Patent Grant
10869459
The present invention relates to mixed salts of sodium and aluminum, and more particularly to their use as poultry and livestock litter additions.
Animal litters produce ammonia as a byproduct of microbial growth. Aluminum sulfate and sodium bisulfate have been widely used to reduce the ammonia volatilization that occurs in animal litters. Aluminum sulfate and sodium bisulfate are both acidulants that neutralize ammonia by lowering the pH. Aluminum sulfate can also react with ammonia to form nonvolatile compounds. Volatile ammonia can be expressed as ammonium hydroxide (NH4OH). Ammonium hydroxide neutralization with sodium bisulfate can be expressed as follows:
2NaHSO4.H2O+2NH4OH→(NH4)2SO4+Na2SO4+4H2O (1)
Ammonium hydroxide neutralization with aluminum sulfate can be expressed as follows:
6NH4OH+Al2(SO4)3.14H2O→3(NH4)2SO4+Na2SO4+4H2O (2)
Other side reactions that may occur, which also help to dry the animal litter include:
Al2(SO4)3.14H2O+Na2SO4+10H2O→2NaAl(SO4)2.12H2O (3)
and
Al2(SO4)3.14H2O+(NH4)2SO4+10H2O→2NH4Al(SO4)2.12H2O (4)
Both aluminum sulfate and sodium bisulfate have certain drawbacks in their effectiveness as a litter amendment. Sodium bisulfate reacts quickly and has good hydroscopic properties, but it is also exhausted quickly. Sodium bisulfate can also leave a wet litter that can be detrimental to the health of the animals. In addition, sodium bisulfate does not have the ability to bind phosphorous. This is an issue when animal litter is applied as a fertilizer, and the phosphorous is not retained in the soil to benefit the crop. Instead, the phosphorous tends to leach its way into bodies of water where it fertilizes algae causing uncontrolled algae growth.
Aluminum sulfate has the benefit that it reacts with phosphorous in the litter to make an insoluble compound that will not leach out of the litter when used as a soil amendment. However, aluminum sulfate has difficulty activating in low humidity environments and can stop working altogether under these conditions. Therefore, aluminum sulfate is not effective during the winter when relative humidity and litter moisture content are reduced.
In accordance with one embodiment of the invention, a method for producing a mixed salt of sodium and aluminum includes providing a solution comprising water, sodium chloride and sulfuric acid, heating the solution to a temperature between 180° F. and 300° F. (82° C. and 149° C.) so that the sodium chloride reacts with the sulfuric acid to form sodium bisulfate and hydrochloric acid and then continue heating until the solution is essentially free of the hydrochloric acid, adding aluminum or an aluminum compound to the solution to form the mixed salt comprising a sodium aluminum sulfate compound and solidifying the mixed salt to form the sodium aluminum sulfate compound.
In related embodiments, the sodium aluminum sulfate compound may include sodium aluminum sulfate, sodium aluminum bisulfate and/or sodium aluminum hydrosulfate. The sodium aluminum bisulfate may be of the formula Na2Al2H2(SO4)5-(x+6)H2O where x is a positive integer ranging from 6 to 14. The sodium aluminum sulfate compound may be sodium aluminum bisulfate and the method may further include digesting aluminum oxide trihydrate in an aqueous solution of sodium bisulfate and the sulfuric acid to form the sodium aluminum bisulfate. The method may further include reacting sulfuric acid and the sodium chloride to form the sodium bisulfate. A ratio of the sodium bisulfate to the aluminum compound may be about 20:80 wt % to about 40:60 wt %, and preferably about 30:70 wt % to about 35:65 wt %. The method may further include off-gassing HCl from the mixed salt. The aluminum compound may be selected from the group consisting of Al2O3, Al2O3.3H2O, bauxite and/or aluminum clay. The solidifying may include cooling the mixed salt to below its freezing point.
In accordance with another embodiment of the invention, a sodium aluminum sulfate compound is manufactured according to any of the methods mentioned above. The sodium aluminum sulfate compound may be essentially free of sulfuric acid. The sodium aluminum sulfate compound may include sodium aluminum sulfate, sodium aluminum bisulfate and/or sodium aluminum hydrosulfate.
In accordance with another embodiment of the invention, a poultry or livestock litter amendment includes the sodium aluminum sulfate compound mentioned above manufactured according to any of the methods mentioned above.
In accordance with another embodiment of the invention, a method for controlling ammonia levels in an enclosure for raising poultry or livestock includes providing the litter amendment mentioned above and applying the litter amendment to a portion of the enclosure. In related embodiments, the enclosure may have an atmospheric humidity of below 45% or below 35%. The enclosure may have a temperature of below about 86° F. (30° C.).
The foregoing features of embodiments will be more readily understood by reference to the following detailed description, taken with reference to the accompanying drawings, in which:
Definitions. As used in this description and the accompanying claims, the following terms shall have the meanings indicated, unless the context otherwise requires:
A “mixed salt” is a compound with a given proportion of two salts, in some instances sharing either a common cation or common anion.
The “moisture content” of a composition such as a litter amendment is expressed as the percentage of weight change exhibited by the composition in relation to its original, dry weight.
A mixed salt product was formed according to embodiments of the present invention that optimizes the benefits of both sodium bisulfate and aluminum sulfate and also minimizes the drawbacks of the individual products. The mixed salt product has the ability to absorb ammonia from animal manure, even in conditions of low humidity, while still binding the phosphorus from the manure. In addition, the mixed salt product may be added as a litter amendment with a stable granular formulate that is easy to apply to a portion of barns and henhouses to reduce the ammonia emissions.
NaCl+H2SO4+H2O→HCl+NaHSO4.H2O (5)
The heating is continued to allow the off-gassing of the hydrochloric acid until the solution is essentially free of the hydrochloric acid (step 130). The solution may have additional sulfuric acid left over after the reaction. For example, the reaction may be as follows:
2NaCl+5H2SO4→2HCl+2NAHSO4+3H2SO4 (6)
Alternatively, an additional amount of sulfuric acid may be added to the solution, either before or after the continued heating in step 130 that drives off the hydrochloric acid, in order to tailor the reaction parameters. An additional amount of water may also be added to the solution.
In step 140, aluminum or an aluminum compound is added to the solution to form a mixed salt that includes a sodium aluminum sulfate compound. For example, the aluminum compound may include alumina (Al2O3), either dry or in its hydrated forms (e.g., Al2O3.3H2O), bauxite, and/or aluminum clays. For example, the mixed salt may be made by digesting aluminum oxide trihydrate in an aqueous solution of sulfuric acid and sodium bisulfate. The sodium bisulfate may be generated in situ by the reaction of sodium chloride with the sulfuric acid. For example, the reaction may be expressed as follows:
2NaHSO4+3H2SO4+Al2O3-3H2O+xH2O→Na2Al2H2(SO4)5−(x+6)H2O (7)
Where x=6 to 14.
The relative amounts of sodium bisulfate to the aluminum compound may be in a weight-to-weight ratio of about 20:80 wt % to about 40:60 wt %. For example, the relative amounts of sodium bisulfate to the aluminum compound may be in a weight-to-weight ratio of about 30:70 wt % to about 35:65 wt %. In instances where the sodium bisulfate is produced in situ, the amount of sodium chloride in the first reaction (shown in Equations 5 or 6) should be sufficient to yield sodium bisulfate in amounts within the ranges specified above. The aluminum compound may be aluminum sulfate having a standard particle size in the range of about 180 μm to about 1700 μm in diameter (e.g., about 600 μm to about 1400 μm), a smaller, finer particle size in the range of about 10 μm to about 1400 μm in diameter (e.g., about 10 μm to about 600 μm), or a mixture of the two particle sizes.
In step 150, the mixed salt is solidified in order to form the sodium aluminum sulfate compound. For example, the sodium aluminum sulfate compound may be solidified by cooling the mixed salt to below its freezing point. The sodium aluminum sulfate compound may be sodium aluminum bisulfate, sodium aluminum sulfate and/or sodium aluminum hydrosulfate. The structure of this compound is confirmed by X-ray diffraction analysis, as shown in
The sodium aluminum sulfate compound may be used as an active ingredient in poultry or livestock litter amendment compositions. When applied to animal litter, the sodium aluminum sulfate compound activates under low humidity conditions, can last long enough to prevent ammonia breakthrough, and can reduce the amount of phosphorous that leaches out of the animal litter. Accordingly, embodiments of the present invention provide a litter amendment composition that may be used to treat animal waste, for example livestock manure in barns or poultry droppings in henhouses. At the same time, the amendment is capable of retaining phosphorus at levels attained by aluminum sulfate. As a result, the litter amendment composition of the present application combines the desirable properties of sodium bisulfate and aluminum sulfate while minimizing their respective drawbacks.
In a further embodiment of the invention, there is provided a method for controlling ammonia levels in enclosed spaces where poultry or livestock are raised, such as barns and henhouses. The method includes providing the litter amendment with the sodium aluminum sulfate compound formed according to embodiments of the present invention and applying the litter amendment to a portion of the enclosure. By applying the litter amendment to surfaces where droppings tend to accumulate or are collected, the production and emission of ammonia is reduced while the phosphorus in the droppings is retained, thereby protecting the animals in the enclosure from unhealthy or toxic levels of atmospheric ammonia while producing a phosphorus-rich fertilizer. The litter amendment with the sodium aluminum sulfate compound may be particularly beneficial for controlling ammonia emissions in conditions with low atmospheric humidity and low amounts of moisture in the litter, such as seen during the winter months. For example, the enclosure may have an atmospheric humidity of below 45% or below 35% and may have a temperature of below about 86° F. (30° C.).
Several attempts to make the mixed salt were conducted with various amounts of the sodium bisulfate to the aluminum compound ratio. The amounts of the components are shown in Table 1 for Examples 1-5. The sodium bisulfate and the aluminum compound used for Examples 1-5 had a particle size in the range of about 10 μm to about 2000 μm in diameter.
The salt (sodium bisulfate) and alumina was reacted with the sulfuric acid to form a salt slurry that immediately began to release hydrogen chloride. The ratio of Sodium Bisulfate to dry Alum (aluminum sulfate) was chosen to be 40:60 wt %. The slurry was heated and allowed to react until all of the salt had dissolved. At this point the addition of the hydrate and water began to form a solution. Once the solution began to solidify, the solution was poured into a mold and allowed to cool. Once cool, the product produced a white odorless solid that was difficult to grind. The material wanted to smear rather than grind. The processing parameters are shown in Table 2.
Followed the sequence used for Example 1 except changed the ratio of Sodium Bisulfate to alum and used a ratio of 20:80. The sample produced a white odorless solid that was easy to grind. The processing parameters are shown in Table 3.
Repeated the sequence used for Example 1 with the ratio of Sodium Bisulfate to alum of 40:60. The sample produced the same results as Example 1. The processing parameters are shown in Table 4.
Followed the sequence used for Example 1 except changed the ratio of Sodium Bisulfate to alum and used a ratio of 30:70. The sample produced a white odorless solid that was easy to grind. The processing parameters are shown in Table 5.
Followed the sequence used for Example 1 except changed the ratio of Sodium Bisulfate to alum and used a ratio of 35:65. The sample produced a white odorless solid that was easy to grind. The processing parameters are shown in Table 6.
Sodium bisulfate may be incorporated into the dry alum and still produce a dry material that can be commercially processed up to at least a ratio of 35:65. The hydroscopic properties and corrosiveness of the material was further evaluated to see if the resulting product had achieved the desired properties.
The relative humidity thresholds for activation were analyzed for different litter amendments: aluminum sulfate, sodium bisulfate, and a mixed salt product produced according to Example 5 above. A temperature and humidity controlled chamber was used to determine the relative humidity threshold for activation. The temperature of the chamber was controlled by a heater and set to 88° F. (31.1° C.), which is the typical set point for broiler houses during brooding periods. The relative humidity of the chamber was set to 35, 40, 45, 50, and 60%. Three grams of each litter amendment were placed in glass containers and exposed to the different relative humidity levels at 88° F. over a three-day period.
The results are shown in
Aluminum sulfate absorbed the least amount (1% to 3.5% by weight) of water over the three-day period at all relative humidity levels. Sodium bisulfate exhibited a low water absorption rate (<7%) when relative ambient humidity was lower than 45%. The water absorption rate of sodium bisulfate increased to 19% at 45% relative ambient humidity and the bulk of water absorption took place during the first 24 hours. The mixed salt was more hydroscopic than the other amendments when relative humidity was less than 45%, and absorbed 9% to 12% water from the ambient air. The water absorption rate of the mixed salt increased to 23% when relative humidity was at 60%. The results show that ambient air could not provide sufficient water to activate aluminum sulfate under normal conditions during the beginning of a winter flock season when relative humidity was lower than 60%. The relative humidity threshold for sodium bisulfate was about 45%. The results indicated that the inclusion of sodium bisulfate may assist the activation of aluminum sulfate when relative humidity was 45% or higher. The mixed salt was a better option to control ammonia when relative humidity is lower than 45%.
The effect of threshold relative humidity on litter moisture content changes was evaluated. The results are shown in
The effect of a dry mixture of aluminum sulfate and sodium bisulfate was measured to determine its effectiveness to control the ammonia emissions. The results are shown in
The ammonia emissions of the treated litter samples were compared to determine the effectiveness of the different mixtures. Surface application of aluminum sulfate, without or with sodium bisulfate, on broiler litter substantially reduced NH3 emission during the three-day storage period. The extent of the reduction was generally affected by the amount of sodium bisulfate included with the aluminum sulfate. Aluminum sulfate with smaller particles (e.g., particle size in the range of about 10 μm to about 600 μm in diameter was used since there were no difference between the two different particle sizes on the water absorption evaluated in Example 6. Therefore, the product with smaller particle size may be activated easier with its larger surface area. The NH3 reduction rates of 0% and 5% inclusion rates were much lower than the higher rates while there was no significant difference among the three higher rates (10%, 20%, and 40%). The results suggested that 10% inclusion rate of sodium bisulfate is sufficient to activate aluminum sulfate when relative humidity was about the threshold level 45%.
The ammonia management guidelines were determined under winter conditions during brooding for aluminum sulfate, sodium bisulfate, a dry mixture of aluminum sulfate and sodium bisulfate, and a mixed salt produced according to embodiments of the present invention. The parameters used are shown in Table 7 below and the results are shown in
120% was selected as sodium bisulfate inclusion rate on the basis of Examples 6-8.
2TH (45% at 30° C.) is the relative humidity threshold of initial activation.
Twelve 19-L emission vessels were used to determine the environmental management guidelines. The vessels were placed in an environment-controlled room that was kept at a constant temperature of 30° C. while the relative humidity was maintained at two different levels, 45% and 35%. The room relative humidity control system included PC-based humidity control program, relative humidity sensors, a dehumidifier, and a humidifier. The vessels were operated under positive pressure. A pump was used to supply fresh air to the emission vessels. The flow rate of the fresh air supply was controlled and measured with an air mass flow controller. A flow rate of 2.5 LPM (liters per minute) was established inside each vessel, resulting in an air exchange rate of 10 air changes per hour (ACH).
Samples of the exhaust air from each of the vessels, the supply air and the ambient air were sequentially taken and analyzed at 5 minute intervals, with the first 4 minutes for stabilization and the last 1 minute for measurement. This yielded a measurement cycle of 1 hour for each vessel. The ammonia concentrations were measured with the same ammonia gas analyzer that was used for the mini vessel system used in Example 6.
The mixed salt, the aluminum sulfate with two different particle sizes, and the sodium bisulfate were tested to determine optimal application rates during brooding under different relative humidity levels simulating the winter conditions. Used litter samples from a commercial farm at two moisture contents (20% and 25%) were treated with five different amendments and compared with untreated litter in the 12-bucket emission system. Different treatments were topically applied to the litter samples (4 inches depth). Two application rates (50 and 100 lbs./1000 ft2) were tested. The ammonia emissions of the treated litter samples were compared to determine the effectiveness of the different amendments.
As shown in
The results indicated that there was not enough moisture to activate aluminum sulfate without the inclusion of sodium bisulfate. The reduction in ammonia emission in the presence of the aluminum sulfate without sodium bisulfate was higher than 70% for only two days and the nine-day average reduction rate was 46% while the rate was 90% when 20% sodium bisulfate was used. The performance of the mixed salt was lower than in Test 1, which started at a higher relative humidity level. Therefore, higher relative humidity (45% or higher) is important to maintain to ensure the activation of the mixed salt.
As shown in
There was no significant difference between treatments with sodium bisulfate and aluminum sulfate with 20% sodium bisulfate during the first three days when relative humidity was kept at 45% or higher. Sodium bisulfate had better ammonia reduction than sodium bisulfate when relative humidity was below 40%. There was a layer of crust formed at the surface of the treated litter when sodium bisulfate deliquesced. The crust appears to serve as a barrier or shell that reduced the litter surface area exposed to air and thus reduced ammonia emission.
The aluminum sulfate with a finer particle size had very slight better performance than the aluminum sulfate with a standard particle size due to the smaller particles and large surface area contacting the litter. The results show that the mixed salt formed according to embodiments of the present invention can be used to control ammonia emission with a comparable application rate used for sodium bisulfate and aluminum sulfate. Ammonia emission is affected by litter moisture condition and nutrient composition. Therefore, the actual aluminum sulfate application rate should be adjusted based on litter condition. Windrowing litter could cause high ammonia emission from litter due to the composting effect. A windrowed animal enclosure should be vented for at least 48 hours to flush the built-up ammonia in the litter prior to litter amendment application.
Data Analysis of Examples 6-9
Statistical analyses of the water absorption, moisture loss, and ammonia emission reduction data discussed in Examples 6-9 were performed with multiple comparison (JMP 11.0, SAS). Significant differences for all comparisons were based on P<0.05.
Although the above discussion discloses various exemplary embodiments, those skilled in the art may make various modifications to, or variations of, the illustrated embodiments without departing from the inventive concepts disclosed herein.
This patent application claims the benefit of U.S. Provisional Patent Appl. No. 62/612,951 filed Jan. 2, 2018, the disclosure of which is incorporated by reference herein in its entirety.
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| Number | Date | Country | |
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| 62612951 | Jan 2018 | US |
