozen until analyzed. Soluble reactive phosphorus (SRP) was determined using the Murphy-Riley method on a Technicon Auto-analyzer. Soluble metals were analyzed using ICAP. Unfiltered samples were analyzed for pH, EC and alkalinity.
Both aluminum chloride and aluminum sulfate additions greatly reduced soluble phosphorus levels and pH, with the lowest soluble phosphorus levels and pH observed with aluminum chloride (FIG. 3). Aluminum chloride additions resulted in a decrease in soluble phosphorus of about 100 fold.
EXAMPLE 3
In order to apply liquid aluminum chloride to poultry manure, such as dry broiler litter, one would spray the liquid onto the surface of the manure. One way to achieve this would be by adding liquid aluminum chloride to a plastic (or some other compatible material that is acid resistant) tank that is mounted on a truck, tractor or trailer. The tank would have a hose or hoses which would deliver the liquid nozzles which sprayed the liquid aluminum chloride on top of the manure. In the preferred embodiment, the tank would be pressurized and the flow of liquid through the nozzles regulated so that the delivery of aluminum chloride could be precisely controlled by keeping the movement of the truck, tractor or trailer at a steady speed. Although the preferred method of pressurization would be by air, the liquids could also be pumped out. The liquid aluminum chloride or aluminum nitrate could be added either as a concentrated solution or a dilute solution. If the broiler litter is very dry, as is often the case in some areas of the country, then the preferred method would be to add sufficient water to the litter to add in activation. The amount of dilution would vary, depending upon how dry the litter is. In general, the amount of liquid added (water plus aluminum chloride or aluminum nitrate) should be sufficient so that the dry litter is wetted at the surface to a depth of 0.05 to 5.0 cm, with the preferred depth of treatment being about 0.5 to 1.0 cm.
The exact amount of aluminum chloride or aluminum nitrate added can vary depending on the nature of the problem. If, for example, a farmer would like to lower the soluble phosphorus in the litter in order to decrease non-point source phosphorus pollution, then the amount of aluminum to be added should be sufficient to result in a mole ratio of aluminum to phosphorus in the range of about 0.05 to 5.0, and more preferably from about 0.25 to 1.5, as indicated earlier. On the other hand, if the goal is to reduce manure pH to reduce ammonia emissions or inhibit the growth of pathogens or other microorganisms, then the litter could be titrated with aluminum chloride or aluminum nitrate as described earlier.
Throughout this application, various publications are referenced. The disclosures of these publications in their entireties are hereby incorporated by reference into this application in order to more fully describe the state of the art to which this invention pertains.
It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the scope or spirit of the invention. Other embodiments of the invention will be apparent to those skilled in the art from consideration of the specification and practice of the invention disclosed herein. It is intended that the specification and examples be considered as exemplary only, with a true scope and spirit of the invention being indicated by the following claims.

## Claims

1. A method of treating dry animal manure solids, comprising contacting the solids with an effective treatment amount of a treatment composition comprising AlCl3.nH2O or Al(NO3)3.mH2O to form a treated waste product having an improved environmental, health and/or animal performance property, wherein n is from 0 to 10, and m is from 0 to 12.

2. The method of claim 1 wherein the treatment amount is effective to reduce phosphorus solubility in the manure.

3. The method of claim 1 wherein the treatment amount is effective to reduce phosphorus runoff and/or phosphorus leaching from fields fertilized with manure.

4. The method of claim 1 wherein the treatment amount is effective to inhibit ammonia volatilization from the manure.

5. The method of claim 1 wherein the treatment amount is effective to improve weight gains, feed conversion, and/or disease resistance of animals.

6. The method of claim 1 wherein the treatment amount is effective to reduce ammonia emissions from manure.

7. The method of claim 1 wherein the treatment amount is effective to reduce pathogens in the manure.

8. The method of claim 1 wherein the treatment amount is effective to increase the nitrogen content of the manure.

9. The method of claim 1, wherein the treatment amount is effective to reduce at least one of acid rain, atmospheric nitrogen loading and particulate matter less than 10 microns associated with the manure.

10. The method of claim 1 wherein the treatment amount is effective to reduce energy use in an animal rearing facility.

11. The method of claim 1 wherein the manure is from poultry.

12. The method of claim 1 wherein the treated waste product comprises from about 0.001 to about 50 parts by weight of AlCl3.nH2O or Al(NO3)3.mH2O and about 50 to about 99.999 parts by weight animal manure solids.

13. The method of claim 1 wherein the treated waste product comprises from about 0.1 to about 20 parts by weight of AlCl3.nH2O or Al(NO3)3.mH2O and about 99.9 to about 80 parts by weight animal manure solids.

14. The method of claim 1 wherein the treatment composition comprises AlCl3.nH2O and n is from about 4 to about 8.

15. The method of claim 1 wherein the treatment composition comprises Al(NO3)3.mH2O and m is from about 7 to about 11.

16. The method of claim 1 wherein the treatment composition comprises aluminum chloride hexahydrate.

17. The method of claim 1 wherein the treatment composition comprises aluminum nitrate nonahydrate.

18. The method of claim 1 wherein the treatment composition comprises a liquid including from about 0.05 to about 500 grams of solution residue of AlCl3.nH2O or Al(NO3)3.mH2O per liter of liquid.

19. The method of claim 1 wherein the treatment composition comprises a liquid including from about 0.5 to about 100 grams of the solution residue of AlCl3.nH2O or Al(NO3)3.mH2O per liter of liquid.

20. The method of claim 1 wherein the treated waste product has a pH of about 7.5 or below.

21. The method of claim 1 wherein the treated waste product has a pH of about 6.5 or below.

22. The method of claim 1 wherein the level of soluble phosphorus in the treated waste product is less than the level of soluble phosphorus in the animal manure solids.

23. The method of claim 1 wherein the treatment amount is effective to reduce odor emissions from manure.

24. The method of claim 1 wherein the treatment amount is effective to reduce transmission of one or more bacteria or pathogen from manure to animals and/or humans.