The present invention generally relates to fertilizers and systems and processes capable of producing such fertilizers, and in particular organic fertilizers from an effluent derived from one or more organic sources.
High yields and healthy growth in food crops, gardens, and lawns require a high soil nitrogen content. High ammoniacal nitrogen fertilizers are commonly used to meet this need by delivering the necessary nitrogen directly to soil and crops. However, most high ammoniacal nitrogen fertilizers currently available are synthetic fertilizers which precludes them from being used to produce organic crops, one of the fastest-growing sectors of the agricultural economy. In the United States, organic crops are regulated by the National Organic Program (NOP) standards developed under the Organic Foods Production Act of 1990 (7 C.F.R. § 205), and the term “organic crops” is used herein consistent with the NOP standards. By 2031, the demand for organic fertilizer with high nitrogen content is predicted to increase tenfold in the United States. Currently, very few companies offer an organic fertilizer that meets these needs.
Processes for producing organic fertilizers may produce significant volumes of carbon dioxide (CO2) as a byproduct that may result in environmental concerns if released into the environment. Additionally, it may be desirable to capture and sequester such carbon dioxide in exchange for carbon credits which may then be sold in a carbon emission cap and trade market. To this end, some processes include sequestering the carbon dioxide as ammonium carbonate. While this may reduce the overall carbon emissions of such processes, there are several drawbacks to producing ammonium carbonate. For example, ammonium carbonate, commonly known as smelling salt, has a strong ammonia odor. For this and other reasons, drying and storing ammonium carbonate can be quite challenging.
In view of the above, it can be appreciated that it would be desirable if processes were available for producing fertilizers that are produced in accordance with the standards of the National Organic Program and that were capable of sequestering carbon dioxide byproducts in stable and easy to store products.
The present invention provides method for producing ammonium bicarbonate from organic sources.
According to one aspect of the invention, a method is provided for producing a solid ammonium bicarbonate product that includes the steps of preparing an organic feedstock that contains at least one nitrogen compound by causing organic animal manure and/or organic food waste to undergo anaerobic digestion, removing solids from the organic feedstock to produce an organic liquid effluent that contains at least one of ammonium and ammonia, performing a distillation process on the organic liquid effluent to strip and concentrate a vapor mixture therefrom that contains ammonia, carbon dioxide, and water and cool the vapor mixture to produce a condensed solution containing ammonium bicarbonate and/or ammonium carbonate, contacting the condensed solution with carbon dioxide to cause an ammonium bicarbonate precipitate to form from the condensed solution, and performing an evaporation process on the ammonium bicarbonate precipitate to remove water therefrom and produce the dry, solid ammonium bicarbonate product.
Technical effects of the fertilizers described above preferably include the ability to more efficiently produce ammonium bicarbonate and promote ease of storage thereof relative to ammonium carbonate.
Other aspects and advantages of this invention will be appreciated from the following detailed description.
The following disclosure describes various aspects of systems and processes that are schematically represented in
In
The term “stabilized” as used in reference to stabilized products refers to products that are not and do not contain gaseous ammonia, which would be objectionable for safety and environmental reasons, and instead the ammonia and nitrogen are contained in stable compounds, such as a stabilized ammonium sulfate compound. The stabilized products produced in the process of
In view of the desire to produce organic products, it should be understood that the terms “organic feedstock” or “organically derived feedstock” refer to entirely natural source materials having containing ammoniacal nitrogen from which the liquid organic waste filtrate (effluent) used herein is produced. The term “ammoniacal nitrogen” will be used herein to refer to nitrogen that is contained in ammonium, and preferably can be provided to a plant in a water-soluble form that is readily available to the plant for use as a nutrient. These natural source materials may include, but are not limited to, animal manure (including cattle manure effluent and hog manure effluent), organic food waste, blood meal, feather meal, guano, bone meal, and wastewater from a variety of food and liquid processing operations. The organic feedstock is preferably anaerobically digested to remove pathogens and convert organic matter into ammoniacal nitrogen. As known in the art, anaerobic digestion is a collection of processes by which microorganisms break down biodegradable material (biomass) within a digester and in the absence of oxygen. Within a digester, various types of bacteria may be used to break down the biomass into byproducts including biogas (e.g., methane, carbon dioxide, etc.) and a liquid effluent, commonly referred to as digestate. Although synthetic substances may not necessarily inhibit or have a significant effect on the processes disclosed herein or their ability to produce high nitrogen fertilizers, to achieve organic certification under the National Organic Program standards, the feedstock is preferably digested while avoiding any contact with any synthetic substances or materials, such as polymers that are commonly used in certain solid separation processes for animal manure affluent. Effluents produced from these feedstocks and processed as described herein preferably do not contain any suspended solids greater than 15 microns, and preferably have a total suspended solids (TSS) of about 2.5% or less.
Also consistent with the desire to produce organic products, additives used in the process represented in
Suspended solids are preferably removed from the digestate, for example, to produce an effluent having the aforementioned maximum suspended solids particles size of not greater than 15 microns and a total suspended solids (TSS) of about 2.5% or less. In
The effluent is generally the product of a pretreatment section of the system of
The distillation tower 15 is preferably a packed media column, although other distillation methods such as sieve trays may be used. Within the distillation tower 15, the heated effluent enters a stripping section 7 configured to strip and remove ammonia from the effluent. In the nonlimiting embodiment represented in
The gaseous ammonia is entrained in a vapor mixture (Tops Vapor in
The vapor mixture is conducted to a condenser 12 where the vapor mixture is condensed to yield a condensed aqueous solution that contains aqueous ammonia, ammonium bicarbonate, and/or ammonium carbonate. The condenser 12 is represented in
The tower 15 also releases a liquid mixture 9 (bottoms liquid in
The distillation tower 15 is preferably constructed to maintain organic process controls as defined by the National Organic Program and/or other relevant institutions. This includes, without limitation, the total absence of synthetic substances in areas that come into contact with the effluent and product as well as precautions to ensure that potential spills or leaks cannot introduce synthetic materials to the system. Additionally, organic process controls are preferably applied to the maintenance, operation, and sanitation of the equipment. Automation may also be used in the system to efficiently regulate the temperature and pressure inside the system.
A fraction of the vapor mixture that enters the condenser 12 and a fraction of the condensed aqueous solution condensed within the condenser 12 are shown in
CaSO4.2H2O+(NH4)2CO3→CaCO3+(NH4)2SO4+2H2O Eq. 1
CaSO4.2H2O+2(NH4)HCO3→CaCO3+(NH4)2SO4+3H2O+CO2 Eq. 2
The first tank 17 contains a relatively small amount of gypsum, which quickly reacts with the ammonium carbonate in the condensed aqueous solution. The first tank 17 also includes a small amount of ammonium sulfate and a small amount of calcium carbonate as a result of the reaction of Equation 1. The calcium carbonate formed in the tank 17 exits the tank 17 via a circulation stream 29 from which the calcium carbonate is removed with a filter 30. The resulting filtered calcium carbonate stream 44 is dried with a dryer/evaporator 33 to produce dried cakes thereof to be stored in a storage vessel 34. A filtrate slurry 32 containing the remaining ammonium carbonate/bicarbonate and ammonium sulfate originally in the circulation stream 29 enters the second tank 19, which contains a higher concentration of gypsum than the tank 17 as a result of gypsum being directly added to the tank 19 from a gypsum source 24. In addition, excess gases 18 from the first tank 17 may be diverted to the second tank 19.
Within the second tank 19, the gypsum reacts quickly with the ammonium carbonate, so that the reaction products within the tank 19 are primarily ammonium sulfate and calcium carbonate. The resulting slurry stream 20 containing ammonium sulfate and calcium carbonate exits the tank 19, and a stabilized product 35 (primarily an ammonium sulfate solution) is removed from the slurry stream 20 with a filter 27 before being sent to concentration stages of the process. In
The stabilized product 35 collected in the tank 21 may be transferred through a conduit 53 to a liquid product packaging system 22 to be packaged as a liquid ammonium sulfate solution fertilizer. Alternatively or in addition, a fraction of the condensed aqueous ammoniacal nitrogen solution produced by the condenser 12 may be transferred through a conduit 23 to and collected in a storage tank 16, and then transferred through a conduit 52 to the liquid product packaging system 22 to be packaged as a liquid ammoniacal nitrogen solution fertilizer. The solid ammonium sulfate crystals stored in storage vessel 37 may be transported through conduit 55 to a solid product packaging system 51 for packaging as a solid ammonium sulfate crystal fertilizer. Alternatively or in addition, the dried calcium carbonate cakes stored in the storage vessel 34 may be transported through conduit 54 to the solid product packaging system 51 for packaging as a solid ammonium calcium carbonate product.
In this embodiment, carbon dioxide is introduced into the storage tank 16 to cause precipitation of at least some of the ammonium bicarbonate from the condensed aqueous ammoniacal nitrogen solution stored therein. Optionally, the carbon dioxide may be recycled from other stages of the system. For example,
The ammonium bicarbonate precipitate 47 accumulated in the bottom of the storage tank 16 may be removed and dried in a dryer/evaporator 48 to produce solid ammonium bicarbonate crystals and stored in storage vessel 49. The solid ammonium bicarbonate crystals stored in storage vessel 49 may be transported through conduit 56 to the solid product packaging system 51 for packaging as a solid ammonium bicarbonate crystal fertilizer. The solid ammonium bicarbonate crystals are substantially odorless and relatively easy to dry and store, especially relative to ammonium carbonate.
In all embodiments of the water bath (tanks 17, 19, and 114), the resulting liquid is removed and heated to increase the concentration of ammonia and sulfur in the liquid. Although not shown, the ammonium sulfate solution can be diverted to a mechanical dryer to evaporate all the water off the product to create solid ammonium sulfate crystals using components similar to those represented in
The systems and processes described above produce a liquid or solid organic fertilizer or product containing soluble ammoniacal nitrogen and organic sulfur. The majority of organic fertilizers currently commercially available contain relatively low levels of nitrogen in forms that are slowly released over the course of weeks or months. In contrast, the ammoniacal nitrogen in the products produced by the processes described herein is immediately available to plants/crops upon contact with the fertilizer.
The liquid fertilizer produced preferably has a pH between 4.5 and 6.5, most preferably about 5. Water is preferably present in the liquid fertilizer in an amount of at most 83.5 wt %, for example, about 67 wt % of the product. The liquid fertilizer preferably contains at least 16.5% dissolved solids, for example, about 33% dissolved solids, and may contain trace amounts of calcium carbonate, calcium sulfate (e.g., gypsum), and other mineral residues. The fertilizer is preferably free of or substantially free of pathogens, nitrates, and phosphate. The nitrogen in the liquid fertilizer is preferably in concentrations between 3.5 and 9%, more preferably 6 to 8% and, most preferably about 7%. The sulfur in the liquid fertilizer is preferably in a concentration of 4 to 10%, more preferably 7 to 9%, and most preferably about 8%. The nitrogen-to-sulfur ratio in the liquid fertilizer is preferably 7:8, that is, the nitrogen:sulfur by weight ratio of ammonium sulfate. Any nitrogen and sulfur outside of the 7:8 ratio may reflect changes in the amount of gypsum added to the ammonium carbonate/bicarbonate solution and such difference may be due to undissolved ammoniacal nitrogen remaining in the product. In certain embodiments, the liquid fertilizer may have a nitrogen-to-phosphorus-to-potassium-to-sulfur (N—P—K—S) ratio of 7:0:0:8.
The dry fertilizer produced preferably contains about 21% nitrogen and about 24% sulfur. In certain embodiments, the dry fertilizer may have a nitrogen-to-sulfur ratio of 21:24. In certain embodiments, the dry fertilizer may have a nitrogen-to-phosphorus-to-potassium-to-sulfur (N—P—K—S) ratio of 21:0:0:24. The higher nitrogen content in the dry fertilizer may lead organic certifying agents to require the fertilizer to be mixed with compost or only be used to supply 20% of a crop's nitrogen needs during a single harvest.
The fertilizer produced is preferably produced in accordance with the standards of the National Organic Program and other relevant organic certifying institutions in order for the fertilizer to be approved as an input in organic crop production.
The resulting liquid fertilizer is excellent for providing both significant levels of nitrogen and sulfur to organic crops in a single concentrated product. The fertilizer provides a more cost competitive cost-per-pound of nitrogen as opposed to other commercially available products. The nitrogen is in a water soluble form easily taken up by plants, a faster release time than nitrogen found in compost or other organic fertilizers which have nitrogen release times stretching over several weeks to even months. The sulfur in the resulting liquid fertilizer is believed to be a preferred concentration for specialty organic crops such as berries and legumes. In particular, the berry market is currently one of the fastest growing sectors of the organics industry and current limitations of organic fertilizers have increased the overhead costs of growing organic berries. An organic ammonium sulfate product such as the fertilizers disclosed herein are believed to have the potential to reduce these overhead costs and encourage innovation in the organics industry. Traditional row crops such as wheat may also benefit from the product described therein.
The fertilizer produced is concentrated and easy to transport compared to other organic fertilizers on the market including compost, feather meal, urea, and other products, reducing the carbon footprint of organic crop production. The dry fertilizer can also be mixed with current composts and other fertilizers on the market, necessitating smaller amounts of compost and other fertilizers to be transported.
Additionally, the fertilizer produced sequesters carbon in the form of calcium carbonate during the ammonium sulfate production process. The carbon sequestered would otherwise be released into the atmosphere if the effluent used in the system was disposed of otherwise. The carbon sequestered amounts to roughly 1.5 pounds (about 0.7 kg) of carbon dioxide per pound (about 0.5 kg) of nitrogen in the fertilizer. This equates to roughly 1.5 carbon credits per 3,450 gallons (about 13,060 L) of fertilizer applied. This sequestration provides for a method of environmental management on the animal feedings operations where the organic waste filtrate required by the present invention can be sourced from anaerobically digested manure.
In investigations leading to aspects of the present invention, the above-noted process was used in the production of dry ammonium sulfate using an automated 24 foot (about 7.3 m) tall distillation tower connected to a 110,000 BTU (about 116,056 kJ) boiler. Specifically, 0.3 gallons (about 1.14 L) per minute of digested dairy cow manure effluent containing 1800 ppm ammonia filtered to 15 microns was preheated to 150° F. (about 65° C.) using a heat exchanger and then further heated to 180° F. (about 80° C.) using another heat exchanger before entering the tower. The second heat exchanger used heat captured from the Bottoms exiting the distillation tower at approximately 210° F. (about 100° C.).
The 180° F. (80° C.) effluent was pumped to the distillation tower to a point 16 feet (about 4.9 m) high on the tower. The tower was a packed media distillation column with a six inch (about 15 cm) diameter in the ammonia stripping portion. Live steam from the boiler was injected into the tower at 12 to 15 psi (about 82 to about 104 kPa) above the bottoms collection tank at the base of the tower. The ammonia from the effluent was stripped in the lower 16 feet (about 4.9 m) of the tower and then concentrated in the upper 8 feet (about 2.5 m) of the tower. The concentration portion had a diameter of 6 inches (about 15 cm) at the feed line to 2 inches (about 5 cm) at the top. CO2 and H2S was also stripped from the manure in the column. A mixture of ammonia, CO2, H2S, and water vapor exited the top of the tower as a vapor mixture. The vapor mixture exited the tower at approximately 180° F. (about 80° C.).
The concentration of the ammonia occurred using internal reflux condensation in jacketed cooling cans in the tower. Cold groundwater was run through the jacketed portions and the flow of the water was managed by control valves. The distilled vapor mixture was piped into a multistage gypsum slurry bath resulting in the production of ammonium sulfate and calcium carbonate slurry. The gypsum bath was maintained at approximately 110° F. (about 43° C.). The calcium carbonate was filtered out of the slurry resulting in an ammonium sulfate liquid. The calcium carbonate was dried resulting in a calcium carbonate cake.
Analysis of the liquid ammonium sulfate product concluded that the product contained at least 3% ammoniacal nitrogen and at least 3.4% sulfur. Lab analysis showed that there was more than an 80% ammonia removal efficiency from the effluent. A portion of the liquid ammonium sulfate product was evaporated and dried to produce dry ammonium sulfate crystals.
While the invention has been described in terms of specific embodiments, it is apparent that other forms could be adopted by one skilled in the art. For example, the physical configuration of the system could differ from that shown, and materials and processes/methods other than those noted could be used. Therefore, the scope of the invention is to be limited only by the following claims.
This is a continuation-in-part patent application of co-pending U.S. patent application Ser. No. 17/319,712, filed May 13, 2021, which is a continuation-in-part patent application of co-pending U.S. patent application Ser. No. 17/096,533, filed Nov. 12, 2020, which claims the benefit of U.S. Provisional Application No. 62/934,279 filed Nov. 12, 2019. The contents of these prior applications are incorporated herein by reference.
Number | Date | Country | |
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62934279 | Nov 2019 | US |
Number | Date | Country | |
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Parent | 17319712 | May 2021 | US |
Child | 17935189 | US | |
Parent | 17096533 | Nov 2020 | US |
Child | 17319712 | US |