FERTILIZERS CONTAINING HIGH VALUE ORGANIC COMPOUNDS AND MANUFACTURING METHODS

专利摘要:
the invention is directed to the manufacture of fertilizers having commercial levels of nitrogen reacted with organic substances. the process comprises treating organics with acid which acidifies and heats a mixture causing hydrolysis of the polymers. the acidified organic mixture is subsequently injected with a nitrogen base under conditions that result in a partially neutralized melt. liquefied and sterilized organic matter is disbursed onto recycled material to produce granules in a granulator before final drying. the process is green, scalable, and safe for locating community organics processing facilities in locations without creating a nuisance to local communities. when applied to the crop the fertilizers also provide a dual green nitrogen release profile by releasing a bolus of nitrogen for one to two weeks following application followed by a continued slow release of improved efficiency of nitrogen for a growing season.
公开号:BR112017025589B1
申请号:R112017025589-8
申请日:2016-06-06
公开日:2021-09-08
发明作者:Jeffrey C. Burnham；Gary L. Dahms；Barry R. Jarrett；Larry S. Murphy
申请人:Anuvia Plant Nutrients Holdings, Inc；
IPC主号:

专利说明:

Reference to Related Orders
[0001] This application claims priority from US Provisional Application No. 62/171,541 entitled "High Value Fertilizers and Methods of Manufacture" filed June 5, 2015, the entirety of which is incorporated herein by reference. Fundamentals 1. Field of invention
[0002] This invention is directed to the methods, systems, and processes for the manufacture of fertilizer and the fertilizer product manufactured by these methods. In particular, the invention is also directed to the manufacture of fertilizers with predetermined concentrations or absences of nitrogen, phosphate and/or potassium. 2. Description of Fundamentals
[0003] The disposal of municipal organics is a big problem in society today. Wastewater sludge, for example, is estimated to be produced at a rate of more than 7.5 million dry metric tons annually or nearly 64 dry pounds of biosolids for every individual in the United States. The term sludge has been replaced with the term biosolid which can include all forms of municipal organic waste such as, for example, domestic sewage, farm and factory organic waste that is collected or otherwise finds its way to wastewater treatment , sewage discharges, pharmaceutical residues including fermentation and processing residues, microbial digesters, food residues and food by-products, animal sewage, digested animal sewage, organic sludge, organisms and microorganisms and all combinations thereof. Most of all industrial organic waste finds its way to municipal sewage or is otherwise disposed of in landfills or as may be common in private industry. As might be thought, all forms of material containing discarded organics can and typically wrap themselves in municipal sludge including biologically active molecules such as pharmaceuticals as well as their metabolized products, paper, plastics, metals and most all forms of waste .
[0004] Wastewater biosolids are typically collected by municipalities through existing infrastructure such as sewers and other types of residential and industrial pumping systems. Collected material is sent to one or more central facilities referred to as wastewater treatment plants. In these plants water is separated from solids and sent through purification procedures for claim. Solids are either combusted or transported by truck to bury or used in a land application program as a weak fertilizer. Burning or incineration and backfilling have become more common in part because of the warning of the dangers of unprocessed biosolids. In all biosolids are assumed to have not only dangerous chemicals, but also bioactive pathogens, and pathogens. Federal, state and local regulations exist that strictly control the handling of biosolids for the safety of both workers and the public. But whether burned or buried, such procedures are highly ineffective and extremely costly.
[0005] Burning destroys most of the hazardous materials present in biosolids, but the cost of damage to the environment is always tremendous. Incinerators were built specifically to handle municipal waste. These incinerators create large amounts of contaminated smoke that contaminate the air within hundreds of square miles around the facility. The smoke that is emitted contains any contaminants that were present in the biosolids such as metals and other non-combustible components. These contaminants decant into fields and bodies of water creating ecological nightmares around plants and sometimes further windward distances to plants. Although burning produces energy, energy production is highly inefficient, requiring large amounts of biosolids to become cost-effective. The amount of energy produced is always small compared to the amount of material incinerated. Even after firing, large amounts of ash remain which must be removed and discarded. Compared to the original biosolids, the ash is devoid of any positive impact on the environment whatsoever and is simply and unceremoniously burned. Global burning negatively increases the impact of sewage disposal into the environment and for many years into the future.
[0006] Biosolids that have been treated to some degree of processing are classified according to federal standards established by the US Environmental Protection Agency as Class A or Class B with respect to microbial safety. “Class A” biosolids are considered to be free of detectable pathogens and safe enough as a fertilizer for use in human or animal harvests. Pathogens such as, for example, Salmonella sp. bacteria, fecal coliform indicator bacteria, enteric virus, and viable egg helminths should be below published levels. When pathogenic indicative organisms such as fecal coliform can be detected in biosolids at levels greater than one million per gram of dry product, USEPA has classified such treated biosolids as “Class B” implying that they are of a lower standard than that biosolids treated as “Class A” should contain less than 1000 indicator organisms per gram of dry product. Since Class B biosolids contain pathogenic indicators - and therefore potential pathogens, they are restricted in the way in which they can be applied to a crop intended for human and animal consumption.
[0007] The rule of Part 503 (Line 40 of the Code of Federal Regulations, Part 503, incorporated herein by reference) lists six alternatives for treating biosolids such that they can be classified as Class A with respect to pathogens. Alternative 1 requires biosolids to be subjected to one to four time-temperature regimes. Alternative 2 requires biosolids processing to meet pH, temperature and air drying requirements. Alternative 3 requires that when biosolids are treated in other processes, it must be demonstrated that the process can reduce viable enteric viruses and helminth eggs, and operating conditions used in the demonstration after the pathogen reduction demonstration is completed must be maintained. Alternative 4 requires that when treated in unknown processes, biosolids are tested for pathogens at the time the biosolids are used or discarded, in certain situations, prepared for use or disposal. Alternative 5 requires biosolids to be treated in one of the Processes to Further Reduce Pathogens. Alternative 6 requires that biosolids be treated in a process equivalent to one of the Processes to Further Reduce Pathogens, as determined by the qualifying authority.
[0008] Class A pathogen biosolids must also have a fecal coliform density of less than 1000 most likely numbers (MPN) per gram of total solids (dry weight basis) or a density of Salmonella sp bacteria. Less than 3 MPN per 4 grams of total solids (dry weight basis). Either of these two requirements must be met at one of the following times: when biosolids are used or disposed of; when biosolids are prepared for sale or given in a bag or other container for land application; or when biosolids or derived materials are prepared to meet the requirements for Exceptional Quality biosolids.
[0009] All biosolids applied to land must meet the ceiling concentration for pollutants, comprising nine heavy metal pollutants: arsenic, cadmium, chromium, copper, lead, mercury, nickel, selenium and zinc. If a limit for any of these is exceeded, biosolids cannot be applied to land without incorporating significant restrictions. Exceptional Quality (EQ) is a term used by the USEPA Guide Part 503 Rule 7 to characterize biosolids that meet low pollutant limits and Class A pathogen reduction (virtual absence of pathogens) and that have a reduced level of vector-attracting degradable compounds. Achieving EQ standards is an important goal for high quality products that contain an organic biosolids material.
[00010] Biosolids that are merely dry have several disadvantages for agricultural use. Biosolids have a low fertilization value, typically having nitrogen content of only about two to six percent. Volume is large and costs per unit of nitrogen are high. Heat-dried biosolids often have an unpleasant odor, particularly when wet. Also, dry pellets have low density and hardness and when mixed with other commercial fertilizer materials, the pellets may segregate, and disintegrate and may not spread evenly across the field with other denser ingredients. The unpleasant odor associated with the use of biosolids, unless properly treated, will continue to be present during further processing of a nitrogen-rich fertilizer product, and may continue to be present in the final product. This complicates the placement of suitable fertilizer processing plants for locations that are not in close proximity to residential communities. Additionally, the greater distance that biosolids must be transported increases the costs and logistics of disposing of this waste product. Another disadvantage of current improved biosolids fertilizers is that bacterial action can continue when the material becomes wet, and under storage conditions, the material temperature can rise to the self-ignition point through the oxidation of contained organic materials. Thus, except for special markets that value organic content for soil reclamation or landfill in mixed fertilizer, there is relatively little demand for heat-product dry biosolids. In many cases municipalities must pay freight charges, or may offer other incentives for commercial growth to use the material. However, this is often even more cost-effective than alternative disposal schemes.
[00011] The market value for agricultural fertilizers is mainly based on their nitrogen and sulfur content. A need exists for an economical, safe and practical method to increase the nitrogen and sulfur content of biosolids to a level approaching that of commercial mineral fertilizers, eg eight to twelve percent for nitrogen. If such municipal organics containing fertilizer can be manufactured, then the overall value of the product and demand for the product is likely to increase. Also, a properly manufactured organic-containing fertilizer will have the advantage that much of your nitrogen will be of the slow-release type. A slow-release or controlled-release fertilizer or Improved Efficiency Fertilizer ("EEF") is one in which the nutrient, eg nitrogen as in ammonium ions, phosphorus as phosphate and/or sulfur as sulfate, becomes available in the column of soil at slower rates than readily available nutrients as from traditional fertilizers such as urea, ammonium sulfate and diammonium phosphate. This slower action and/or prolonged availability of the nutrient in the soil column is quite desirable and provides nutrients to the plant throughout the plant's growth cycle with the implication that less nitrogen needs to be applied to the soil or crop thereby reducing the potential for environmental contamination and reducing the cost of using fertilizer. Additionally, slow release fertilizers are much greener than traditional inorganic fertilizers. For example, slow release fertilizers not only provide nutrients to plants for most of their cropping cycle, but also retain more of the nutrients contained in the soil column thus preventing nutrient loss through the leach into the soil water. The most advantageous slow release fertilizers additionally do not volatize their contained nutrients, especially nitrogen, to the environment upon application to the soil environment. Slow release nitrogen fertilizers from traditional inorganic manufactures come at a price many times that of common mineral nitrogen fertilizers. Under the scenario of fertilizer production that contains biosolids with high nitrogen content from their biosolids, municipalities can enjoy public and regulatory support for their biosolids disposal program. Such a program can ensure the regular removal of your dry or dehydrated biosolids, for example, by recycling the biosolids to a fertilizer with a high nitrogen content which can then be sold directly to the domestic fertilizer fertilizer distribution industry, thereby eliminating one of the main problems traditionally associated with biosolids treatment programs.
[00012] Previous attempts have been made to achieve part of these goals. US Patent Nos. 3,942,970, 3,655,395, 3,939,280, 4,304,588, and 4,519,831 describe processes for converting sewage biosolids to fertilizer. In each of these processes a urea/formaldehyde condensation product is formed on site with the biosolids. Thus, the processes require the manipulation of formaldehyde, a highly toxic lacrimator and suspected cancer-causing agent.
[00013] Other processes require highly costly equipment and/or special conditions not readily incorporated into existing sewage treatment facilities (see, Japanese Patent No. 58032638; French Patent No. 2,757,504).
[00014] A simple method to increase nitrogen in biosolids can be to mix commercial nitrogen fertilizer materials with the wet biosolids before drying and pelletizing. There are significant drawbacks to such a strategy. There are only a few high nitrogen fertilizer materials that are economical for agricultural use. Examples include: ammonia (82 weight percent N), urea (46 weight percent N-{nitrogen}), and ammonium nitrate (33.54 weight percent N). Ammonia has high volatility and is subject to strict regulation of discharges to the atmosphere. Urea is a solid that readily adsorbs moisture and makes mixed organics more difficult to dry. Urea is also highly susceptible to breakdown to ammonia by microbes and enzymes in biosolids and soil if they are not properly prepared, resulting in nitrogen loss and an odor problem. Ammonium nitrate is a strong oxidant and can result in a potential explosion problem that has all eliminated this fertilizer from the commercial market after 2001. All of these fertilizers have high nitrogen content, but are less than ideal to combine with such municipal organics. as biosolids or special processing absent in food waste.
[00015] Other references, such as European Patent No. 0143392, Japanese Patent No. 9110570 A2, and "Granulation of Compost from Sewage Sludge. V. Reduction of Ammonia Emission from Drying Process”, Hokkaidoritsu Kogyo Shikenjo Hokoku, 287, 85-89 (1988) fail to publicize the use of acids with ammonium sulfate additions and do not discuss the problem of corrosion of steel process equipment under acidic conditions.
[00016] For the past thirty years, alkaline stabilization of biosolids has been a successful standard and method of manufacturing biosolids to beneficially use materials that can be used primarily as soil conditioning materials. Since these alkaline stabilized biosolids products have high calcium carbonate equivalences, they have been produced and manufactured as agricultural or acute Ag fertilizer materials, commonly as a replacement for calcium carbonate in farm soil management strategies. Because of this usage, the value of these materials has been restricted to just a few dollars per ton of product. However, transportation costs are high in large part due to the significant water content of the finished material. Water amounts of up to fifty or sixty percent make transport economically and geographically restricted to areas close to the source of your treatment.
[00017] Thus, there is a long existing need for practical means of increasing the economic value of municipal organic materials by increasing their nitrogen content, and increasing their spreadability as well as a need to treat these materials as they are. converted to commodity and specialty fertilizers with physical and chemical properties and nutrients such that they can command significant value in the domestic and international commodity fertilizer market. A series of US Patents, US Patent Nos. 5,984,992; 6,159,263; 6,758,879 and 7,128,880 describe methods of producing organically enhanced high nitrogen ammonium sulfate fertilizers made with biosolids using a cross tube reactor as originated by the Tennessee Valley Authority (TVA). The tube, tee and cross tube reactor are defined by the International Fertilizer Development Center (IFDC) in the IFDC Fertilizer Handbook (1998), p 440 as: “The tube reactor basically consists of a length of corrosion resistant tube (about 5 to 15 m long) where phosphoric acid, ammonia and generally water are simultaneously added at one end through a piping configuration that resembles a T, hence the name 'T reactor.'” The T reactor has been modified by TVA to also accept an additional flow of sulfuric acid through another tube inlet located opposite the phosphoric acid inlet, giving the unit a “cross tube” configuration and thus the name “cross tube reactor”.
[00018] Both the IFDC Fertilizer Manual (1998) and the Fertilizer Technical Data Book (2000) refer to cross tube reactors. Cross tube reactors deliver a concentrated mixture to the granulator forming device and more efficiently evaporate unwanted water from the fertilizer mixture than other devices, but these references demonstrate a much-felt need for improvement, indicating that one of the disadvantages of Cross tube reactor is the formation of scale inside the tube which can result in clogging.
[00019] The methodologies taught by this group of patents (US Patent Nos. 5,984,992; 6,159,263; 6,758,879 and 7,128,880) are attacked by problems related to the clogging of these “cross tube” reactor configurations narrow (with respect to their length), the very short duration of the reaction time in such "cross tube" reactors and the difficulty of controlling the reaction temperature and the pressure and retention time of the mixture within such tube reactors crossed. These cross tube reactors are narrow in contrast to their length, for example, up to six to eight inches in diameter and usually fifteen feet in length or more. The plant practicing the manufacture of organically improved ammonium sulfate fertilizers usually needs to shut down and disassemble the cross tube reactor both due to blockage from biosolids buildup and destruction by heating in such reactors such that the Teflon® coating commonly used on the inner reaction side of the reactor melts and is ruined. Additionally, the use of the cross tube reactor has the distinct disadvantage of having very short reactor times (commonly less than twenty seconds) which is an advantage in the manufacture of traditional fertilizers like ammonium sulphate, but is a disadvantage when coupled with simultaneous processing of biosolids. Such short processing time increases the probability of inhomogeneous or untreated mixing as the three material inputs pass through this reactor. This further limits the lack of control over atmospheric pressure within such cross tube reactors as these reactors commonly have open end discharges directly to a granulator. Related to, but distinct from, the lack of control of internal pressures, cross tube reactors also have little to no temperature control over the passage of the mixture through the reactor.
[00020] Robinson's US Patent No. 4,743,287 describes a method for using two sequential reaction vessels to incorporate organic biosolids into low or medium nitrogen concentration nitrogen fertilizers (a range of four percent by weight of nitrogen up to a maximum nitrogen concentration of ten percent by weight). Robinson uses his first reaction vessel to achieve very low pH values of the mixture (pH 0.2 to 1.5) to achieve hydrolysis of molecules present and to prepare the mixture for reaction in a second reaction vessel. Robinson indicates that a single reactor can be used, but only in a batch configuration and not in a continuous-flow fabrication method. Robinson also indicates that acid and ammonia cannot be injected in any order, but must be injected sequentially. This patent describes reaction vessels capable of achieving high pressures (30 psig) with relatively long retention times compared to cross tube reactors. However, Robinson fails to satisfy the need for a new and practical continuous flow method of manufacturing fertilizer products with high nitrogen content (greater than 8 percent by weight Nitrogen) and fertilizer products that contain biosolids under the advantages of defined reaction temperatures, pressures and retention times.
[00021] Thus, an urgent need exists for an effective, efficient, and cost-effective process to treat biosolids. In addition, there is an urgent need for a variety of fertilizers that can be specifically tailored for a particular crop such that the nutrients provided by the fertilizer follow the nutrient needs of the crops over a particular period or even a growing season. Invention Summary
[00022] The present invention overcomes the problems and disadvantages associated with current strategies and designs, and provides new tools and methods for the manufacture of fertilizers.
[00023] An embodiment of the invention is directed to methods for manufacturing a fertilizer with a predetermined nutrient release profile comprising: conditioning an amount of an organic material to a predetermined degree of moisture, wherein the type and/or amount of organic material establishes the fertilizer's slow-release nutrient profile; adding an odor control agent to the conditioned organic material to form a mixture; transferring the mixture to a first vessel in which a concentrated acid is added creating an exothermic reaction, wherein the amount of acid added creates a predetermined temperature forming a liquid mixture; stir the acidified mixture for a first period of time; transferring the liquid mixture under pressure to a second vessel in which an amount of anhydrous ammonium is added sufficient to further increase the temperature and pressure of the liquid mixture such that the liquid mixture contains a predetermined amount of nitrogen; stir the liquid mixture in the second vessel for a second period of time; and discharging the liquid mixture from the second pot to form fertilizer with a predetermined slow release profile of nitrogen, sulfur and/or phosphorus. Preferably the nutrient release profile is a profile of the release of one or more of nitrogen, phosphorus, potassium, sulfur, iron, organics and combinations thereof, and in general can correspond to the growth needs of a particular crop for a particular crop. or more of nitrogen, phosphorus, potassium, sulfur, iron, organics and combinations thereof. Preferably the nutrient release profile comprises the rate, amount and/or differential release of one or more nutrients from the fertilizer. Preferably organic material comprises one or more of municipal biosolids, heat-dried biosolids, pharmaceutical fermentation residues, microbial digestions of organic products, agricultural waste products, digested food products and food products, food by-products, animal sewage, digested animal sewage, organic biosolids, biosolids containing microorganisms, plant biosolids from wastewater, liquid organic fractions extracted from municipal solid waste, animal waste and digested animal waste, algae collected from eutrophic surface water sources, iron humates containing fulvic acid and/or humic acid, and combinations thereof, and also that plastic and hair that may be present do not require removal prior to processing as they are liquefied. Preferably additional ingredients are added such as, for example, zinc sulfate and/or soluble forms of boron, nutrients, peptides, vitamins, polypeptides, amino acids, saccharides, polysaccharides, herbicides and/or pesticides to the organic material, the mixture and/ or the liquid mixture. In addition, one or more agents that create and/or reduce that electrostatic state of the organic material can be added to the organic material, the mixture and/or the liquid mixture. Such agents include, but are not limited to one or more of anionic and cationic chemicals, chelating agents, ion sequestering agents, metal ions, citric acid, amino acids, glutamic acid, histidine, lysine, glycine, peptides, proteins, sugars, saccharides and polysaccharides, iron, sulfur, phosphorus and nitrogen-binding compounds and combinations thereof. Preferably the predetermined degree of moisture comprises a solids percentage of 15 to 30%, and most preferably the aqueous liquid removed from the organic material is recycled. Preferably the odor control agent comprises one or more of calcium ferrate, sodium ferrate, potassium ferrate, ferrous sulfate heptahydrate, rozenite, melanterite, ferric chloride, ferrous sulfate, ferrous sulfate monohydrate, hydrogen peroxide, ozone and salts, derivatives and combinations thereof. Preferably the concentrated acid comprises sulfuric acid or phosphoric acid concentrated to 90% or greater, the amount of acid creates a temperature of 100°C or greater, the first time period is 2 to 20 minutes, the second vessel has a pressure of 2 atmospheres or greater and a temperature of 120°C or greater, the second time period is 5 minutes or greater, and discharging comprises coating the liquid fertilizer onto recycled fertilizer granules (an alternative embodiment may be where the first and second vessels may be at ambient pressures or close to ambient pressures). Preferably the liquid mixture has a viscosity of 2000 cP or less which increases after the addition of anhydrous ammonium. Still preferably the coated recycled fertilizer granules are dried to a solids content of 98% or greater. Preferably a stiffening agent is added to the fertilizer such as, for example, lignosulfonate, molasses, alum or a combination thereof or where the stiffening agent is used. Preferably the fertilizer is formed into granules and granules are sorting granules by size. Preferably granules between 0.5 and 4 mm are selected, and granules which are larger than 4 mm are crushed and combined with granules which are smaller than 0.5 mm and comprise recycled fertilizer granules. Preferably the predetermined amount of ammonium is that amount that creates 5% or more nitrogen in the fertilizer.
[00024] Another modality of the invention is directed to the fertilizer made by the methods of the invention. Preferably fertilizers, when applied to a crop, release nitrogen and other nutrients to the soil at a slower rate than nitrogen release by inorganic fertilizers containing the same nutrients such as urea as a source of nitrogen. Preferably the nutrients comprise one or more of nitrogen, phosphorus, potassium, sulfur, iron, manganese, magnesium, copper, calcium, selenium, boron, zinc and combinations thereof, and also preferably are chelated or electrostatically bound with organic matter of the fertilizer. Preferably the fertilizers are homogeneous in composition, non-hygroscopic and black or otherwise very dark in color. Preferably fertilizers improve soil tillage, crop stress resistance to heat and drought, and soil microecology compared to non-organic fertilizer. Still preferably, fertilizers of the invention have a hardness between 4 and 9 pounds, even more desirably between 6 and 8 pounds and/or a bulk density between 52 and 56 pounds/cubic foot, and 8 to 17% nitrogen, of 0 to 10% phosphorus, 0 to 10% potassium, 5 to 20% sulfur 5 to 20%, 0 to 5% iron and 5 to 20% organics. Still preferably, fertilizers, once applied to a crop, provide one or more nutrients to the crop sufficient for all or a portion of a single growing season.
[00025] Another embodiment of the invention is directed to methods for manufacturing a fertilizer comprising: providing an organic material that preferably contains municipal organics wherein the organic material has a solids content of at least eight percent; optionally adding an odor control agent to the organic material to create a mixture; adding an acid to the mixture under a first pressure and elevated temperature for a first period of time forming a liquified mixture; add ammonia to the liquefied mixture under a second pressure and elevated temperature for a second period of time; and processing the liquefied mixture to form the fertilizer. The phrase organic material includes all biosolids, but is not limited to biosolids such as organic biosolids, biosolids containing microorganisms, municipal biosolids or heat-dried biosolids, and also includes laboratory and pharmaceutical processing and fermentation residues, agricultural and farm waste , digested and decayed organic materials, mined humates and fulvic and humic acids, harvested plants including the cultivated harvest materials such as forage and corn silage and soy plants as well as wheat, rice and barley plants, algae and cyanobacteria which may be harvested from lakes and other bodies of water, bacteria, mold and fungi, industrial waste and its by-products, microbial, chemical and enzymatic digestion of organic products, animal and plant foods, food products, and by-products, recycled fertilizers, and all combinations thereof. One element of the invention is that organic material containing plastic and hair and similar material does not need to be removed before processing. Preferably, the organic material is dehydrated or hydrated to a solids content between 14 and 40 percent, more preferably the organic material has a percent dryness of about 22 percent plus or minus 5 percent. In addition, a portion of the organic material can be dehydrated to a dryness greater than 70 or 85 percent, and mixed with the remaining portion of the organic material to achieve a desired percent dryness. Preferably, the organic material is hydrated with process water recovered from one or more method steps to minimize or prevent any loss of nutrient-containing water.
[00026] Optionally, odor control agents can be added to the organic material. Preferred odor control agents include, but are not limited to, one or more of calcium ferrate, sodium ferrate, potassium ferrate, ferrous sulfate heptahydrate, rozenite, melanterite, ferric chloride, ferrous sulfate, ferrous sulfate monohydrate, ferrous sulfate heptahydrate , ferric humate, hydrogen peroxide, ozone and salts, derivatives and combinations thereof, as well as various salts thereof. Preferably, the mixture of the organic material with the odor control agent forms a thixotropic mixture. The mixture can optionally be heated prior to addition of acid, which is useful in climates where organics are kept at about 4°C (about 40°F). Still preferably, process heating is carried out in a first pressure vessel and the first pressure is maintained between 20 and 60 psig, the first temperature is between 66°C (150°F) and 127°C (260°F), and the first time period is between 2 minutes and 30 minutes. More preferably, the first temperature can be between 93°C (200°F) and 121°C (250°F) and the first time period can be between 5 minutes and 10 minutes. Preferably the viscosity of the heated acidified mixture is about 1000 cP or less. The acid added to the mixture is preferably a phosphoric acid, a sulfuric acid, or a combination thereof. After acidification, the liquified mixture is transferred to a second pressure vessel and, preferably, ammonia is heated under pressure to form a gas before being added to the liquified mixture. The second preferred temperature in the second pressure vessel is between 121°C (250°F) and 199°C (390°F), the second preferred time period is between 1 minute and 30 minutes, and the preferred pressure within the second pressure vessel is maintained between 30 and 150 psig. The viscosity of the ammonia mixture is preferably about 1200 cP or less. Processing of liquefied mixture comprises forming the useful fertilizer. Preferably, processing comprises drying the blend to a solids content of greater than 92 percent, or more preferably to a solids content of at least 98 percent. One or more stiffening agents may be added during processing such as, for example, lignosulfonate, molasses, alum or a combination thereof. Preferably processing is carried out in a granulator to form granules and the granules are sized and granules between 0.5 and 4 mm selected. Preferably, granules of greater than 4 mm are further crushed, and combined with granules of less than 0.5 mm, and both are added during processing. An element of the invention is that each step of the method can be carried out in a continuous process without interruption, although batch processing is also possible. The processes of the invention preferably also comprise a dust control system that collects and recycles dust material created from the processing.
[00027] Another modality of the invention is directed to the fertilizer manufactured by the methods of the invention. Fertilizers will typically contain hydrolyzed polymers from one or more of plastics, pharmaceutical compounds, antibiotics, hormones, hormone-like molecules, biologically active compounds, macromolecules, carbohydrates, nucleic acids, fats, lipids, proteins, and microorganisms that are present in biosolids. Preferably the hydrolyzed polymers are polypeptides and amino acids of various chain lengths, most of which are not destroyed during the processing method, which supplement and substantially increase the value of the fertilizer. Preferably, the fertilizer of the invention has a nitrogen content between 6 and 20 percent, a phosphate content between 0 and 10 percent, a potassium content between 0 and 5 percent, a sulfur content between 9 and 25 percent, an iron content between 0 and 10 percent, and an organic content between 4 and 30 percent. Yet preferably, the fertilizer has no or almost no unpleasant or bad odors.
[00028] Another modality of the invention is directed to processes for the manufacture of a fertilizer with a predetermined content of one or more of nitrogen, phosphate and potassium comprising: providing an organic material containing biosolids in which the organic material has a solids content of at least eight percent; optionally adding an odor control agent to the organic material to create a mixture; adding an amount of a predetermined acid to the mixture, thereby creating an exothermic heat hydration reaction and forming a liquified mixture; add a predetermined amount of ammonia to the liquefied mixture under pressure and heat the mixture to a second temperature for a second period of time, wherein the amount of ammonia added is determined from the composition of the organic material and the amount of acid contained ; and processing the liquefied mixture to form fertilizer with a predetermined pH that is compatible with the soil and crop with predetermined content of one or more of nitrogen, phosphate, potassium and sulfur. The process of the invention optionally may further comprise adding one or more plant nutrients even during processing. Such plant nutrients that can be added include, but are not limited to one or more of urea, ammonium nitrate, ammonium sulfate, monoammonium phosphate, diammonium phosphate, urea ammonium nitrate, liquid urea, potash, iron oxide, soluble iron, chelated iron and combinations thereof. The process preferably further comprises adding and one or more stiffening agents during processing such as, for example, ferric oxides, attapulgite alum clay, industrial molasses, lignin, lignin sulphonate, urea formaldehyde polymerizer and combinations thereof. The process can also be carried out without a hardening agent such as, for example, when the granules produced are of acceptable hardness for use.
[00029] Another modality of the invention is directed to systems for the manufacture of a fertilizer comprising: a mixer that mixes municipal organics with an odor control agent; a first pressure or reaction vessel in which the mixed organic materials are mixed with an acid and heated to a first predetermined temperature and pressurized to a first predetermined pressure for a period of time forming a liquid; a second pressure or reaction vessel in which the liquid is mixed with ammonia from an ammonia source and heated to a second predetermined temperature and pressurized to a second predetermined pressure for a second period of time; and a rotary granulator in which the ammonia-containing liquid is mixed with preformed granules to form dry granules of the fertilizer. Preferably the source of ammonia is liquefied or gaseous ammonia under pressure and each of the first and second pressure or reaction vessels contains an agitator. Systems can also include a screening process to select product sized fertilizer granules, and one or more of a coating and cooling apparatus to reduce temperature and dust control prior to storage. Optionally, the cooler can include an ozone generator that provides ozone to the coolant fertilizer to eliminate or at least substantially reduce remaining unpleasant odors. Preferably, the systems also comprise a conveyor for transporting municipal organics to the blender and another conveyor for transporting the mixed organics to the first pressure or reaction vessel; a pressurized piping system that transports acidified biosolids from the first pressure or reaction vessel to the second pressure or reaction vessel, ammonia to the second pressure or reaction vessel; and disperses the liquid with ammonia, commonly as a spray, into the granulator. Preferred systems further comprise one or more screens to select granules of a predetermined size and a rotary cooler to cool and polish the sized granules, and both a dust control apparatus that collects and recycles dust from the granulator and a dust recovery system. water in which water extracted from biosolids during processing is recovered and recycled. In certain embodiments, the first and/or second pressure or reaction vessel may be a cross tube reactor, or both the reaction and pressure vessels are cross tube reactors. The process can be carried out as a continuous or batch process.
[00030] Another embodiment of the invention is directed to methods for manufacturing a product comprising: providing an organic material in which the organic material has a solids content of at least eight percent; adding an acid to the organic material under an elevated temperature for a first period of time forming a liquified mixture; add ammonia to the liquefied mixture under a high pressure and temperature for a second period of time; and processing the liquefied mixture to form the fertilizer. Preferably the organic material is bacterial or plant material and or digested food or food material, further preferably a bacterial or plant material is algae, bacteria, fungi or a combination thereof. Preferably there are toxic materials present in organic materials that are hydrolyzed or otherwise rendered non-toxic or inactivated by the process of the invention. Preferably there may only be ambient pressure in the first vessel when the elevated temperature is between 66°C (150°F) and 127°C (260°F) and the first time period is between 2 minutes and 30 minutes. Still preferably, the second pressure and elevated temperature for a second period of time are, respectively, between 30 and 150 psig and between 121°C (250°F) and 204°C (400°F), between 1 minute and 30 minutes . Preferably the product is a fertilizer.
[00031] Another embodiment of the invention is directed to fertilizer manufactured by the methods of the invention. Preferably, fertilizers of the invention have both slow and fast nitrogen release profiles such that a percentage of available nitrogen is released to the soil within 0 to 14 days of fertilizer application, preferably 10 percent to 70 percent, and a second slower release which represents about 30 percent to 90 percent of the available nitrogen content of fertilizer releases to the soil over a period of 2 weeks to 4 months following application. Preferably, nitrogen release is timed to match the needs of growing plants or crops.
[00032] Other embodiments and advantages of the invention are defined in part in the description, which follows, and in part, it may be obvious from this description, or it may be learned from the practice of the invention. Description of Figures
[00033] Figures 1A-C. Fertilizer Plant Flow Chart of an embodiment of the invention illustrated by: unloading municipal organics (Figure 1A); to the reactor (Figure 1B); and for drying (Figure 1C).
[00034] Figures 2A-C. Fertilizer Plant Flow Chart of another embodiment of the invention illustrated from: municipal organic discharge (Figure 2A); to the reactor (Figure 2B); and for drying (Figure 2C).
[00035] Figure 3. Schematic of a modified ammonium sulfate process of an embodiment of the invention.
[00036] Figure 4. Physical and chemical characteristics of organically modified ammonium sulfate fertilizer of an embodiment of the invention.
[00037] Figure 5. The organic matrix provided by the invention showing a variation of binding capabilities.
[00038] Figure 6. Nitrogen release curve showing percent nitrogen release to the soil over the number of days for ammonium sulphate (AS), organically modified ammonium sulphate of the invention (Anuvia), and conventional biomass (MILORGANITE).
[00039] Figure 7. Academic nitrogen release curve of plants fertilized with ammonium sulfate, organically modified ammonium sulfate of the invention, and biosolids showing percent nitrogen release to the soil over the number of weeks.
[00040] Figure 8. Soil nitrogen leach in tomato crop as influenced by nitrogen source.
[00041] Figures 9 (A-C). Results from a controlled condition nitrification study using Anuvia product (Figure 9A), using urea (Figure 9B), and using urea plus agrotain (Figure 9C).
[00042] Figure 10. Treatment effects of endocrine disrupting chemicals (EDC) seeded in biosolids.
[00043] Figure 11. Graph showing percent nitrogen releases over time for selected materials. Description of the invention
[00044] All countries and population regions around the world create waste in the form of organic materials. The phrase organic material includes, but is not limited to biosolids such as organic biosolids, biosolids containing microorganisms, municipal biosolids and heat-dried biosolids, and also includes laboratory and pharmaceutical processing and fermentation residues, agricultural and farm waste, organic materials digested and decayed, harvested plant and plant-like materials such as algae including blue/green algae, bacteria including blue/green bacteria, cyanobacteria (eg blue/green, rust, black), mold and fungi, humates, humic acids and Fulvic acids, industrial waste and its by-products, microbial, chemical and enzymatic digestions of organic products, animal and plant foods, food products, and by-products, animal sewage, processed and digested animal sewage, recycled fertilizers, and all combinations thereof . Disposal of organic waste materials is a major issue as well as expense for all communities. Traditional disposal methods involve burying, burying at sea or incineration. Each of these options addresses the problem by creating unsustainable amounts of pollution that penalize the community as well as the planet. New techniques have been developed that involve heat treatment to inactivate microorganisms and other potential contaminants that can result in a product that can be like a low-value fertilizer. Although these techniques sound ecologically, they have not caught on as, for the most part, the product is of such low value that there is little to no commercial incentive for communities to switch from the traditional burning and burying philosophy, and no fund that allows the creation of secure processing facilities.
[00045] Surprisingly it has been found that high value fertilizers with predetermined and specific release profiles of one or more nutrients can be efficiently manufactured from organic materials, including but not limited to raw or semi-processed organic materials such as biosolids, materials agricultural and industrial waste. Such fertilizers can be specifically tailored to crops so that the release profile of the fertilizer matches the needs that arise during the growth and development of the particular crop. In addition, the process of the invention not only destroys all potentially harmful microorganisms, but hydrolyzes many polymers including forms of biopolymers (eg, DNA, proteins, carbohydrates, toxins, antibiotics, hormones, etc.), forms of composite materials, and even plastic shapes. The resulting fertilizer product is of high value and still contains hydrolyzed monomers (eg amino acids, sugars, etc.) that are beneficial and desirable for a fertilizer.
[00046] The process of the invention allows the production of fertilizers with pre-selected release profiles that can be adapted to specific crops. Unexpectedly it was found that the nutrient content of the selected organic material is not determinant of the release profile. In other words, a fertilizer consisting mostly of algae such as organic matter, which is relatively high in nitrogen, will not have a nitrogen release profile that is significantly different from a fertilizer made from organic material with a low content. of nitrogen. What was found is that the release profile is determined by the electrostatic state or condition of the organic material (see Figure 5). Organic material that has a greater ability to bind and retain, for example, ferrous iron, when processed in accordance with the invention will have a specific release profile for ferrous iron. Similarly, organic material that has a greater ability to bind and retain, for example, nitrogen, when processed in accordance with the invention will have a specific release profile for nitrogen. In other words, the quantity and type of organic materials can be manipulated in processing according to the invention to predetermine the fertilizer release profile. Thus, fertilizers can be created with nutrient release profiles that closely or exactly match the nutrient requirements of the particular plant or crop. The availability of specific nutrients can determine one or more growth characteristics of a plant. For example, making a certain nutrient or combination of nutrients more or less available to a plant during various aspects of a growth cycle can shift growth to more or less seeds, more or less flowers, more or less leaves, fruits, or global biomass, or various combinations thereof. The growth characteristics of various plants are well known to those skilled in the art, and the fertilizer can be matched with the particular growth characteristics desired.
[00047] In addition, it has also surprisingly been found that the release profile of organic material can be changed by combining different organic materials and/or adding one or more agents that create and/or reduce that electrostatic state of the material. organic. Various such agents include, for example, anionic and cationic chemicals, chelating agents (eg EDTA, EGTA), ion sequestering agents, metal ions, citric acid, amino acids (eg glutamic acid, histidine, lysine, glycine), peptides, proteins, sugars, saccharides and polysaccharides, iron, sulfur, phosphorus and nitrogen binding compounds, and other chemical compounds and chemicals as well as those known to those skilled in the art. The rate, amount and/or type of fertilizer component released includes, but is not limited to nitrogen, phosphorus, potassium, sulfur, iron, organic components and combinations thereof. The electrostatic state of large collections of different organic matter was surprisingly consistent, although a difference may exist between types. The electrostatic state of organic materials is known or easily determined to those skilled in the art. Regardless, procedures for determining the electrostatic state of a particular organic material or collection can be determined using commercially available equipment by those skilled in the art. As discussed here, this difference can be used by the methods of the invention.
[00048] Thus, fertilizers can be manufactured for the entire growing season or for parts of a growing season for any particular crop. With a nutrient release profile that matches the entire growing season of a specific crop, the invention's fertilizer only needs to be applied once. If nutrient requirements change during a growing season, two or more fertilizers of the invention can be applied at appropriate times during crop growth and development. As the nutrient requirements of agricultural crops are very well known, a person skilled in the art need only pre-select, according to the invention, desired nutrient release profiles for the fertilizer.
[00049] The present invention allows the generation of an ecologically and financially circular economy. This occurs ecologically when organic in terms of food from the farm is consumed by society, organic waste is successfully created and incorporated into a high nutrient content fertilizer and returned to the farm to benefit the health of the soil. This is achieved financially when the fertilizer is manufactured and funds are paid to community businesses for the chemical inputs to create said fertilizer. Once the fertilizer is manufactured it is sold back to community farms to create the soil nutrient environment necessary for optimal crop production.
[00050] An embodiment of the invention is directed to methods for manufacturing a fertilizer with a predetermined release profile of one or more nutrients. The release profile can comprise the amount, rate and/or differential level of release of one or more of the nutrients from the fertilizer. A schematic of the general process of the invention is represented by Figure 3. The method comprises providing an organic material which may contain biosolids or other organic material to which, optionally, an odor control agent is added, which itself can be used as a important plant nutrient in the final fertilizer product, to reduce or eliminate odors that may be present from the organic material or other components of the starting materials. The organic material and/or mixture optionally can be heated. Heating is generally needed in environments where the climate temperature is below 10°C such as below 4°C. The resulting mixture, which may contain added water recycled from other method steps, is preferably mixed thoroughly. To this mixed material is added an acid that reacts exothermically with the organic material and the water in which it is suspended in the resultant increases in both temperature and pressure (when the mixture is contained in a pressure-tight reaction vessel) . The desired temperature rise can be determined by the amount and concentration of the particular acid selected and/or the incubation period. During this time, preferably two to ten minutes, the components are partially or fully liquefied. One skilled in the art can determine the time required for mixing and the intensity of mixing with more vigorous mixing for a short time, or less vigorous mixing for longer times. To the heated liquefied material, which is transferred, preferably under pressure, to a second pressure vessel, ammonia is added, which is preferably also liquefied or vaporized and also under pressure, and the subsequent reaction with the acid component of the mixture serves to further increase plus the temperature and pressure. The liquefied and ammonia-containing biosolids are held for a short period of time under these conditions, preferably two to ten minutes, and then processed, preferably into fertilizer granules. This modality can also be achieved, less efficiently, but sufficient to form a fertilizer melt, if the acidified mixture is transferred to a second vessel which is maintained at ambient pressure conditions during the addition of ammonia.
[00051] The ammonia reaction can be carried out to the end where all or almost all of the acid is reacted such that the result is a fluid with a viscosity of less than 1200 cP in the form of a fertilizer melt. The combination of acid and ammonia creates a molten mass of salt (a partially ammoniated mixture) (for example, with sulfuric acid the salt produced is ammonium sulphate) that retains fluidity to allow dispersion, such as, for example, spraying, to a granulator that can contain recycled fertilizer material. Preferably, with ammonia salt to melt ratios about 20/80, about 25/75, about 30/70, about 35/65, about 40/60, about 45/55, about 50/50, about 55/45, about 60/40, about 65/35, about 70/30, about 75/25, and about 80/20. The purpose of these reasons is to maintain the fluidity of the melt. If neutralization by ammonia is carried out to completion a complete salt is formed and fluidity may be insufficient to transfer the mixture to a granulator to shape and form the granules. Salt formation can be determined in real time by measuring the pH of the mixture. Preferred melt pH values are between 2.0 and 4.0. It is preferable to partially ammoniate the acid mixture in the reactor (thus forming a molten mass) and complete the ammonia in a second vessel (eg pugmill) or in the granulation process such as a granulator.
[00052] An advantage of this invention is that, since organic materials are liquefied, the liquid can be transported more easily as needed through tubes preferably using pressure differentials compared to any solid, semi-solid or thixotropic material. The liquefied organic materials can also be applied more equally to an acceptor material in the granulator thereby allowing the formation of an equally shaped spherical shaped granule. Although spherical shapes are commercially preferred, any bead shape can be created by one skilled in the art using commercially available equipment. Organic materials are preferably fully liquefied, although mostly liquefied is typically sufficient. Preferably the liquid exhibits a characteristic readiness to flow, little or no tendency to disperse, and relatively high incompressibility.
[00053] Viscosity of organic starting material typically is in excess of 100,000 cP and typically 150,000 cP at room temperature and does not change significantly even at elevated temperatures typical of a processing facility. For comparative purposes, at approximately room temperatures, molasses has a viscosity of about 5,000 to 10,000 cP, honey has a viscosity of about 2,000 to 10,000 cP, chocolate syrup has a viscosity of about 900 to 1,150 cP, and oil of olive has a viscosity of about 81 cP. With the addition of acid and heat according to the invention, the viscosity of the organic material decreases to a range of about 500 to 5,000 cP, and preferably to less than 4,000 cP, more preferably to less than 3,000 cP, more preferably to less than 2,000 cP, and more preferably even less than 1,000 cP. With the addition of ammonia and the added temperature increases from the resulting exothermic reaction, the viscosity increases to a range of 500 to 4,000 cP, and preferably to 2,000 cP or less, more preferably to 1,500 cP or less. Furthermore, problems typically associated with solid debris that are normally present in organic material such as wastewater biosolids, with debris such as plastic and hair, are eliminated as all such material is hydrolyzed also resulting in a decreased viscosity.
[00054] The low viscosity material of the invention facilitates the manufacture of fertilizer allowing the establishment of control related to temperature, pressure and reaction time. Fluidity is advantageous such that problems and inefficiencies commonly associated with clogging solid debris or otherwise blocking transport from one vessel to another and thus necessitating system shutdown for maintenance are eliminated. No solids or semi-solids are present that would otherwise increase wear and tear on the equipment and thus shorten the life of the equipment. Additionally, solid organic materials including, for example, plastic and hair, well known to cause blockages in conventional processing, are completely broken down and hydrolyzed to their monomer components. The acidic reaction hydrolyzes many polymers that may be present such as proteins and other materials including plastics, hair, and biologically active compounds (whether naturally present or artificially created), and disrupts and destroys many, nearly all and preferably all macromolecules and microorganisms that may be present. The environment of acid and subsequent ammonia creates a molten mass of sterile fluid. This increases safety for process workers and additionally simplifies and increases the efficiency of any system cleaning or maintenance that may be required on a periodic basis. This hydrolysis further increases the safety of use of the resulting fertilizer product compared to other fertilizer products that contain additional organics such as those made in alkaline stabilization of biosolids or compost or traditional Class B land application processes. The fertilizer produced is sterile thus meeting the strictest USEPA Class and EQ microbial standards.
[00055] Another advantage of the invention is that, as the process can be easily contained, the need for odor and dust control apparatus within the manufacturing plant is minimized. Processing steps are closed and under negative pressure and no steps are performed in open or areas exposed to the environment or the environment of the installation. Odor control agents are preferably added initially, but optionally can as easily as possible be added at any stage of the process. The key to this invention is that the physicochemical conditions created in the described embodiments eliminate noxious odors from the resulting fertilizer. Alternatively, or in addition to other odor control processing, the granules can be exposed to ozone during formation and/or refrigeration. Ozone will substantially reduce or eliminate unpleasant fertilizer odors. The manufacturing plant features a robust process odor control treatment such that no harmful odors from reduced sulfur compounds, amines, or other organic related odors are present in the manufacturing fence line. Thus the invention is a major improvement compared to conventional fertilizer manufacturing practices where a large manufacturing facility is located as far away from communities as possible thus requiring input materials to be shipped long distances to operate the plant. A good example of this odor problem was the biosolids fertilizer conversion plant located in Helena, Arkansas that practiced the manufacturing processes taught in US Pat. 5,984,992; 6,159,263; 6,758,879; and 7,128,880, and used biosolids that were transported from New York City. This AR plant did not have the necessary odor control system to eliminate harmful odors from being released into the environment.
[00056] Another advantage of the invention is that, as the acid and ammonia are added in a controlled manner, the final components of the fertilizer can be predetermined. The exact amount of nitrogen in the final product can be regulated based on the amount of starting materials including biosolids, acid, base, water, and any other components. Similarly, the exact amount of sulfur, iron, phosphate, potassium and even organic matter can also be regulated or, if desired, eliminated from the final product producing a custom-made fertilizer product. Many crops that require fertilization are grown in areas known to be high in phosphate, sulfur, potassium or other elements. Fertilization with conventional fertilizers, while necessary, typically exacerbates contamination. Fertilizers produced by the methods of the present invention may not only overcome these problems, but may be adapted for use in conjunction with a specific type of soil or the specific need of a select type of crop. In addition, the process of the invention allows for fertilizer supplementation during processing with additional ingredients.
[00057] Another disadvantage of the invention is that it is easily carried out on a large scale, with continuous processing and under automation. No significant retention time is required, thus no delay, so processing continues from start to finish without interruption as may be necessary when material is required to incubate for days as is common for some types of biosolids processing conventional as in composting or alkaline stabilization processes. The process of the invention is scalable to any amount of organic material. This is quite preferred at least as most municipal regions vary in size and thus the amounts of organics such as biosolids produced per day vary widely. Also, quantities are expected to also vary over time. Additionally, each step of the process can be performed under full automation including taking into account the necessary variation per day and over time.
[00058] Another advantage of the invention is that it goes to the placement of facilities for processing organic materials such as biosolids with municipal wastewater treatment plants. Biosolids can then be taken directly from wastewater treatment plants for processing in this way minimizing the transport and potential spillage of potentially hazardous compounds. Another preferred embodiment is to locate close enough to the wastewater treatment plant to be connected by a screw or belt conveyor or a sewage sludge pumping system. Alternatively, another preferred embodiment is to locate adjacent to the wastewater plant. The aim of the present invention is to position the processing plant as close to the wastewater plant as possible. Thus the present invention eliminates most of the transportation cost by locating the physical equipment needed to carry out the manufacturing process adjacent to or close to the biosolids source such as municipal wastewater treatment plants. Fabrication plants of the invention preferably allow for adjacent storage facilities. Again, by being adjacent, transport logistics are simplified or eliminated thereby reducing product transport costs as well as transport costs for inbound organics such as biosolids. Furthermore, the processes of the invention have the advantage that they can be interfaced with other production facilities. These facilities can be associated with an unrelated business venture. Additionally and more commonly, co-locating close to a commercial enterprise that creates excess heat, such as in an oven, or stove, can advantageously allow the use of excess heat by the present invention as in replacing the need for fossil fuels such as natural gas or by co-generating electricity using said excess heat.
[00059] Another advantage of the invention is that as the process minimizes the amount of water and energy (for example, electrical) needed, and the amount of residual by-products formed, compared to conventional processing, the fabrication can be scaled for the service as needs of the size of the particular community in which the plant is located. This retrofit project allows for a fertilizer manufacturing/biosolids processing plant that can process smaller amounts of biosolids (eg less than 3 tons per hour of dehydrated biosolids) or scaled up to larger plants (eg up to 20 tons per hour or more) . In a preferred modality the optimum size is between 10 and 12 tons per hour, which allows local operations and does not require long-distance transport of raw materials.
[00060] Types of community organics that can be used in this invention include municipal biosolids, domestic sewage, agricultural and farm waste, animal sewage, processed and digested animal wastewater, recycled biosolids fertilizers, organic biosolids, biosolids containing microorganisms, and biosolids dried by heat. Other organic materials that can be processed in accordance with the method of the invention include, but are not limited to laboratory and pharmaceutical processing and fermentation residues, organic industrial waste, microbial materials, digested and decayed organic materials, humate and humic acids, and acids fulvic, agricultural and farm waste, collected plant materials such as algae including blue/green algae, kelp and other aquatic plants and aquatic organic debris, bacteria including blue/green bacteria and cyanobacteria (eg blue/green, rust, black), slime, insects and insect biomass (eg body parts, dung), mold and fungi, industrial waste and its by-products, microbial, chemical and enzymatic digestions of organic products, food, food products and food by-products , and combinations thereof. In addition to conventional biosolids, most all organic materials can be processed by the methods of the invention including spoiled or otherwise rotten food products such as, but not limited to vegetables, meat, fish, and agricultural products as well as plastics, and household waste that contains carbon and recyclables.
[00061] Another advantage of the invention is that organic materials, and even in combination with certain non-organic materials, which are otherwise difficult to dispose of can be processed according to the invention as a method of transforming into a useful product than otherwise. shape can be waste material that takes up space in a landfill or the ocean. By way of non-limiting example, algae are scraped from the surface or otherwise collected from eutrophic bodies of water for aesthetic purposes as well as for the general health of the plants and animals that inhabit the environment. Generally algae can be contaminated with natural toxins or toxic compounds absorbed or metabolized and concentrated within the algae from the environment. By processing the algae according to the methods of the invention, the algae can be converted to fertilizer and, importantly, the toxins destroyed or otherwise inactivated. In addition, algae or other plants or bacteria can be intentionally grown and collected to be processed in accordance with the invention.
[00062] The organic material is preferably dehydrated or hydrated to a solids content between 10 and 40 percent, more preferably between 15 and 30 percent, and most preferably between 20 and 25 percent. The optimal solids content of a particular organic material can also be determined empirically or experimentally. Organic material received for processing in accordance with the invention will typically have a lower solids content than the optimum level. Preferably, the organic material of insufficient solids content can be adjusted to the desired concentration by mixing with "dry" organic materials having a solids concentration of 70 to 95 percent and preferably 85 to 92 percent. “Dry” organic materials can be available through third party sources or can be produced with the available organic material through heat drying. Heat drying processes include heated screw conveyors, disk dryers, rotary dryers, block dryers/mixer, fluid bed dryers and other commercially available equipment/processes. Dry organic materials and organic material of insufficient solids concentration will be mixed in a mixing vessel to achieve the ideal solids content as determined empirically or experimentally. The mixing vessel can be a pugmill, screw mixing conveyor, multi-shaft mixer, ribbon paddle mixer, high shear mixer, static mixer or other commercial high viscosity slurry mixer. Less preferably, organic material of insufficient solids content can be adjusted to the desired concentration by heating the material to remove water as necessary to achieve the desired concentration. This can also be done on the same heat drying equipment listed above. Organic materials received for processing may need hydration and, when necessary, additional water is preferably added from water collected during other processing steps. This use of recycled water further adds to both the efficiency and beneficial economics of the invention.
[00063] If necessary during inlet processing, the organic material can be conditioned by the injection of steam, water, and/or heat (eg, thixotropic) and/or subjected to violent agitation and physical interruption to allow or improve the flow or the movement. In these initial steps, the organic material can be mixed with chemical additives such as oxidizing agents or iron-containing compounds, for initial odor control and to prepare the biosolids for the pressure vessel reaction. For example, biosolids can be infused with agricultural grade phosphoric acid or black to minimize odors. In this example, the phosphoric acid added here will change the final phosphate concentration in the fertilizer product. The amount of phosphate added to the product at this step can be as low as 0.5 percent and as large as 16 percent. In addition to odor minimization, phosphoric acid adds a valuable nutrient component to the fertilizer product.
[00064] Preferably the odor control agent is added to the starting organic material to be processed, although one or more odor control agents may be added at any time during processing including during granulation and refrigeration. Preferred odor control agents include, but are not limited to calcium ferrate, sodium ferrate, potassium ferrate, ferrous sulfate heptahydrate, rozenite, melanterite, ferric chloride, ferrous sulfate, ferrous sulfate monohydrate, hydrogen peroxide, and/or ozone as well as various other salts, derivatives and combinations thereof. The amount and type of odor control agent can be determined empirically by one skilled in the art, but typical amounts range from 0.01 percent by weight of the mixture or granules, to 6 percent of the mixture or granules, and is preferably about 0.05%, 0.1%, 0.25%, 0.5%, 0.75%, 1.0%, 1.5%, or 2.0%.
[00065] The organic material, odor control agent and possibly recycle water are distributed to a mixing vessel where they are thoroughly mixed and can form a thixotropic slurry that is pumped or easily transported. The mixing vessel can be a pugmill, a screw mixing conveyor, a multi-shaft mixer, a ribbon paddle mixer, a static mixer, a high shear mixer or other commercial high viscosity slurry mixer. Pugmills, blenders and agitators are mixing chambers having blade-shaped mixing elements mounted on a powerfully driven shaft or shafts that rotate at a variable but controlled speed that divide, mix, back-mix and re-divide the materials to be mixed multiple times per second to produce a completely uniform mixture with reliable consistency.
[00066] Alternatively, the mixing vessel to achieve solids concentration and the mixing vessel for conditioning with recycle water, phosphoric acid, odor control agents or other additives can be combined in a single mixer of suitable size to provide the proper mixing time and energy.
[00067] To the mixture is added acid, in the preferred mode at the inlet of the first pressure vessel, creating an exothermic reaction, which in this way causes additional heating. As pressure is optional, the term pressure vessel does not imply that increased (or decreased) pressure is required, only that a suitable vessel must be used. Acid is added to the mixture by direct injection into a pressure vessel or injection into the vessel inlet. In the pressure vessel the mixture is stirred or otherwise mixed continuously. The acid is at a very low pH and preferably in the range of negative pH 4.0 to positive pH 1.0. As is known to those skilled in the art, with very strong aqueous acids there are too few water molecules to disassociate the acid completely. As a consequence, the true pH is much lower than an actual measurement. A negative pH indicates that the pH calculation can be a negative log of molarity where the molarity of hydrogen ions is greater than 1. Preferred pH values for acids used are, for example, pH 2.0 or less, pH of 1.0 or less, pH of 0.8 or less, pH of negative 1.0 or less, pH of negative 2.0 or less. Preferred acids include, but are not limited to, hydrochloric acid, boric acid, hypochlorous acid, perchloric acid, carbonic acid, phosphoric acid, sulfuric acid, nitric acid, hydrofluoric acid, carboxylic acid, and derivatives, mixtures, and combinations thereof. The amount and type of acid added is determined by one skilled in the art from the amount of organic materials being treated and/or the desired result, which includes but is not limited to one or more of reaching a predetermined temperature or pressure or liquefaction of the mixture. In part, since the organic materials are liquefied, there is little to no build-up of calcium silicate, insoluble phosphate compounds or other insoluble compounds in the pipes, a typical problem with conventional sewage sludge processing facilities. The addition of acid causes an exothermic reaction that heats up and increases the pressure in the vessel (when in a pressure-tight reaction vessel) . This pressure which with the start of the reaction is in ambient can in fact be maintained at ambient pressure as a desired pressure through the acidification process by monitored or controlled ventilation. Alternatively, the pressure may be allowed to increase with increasing temperature due to the exothermic heat of the hydration reaction. Such pressures can reach a range in excess of 40 psig through ventilation control or in the absence of ventilation. In addition, acidification can be carried out under negative pressure. Preferred negative pressure ranges range from one atmosphere (atm) (14.7 psi) to 0.9 atm, to 0.8 atm, to 0.7 atm, to 0.5 atm, to 0.4 atm, to 0.3 atm to 0.2 atm, and for 0.1 atm or less.
[00068] The temperature of the mixture preferably increases to or above 38°C (100°F), to or above 43°C (110°F), to or above 49°C (120°F), to or above 54°C (130°F), up to or above 60°C (140°F), or up to or above 66°C (150°F), such as, for example, up to or above 82 °C (180°F) or 93°C (200°F), and more preferably up to or above 104°C (220°F), 110°C (230°F), 116°C (240°F) , 121°C (250°F). This acidification can be carried out without pressure in the reactor allowing the release of air from the vessel during acidification, however in the preferred modality to facilitate the transfer of the acidified mixture to the second vessel the pressure in the first vessel or acidification vessel will be maintained above the pressure reached by the second vessel. The acidification process is carried out for a retention time between 2 minutes and 30 minutes with a preferred time between 4 minutes and 8 minutes. In an alternative embodiment, all pre-acidification ingredients including organic material, odor control agent, phosphoric acid and possible recycled water can be mixed in the acid reaction vessel either before or simultaneously with acidification.
[00069] After the acid reaction at the desired time, temperature and pressure, the acidified mixture is discharged from the acid pressure vessel and transferred to a second pressure vessel. In the second pressure vessel, ammonia is injected into the mixture either in the second pressure vessel inlet or directly into the second pressure vessel. The amount and form of ammonia added is determined by one skilled in the art from the amount of acidified mixture or organic materials being treated and the desired result, which includes but is not limited to one or more of reaching a predetermined temperature or pressure or liquefying the mixture. The addition of ammonia increases the temperature of the mixture which releases steam which increases the airspace pressure within the second pressure vessel. Pressures can again be regulated with pressure relief valves or by controlling the discharge of molten mass from an ammonia vessel. Subsequent addition of the ammonia base, preferably in a second pressure vessel, further affects the temperature of the mixture, preferably raising the temperature to or above 121°C (250°F) such as 138°C (280°F) or 143 °C (290°F), more preferably at or above 149°C (300°F), more preferably at or above 154°C (310°F), 160°C (320°F), 166°C (330°F) or 171°C (340°F), and more preferably up to or above 177°C (350°F) such as, for example, up to or above 182°C (360°F), 188 °C (370°F), 191°C (375°F), 193°C (380°F), 199°C (390°F), 204°C (400°F) 210°C (410°F , 216°C (420°F), 221°C (430°F), 227°C (440°F) or 232°C (450°F). Preferably heating is carried out for a holding time period which is equivalent to the time required to reach the desired temperature and allow the reactions to end. Preferred reaction time periods, which may include exothermic heating time, are between 1 and 30 minutes, more preferably between 3 and 15 minutes, more preferably between 5 and 10 minutes, or any combinations of these ranges. Furthermore, reaction times can also be dependent on the constituents and/or composition of the mixture being reacted and/or the amount and/or type of acid added. Reactions occur in closed container vessels, and pressure in the airspace of the container vessel also increases. Pressures again can be regulated with pressure relief valves and are preferably maintained between 5 psig and 150 psig, more preferably between 30 psig and 100 psig, and most preferably between 40 and 80 psig. Preferred pressures include, but are not limited to, 5, 10, 20, 30, 40, 50, 60, 70, 75, 80, 90, 100, 110, 120, 125, 130, 140, 150 psig.
[00070] The processes of the present invention with biosolids and other forms of organic materials produce a fertilizer that is preferably safe to handle and work with and preferably meets and/or exceeds the minimum requirements of a USEPA Class A and EQ biosolids. Fertilizer product is preferably sterilized and biological and chemical contaminants are at least partially and preferably completely hydrolyzed and biological agents are denatured to the point of inactivation and/or destruction. Typical chemical or biological contaminants include, but are not limited to, one or more of pharmaceutical compounds, antibiotics, hormones, hormone-like molecules, biologically active compounds, macromolecules, carbohydrates, lipids, proteins, nucleic acids, and combinations thereof.
[00071] The present invention preferably includes stress conditioning for a predetermined retention period that creates stress conditions that meet or exceed those associated with traditional autoclaving of materials. This autoclave effect destroys and/or inactivates or simply sterilizes the organic material. Microorganisms in organic material, including, for example, bacteria, viruses, fungi, parasites, parasite eggs, bacterial and fungal spores and combinations thereof, are destroyed and/or inactivated. In addition, the processes of the invention preferably are designed to hydrolyze macromolecules such as proteins, nucleic acids, lipids, fats, carbohydrates and combinations thereof, and/or other biologically active substances that may be present. Most microbial cells are physically broken down during this processing with the resulting organic compounds that contribute to the organic material or fertilizer matrix.
[00072] At any time during the method steps, one or more stiffening agents can be added to the mixture. Preferred stiffening agents include, but are not limited to, ferric oxides, attapulgite alum clay, industrial molasses, lignin, lignin sulphonate, urea formaldehyde polymerizer and combinations thereof.
[00073] At the desired time, which can be determined empirically or experimentally, the liquid is processed into fertilizer. Preferably the processing involves transfer to a granulator for dewatering and forming dry fertilizer granules. Processing in a granulator which contains 60 to 88 percent by weight of old granules is preferred, and drying the granules preferably with heat to greater than 90 percent solids, and preferably 98 or 99 percent solids or greater. Preferably water extracted from the granules is collected with a portion recycled in the process steps and the remainder treated for discharge. Granules are typically quite hot during the drying process and optionally can be allowed to cool by transfer to a refrigeration environment or refrigeration appliance. During refrigeration, ozone can be injected into the refrigerator as an odor control measure. Preferred amounts of ozone to be injected are from 0.01% to 5% by weight of the granules by cooling, more preferably from 0.1% to 2% and most preferably from about 0.5% to 1 %. Preferably, ozone is introduced to the washing refrigeration apparatus.
[00074] Once dry and formed and optionally after refrigeration, the granules are sized and the granule size of 0.5mm to 4mm is preferred. Most preferred are standard fertilizer granules of about 2.8 mm and "mini" specialty granules of about 1 mm.
[00075] One or more commercially available stiffening agents can be added to the granulator. Preferred stiffening agents include, but are not limited to, lignosulfonate, lignin, molasses, or a combination thereof. Granules larger than 4 mm and less than 0.5 mm are recycled in the granulator. Granules of the desired size are further processed by coating with one or more commercially available dust control agents. Preferably, granules larger than 4 mm are crushed and mixed with granules less than 0.5 mm, and everything is recycled in the granulator.
[00076] The invention preferably provides both dust and odor control systems to ensure acceptance by the manufacturing plant community as well as making the process more efficient by capturing and incorporating valuable nitrogen or other potential plant nutrients and/or fugitives from the plant's processed air.
[00077] Another modality of the invention is the fertilizer manufactured by the methods of the invention. The physical and chemical characteristics of organically modified ammonium sulfate fertilizer of a preferred embodiment of the invention are listed in Figure 4. Fertilizer from organic materials such as biosolids can be left in powder or pellet form, or is preferably in the form of granules which are of a predetermined size and are resistant to crushing. Additionally, preferred granules are generally spherical having a smooth exterior with few pits or cracks and circular or oval in shape. Preferably, the fertilizer does not contain detectable unhydrolyzed polymers or contains negligible detectable unhydrolyzed polymers and preferably the polymers within the organic mixture have been hydrolyzed including, but not limited to plastics, pharmaceutical compounds, antibiotics, hormones, hormone-like molecules, biologically active compounds , macromolecules, carbohydrates, nucleic acids, fats, lipids, proteins, and microorganisms. Hydrolyzed polymers form polymer monomers that accumulate in the product and are preferably multi-chain length polypeptides and amino acids.
[00078] The process of the invention preferably results in the production of USEPA Grade A granules or pellets and/or EQ fertilizer product of adequate dryness, hardness, and chemical quality to produce a valuable, high nitrogen, commercial fertilizer product , low release (eg enhanced efficiency, controlled release, double release, predetermined release) that is able to compete in the national and international market against traditional inorganic fertilizers. Preferably, the fertilizer product has a controlled and preferably slow release of nutrients to the soil, where control can be exerted through the addition of different types and amounts of organic material during manufacture. For example, a product in which different nutrients are converted to a slow-release form due to the sequestration of ions by organic matter in the fertilizer, including nitrogen, phosphorus, potassium, sulfur and various micronutrients selected from the group comprised of iron, manganese , magnesium, copper, calcium, selenium, boron and zinc (see Figure 5).
[00079] Significantly this invention instructs that the degree of slow release nutrients contained in the fertilizer can be adjusted on demand as in a "dial" or controlled capacity for the degree of slow release or improved efficiency. In the preferred embodiment the slow release nutrient, such as nitrogen, may constitute from 10% to 80% of the nutrient concentration by the dry weight contained in said fertilizer. More preferably the slow release nutrient component is from 30% to 70% of said fertilizer. The degree of slow release of the product can be adjusted by changing the amount of organic materials added such as wastewater plant biosolids, digested food products, other microbially digested materials such as pharmaceutical fermentation residue, digested food residue; liquid organic fraction extracted from municipal solid waste; animal waste; digested animal waste and algae collected from eutrophic surface water sources, and/or humates, humic acids, fulvic acids or, iron humates containing fulvic and humic acids. Additionally, the amount of slow-release nutrient can be altered directly by adding specific stabilizing chemicals such as Nutrisphere-N (commercially available from Verdesian Life Sciences), a proprietary nitrogen-binding agent used in agriculture to reduce volatilization and bleach and or other inorganic compounds that react with ammonia to create slowly soluble forms that are then slow-release nutrient compounds in the fertilizer. Additional nutrient binding agents such as nitrogen binding (ammonium ion) can be added to the process, preferably in the second mixer or granulator and include, for example, amino acids such as lysine, polypeptides containing nutrient binding amino acids, and magnesium ammonium phosphate. The addition of such agents directly alters the percentage of nutrient ions that are slow-release. This ability to change the percentage of nutrients that are slow release also directly increases the commercial value of said fertilizer as the conversion of nutrients to a slow release form provides better crop production due to these nutrients being available for longer in the growing cycle. .
[00080] Figure 5 illustrates the electrostatic binding of inorganic nutrients such as the positively charged ammonium ion, the negatively charged sulfate ion and the positively charged ferrous ion to the corresponding opposite charges located on organic molecules such as polypeptides of variable length and monomeric amino acids thus creating the organic matrix entity. This organic matrix serves as a slow-release or efficiency-enhanced release delivery mechanism of nutrients to the soil column over the growing season for the target crops. This slow release of nutrients is facilitated by the action of soil microbes.
[00081] Slow release or dual release fertilizers of the invention allow a single application of fertilizer that provides a first rapid release (eg mold) of nitrogen to growing or emerging plants such as commercial crops (eg fruits, vegetables, grains, grasses, trees), then an amount continued preferably for all or part of a growing season (eg see Figure 7). This minimizes the number of fertilizer applications required per season which provides substantial savings in application costs.
[00082] Stress resistant ammonia binders such as municipal organics can be added to the mixer prior to the first hydrolysis and/or acidification vessel. Compounds that are more sensitive to heat or pressure can be added directly to the granulator as shown in Figures 1A, 1B and 1C. Nutrients are sequestered or chelated by organic molecules in the product wherein said inorganic nutrients are released into the soil environment by the microorganism's metabolism over time after fertilizer application. Organics are comprised of macromolecules obtained from microorganisms broken down during product processing including: denatured proteins; peptides and amino acids; nucleic acids, compounds such as cytokinin, lipids and carbohydrates as well as denatured organics and hydrolyzed from the community organics defined in this invention. Organics form a matrix within the fertilizer that is comprised of a complex of amphoterically charged organic molecules of variable chain length that electrostatically attract and bind both positively and negatively charged inorganic nutrient molecules such as ammonium ion and sulfate ions. The product provides ammonium N which can be used by plants before they develop a nitrate N reduction system and is as a result very energy efficient. Ammonium N (NH4 + ) in the inventive fertilizer requires less of the metabolic energy stored in plants for incorporation into plant components. In this invention it was demonstrated that the conversion from the ammonium ion to the nitrate ion is retarded thus benefiting the target plants. Plants can use either ammonium or nitrate N, but ammonium N is a more energy efficient form of N for plants and is less leachable. This means that more sugars formed from photosynthesis can be stored in grain or fruit as starch resulting in increased yield. It has been estimated that using ammonium nitrogen can save 10 to 17% of the photosynthetic energy in which plants were stored.
[00083] Preferred fertilizer products are those from which the admission of nitrogen since the ammonium ion reduces the possibility of nitrogen losses by leach and denitrification by soil bacteria. Such losses can be sizable from nitrogen fertilizers that do not contain ammonium or are rapidly converted to nitrate N. Multi-nutrient fertilizers are preferably homogeneous and contain several essential nutrients. Figure 8 illustrates soil nitrogen leach in tomato crops as influenced by the nitrogen source.
[00084] A useful range of nutrient concentrations for plant development includes, for example, 8 to 18% nitrogen; phosphorus 0 to 10%; potassium 0 to 10%; sulfur 5 to 20%; iron 0 to 5% and organic 4% to 18%. Preferably, the product of the invention does not lose an amount of its contained nitrogen (N) greater than 3% as ammonia to the atmospheric environment with surface application to a dry soil and not more than 30% as ammonia from a flooded soil. Preferably, the product manufactured in accordance with the invention has an amount of zinc sulfate or soluble forms of boron added as plant nutrients. Sequestration improves the plant's iron use efficiency by retaining the added iron primarily in the form of plant-available ferrous ion. Preferably the product delivers sulfur in plant-available form as the sulfate ion. Organic content contributes to soil carbon pooling that improves soil quality. The product of the invention has an organic nutrient complex that facilitates the admission of ion exchange by the root hairs of the target crop, improves microecology in the root zone and soil cultivation, and increases the target plant's resistance to heat and stress. dry. The preferred product is non-hygroscopic with a granule hardness between 4 and 9 pounds, even more desirably between 6 and 8 pounds, with a bulk density between 52 and 56 pounds/cubic foot optimizing its blendability with other agricultural fertilizers . Preferably, selected herbicides and pesticides can be introduced to the granule surface area or mixed within granules of the product. The fertilizer is preferably uniformly black in color. However, fertilizer of the invention can be manufactured in any color that can be useful for evaluating distribution patterns and marketing advantages.
[00085] A commercial high nitrogen content fertilizer preferably has more than 8 percent nitrogen by the dry weight of the finished fertilizer and more preferably at least 15 percent nitrogen by the dry weight of the finished fertilizer. The Class A characteristic refers to the microbiological quality of the finished fertilizer product, which meets the US Environmental Protection Agency's Class A microbiological standards for a product containing municipal biosolids as defined in 40 C.F.R. § 503. Further, fertilizer of the present invention meets or exceeds this standard based on the stress conditions, retention time, and processing conditions used thereby ensuring that the three conditions associated with USEPA Outstanding Quality (EQ) standards are met. These include the Class A standard as stated above, the metal concentration level in the product as defined in CFR 503 and the Vector Attraction Standards are satisfied (90 percent solids or greater in the finished product) than the fertilizer pellet Finished is optimized for minimal water content by increasing hardness characteristic and eliminating water with respect to finished fertilizer product optimization. The percent solids of the finished product are preferably greater than 92 percent solids, more preferably greater than 97 percent solids, and most preferably greater than 98 percent solids.
[00086] Biosolids treated according to the processes of the invention typically contain low levels of metals such as arsenic, cadmium, copper, lead, mercury, molybdenum, nickel, selenium and/or zinc. Low levels are levels below what is considered hazardous and less than the Outstanding Quality (“EQ”) standard for metals as published by USEPA for products containing municipal biosolids. Thus, by exceeding USEPA regulation and hydrolyser or pressure vessel conditions for macromolecules (eg personal pharmaceuticals such as antibiotics or hormones or hormone substances), the resulting fertilizer is safe for use in agriculture and horticulture (plants and animals) and is exceptionally safe to handle by workers during processing, handling, distribution, sales and agricultural application.
[00087] As the fertilizer product produced contains both biosolids and a desirable high nitrogen content, a preferred embodiment results in a variety of specific nutrient analysis fertilizers of which the following are typical: 16-1-0-18-3 -15 or 16-1-2-17-3-14 (Nitrogen - Phosphorus - Potassium - Sulfur - Iron - Organic). The improved efficiency controlled or slow release granular fertilizer is at least 98 percent dry and exceeds US Environmental Protection Agency (USEPA) Class A and Outstanding Quality Standards (EQ) requirements. Thirty percent of the total product N is slow-release organic nitrogen (16% N x 30% = 4.8% slow-release N) that is bound to the biosolids components. Slow-release ammonium is slowly converted to nitrate which can be leached by soil bacteria from the soil and does not volatilize into the atmosphere as ammonia. The result is greater efficiency in the use of nitrogen by plants and less environmental impact of the nitrogen product.
[00088] The fertilizer product can be adapted to a desirable content of elemental components. Preferably the fertilizer has a nitrogen content between 6 and 20 percent, more preferably 8 to 18 percent, a phosphate content between 0 and 10 percent, more preferably nine to 5 percent, a potassium content between 0 and 5 percent, more preferably from one to four percent, a sulfur content between 10 and 30 percent, more preferably from 15 to 20 percent, an iron content between 0 and 8 percent, most preferably from one to four percent, and an organic content between 5 and 30 percent, more preferably 10 to 20 percent (or any combination of these ranges).
[00089] The fertilizer product contains nitrogen in the form of ammonium ions non-covalently bonded with organic compounds or other chemical compounds in the fertilizer. Unlike ammonium sulfate fertilizer, bound ammonium ions are not all immediately released into the soil upon application. Instead, there is a first release over a period of two weeks after application of an amount of nitrogen to the soil that represents from about 30 to 65% of the available nitrogen in the fertilizer. This rapid release typically varies over a period of one to three weeks, slower than a conventional ammonium sulfate fertilizer which typically releases 90% or more of its available nitrogen to the soil in about 5 to 10 days, but faster than the nitrogen release of 2% to 6% nitrogen in conventional biosolids fertilizers. Over the subsequent days and weeks, the volume of the remaining nitrogen (eg 35%) of the invention fertilizers gradually releases to the soil. Sun, heat, water and/or microbes in the soil act on the fertilizer and slowly break the ionic bonds releasing available nitrogen to the plant's roots. Preferably, nitrogen release is from about 1% to 5% per week, and more preferably from about 2% to 4% per week. A small amount of nitrogen can be covalently bound to the fertilizer compounds, and is thus additionally dependent on the microbial catalysis of the organic molecule for release to soil and plants. Preferably this amount of non-available nitrogen is 5% or less, more preferably 2% or less, and more preferably 1% or less of all nitrogen in the fertilizer product. This dual nitrogen release profile is advantageous for peat and agricultural use and not characteristic of conventional commercial fertilizers.
[00090] Another embodiment of the invention is directed to a process for the manufacture of a fertilizer with a predetermined content of one or more of nitrogen, phosphate and/or potassium. Processing of organic materials proceeds as described here where the acid selected is of the type and amount desired in the final fertilizer product. For example, using a defined amount of phosphoric acid will result in a defined amount of phosphate in the final fertilizer product. With the use of a particular amount of sulfuric acid, a particular amount of sulfur will be retained in the fertilizer. By selecting the type and amount of acid, you can pre-select the content of the fertilizer product produced. Preferably, the fertilizer is supplemented with one or more plant nutrients added during one or more processing steps. The one or more plant nutrients include, but are not limited to urea, ammonium nitrate, ammonium sulfate, monoammonium phosphate, diammonium phosphate, urea ammonium nitrate, liquid urea, potash, iron oxide, soluble iron, chelated iron , micronutrients such as magnesium, manganese, copper, zinc, molybdenum or boron, and combinations thereof.
[00091] Another modality of the invention is directed to a system for the manufacture of a fertilizer. The invention comprises a mixer that mixes the organic component containing biosolids, optionally with an odor control agent. The mixture is then transferred to a first pressure vessel. The pressure vessel is preferably of a construction which permits vigorous mixing with continuous exothermic reaction with the aqueous phase of the conditioned organic slurry and a direct hydrolysis of organic compounds in the material. An agitator/mixer is incorporated for the first pressure vessel. Optional heating elements that can be external to or internal to the vessel can also be incorporated into the pressure vessel. Acid can be mixed directly with the organics in the first pressure vessel or, preferably, the heated acid and biosolids are combined in a mixing tee and together added to the pressure vessel. Within the pressure vessel heat and buildup is continued for a period of time to form a liquid from the paste-like organic mixture. The liquid mixture can be further treated in the same pressure vessel, or preferably transferred to a second pressure vessel via a tube or conduit. The mixture is preferably transferred in a turbulent flow in order to avoid or minimize the possibility of organic material remaining in the conduit. Still preferably, the acidified liquid mixture is combined in a mixing tee with the ammonia from an ammonia source, preferably vaporized ammonia, and forcefully injected together into the second pressure vessel. Preferably the liquid mixture is forced through the conduit by a build-up of pressure by the heating reaction in the first vessel or by a pressure that is added to the system behind the liquid mixture to ensure that all of the liquid mixture has transferred to the second vessel . Preferably the gas, which may be air or another gaseous compound or mixture, is purged, if necessary, by means of a relief valve in the second vessel. Within the second pressure vessel, the acidified and nitrogen-fortified liquid mixture heats exothermically due to acid/base reactions and/or is heated to a second predetermined temperature and pressurized to a second predetermined pressure for a second period of time. Preferably the source of ammonia is liquefied and/or ammonia vaporized under pressure. Still preferred is a system in which each of the first and second pressure vessels contains an agitator or other mechanism that continuously mixes the mixture. Alternatively, the first and second pressure vessels can be the same with the acid and ammonia added in sequence. Following ammonia, the mixture is transferred to a pugmill or granulator where steam and water vapor is released and the ammonia-containing liquid is mixed with preformed granules (commonly referred to as “recycle” to form or shape the new ammonia granules. These granules are then heated in a rotary dryer or fluid bed dryer to form dry granules of the fertilizer. In a preferred embodiment, the entire reaction process is controlled by a closed-loop computer control that continuously monitors and adjusts. the exothermic reaction through the addition of sulfuric acid, ammonia, plant nutrients, pH adjusters and pressure control. The preferred control mechanism is by adjusting the airspace pressure above the biosolids in this pressure vessel and by valve control the output volume. The system still preferably contains a conveyor (eg pump or screw conveyor, conveyor belt) to transporting organic materials to the mixer and another pump to transport the mixed organics with the first pressure vessel; a pressurized piping system that transports acidified organics from the first pressure vessel to the second pressure vessel, ammonia to the second pressure vessel; and disperses the liquid with ammonia melt into the granulator. Thus, the entire process is carried out without the need to stop the continuous flow of biosolids into and out of the pressure vessels.
[00092] From the granulator, or incorporated with it, it is preferably a rotary dryer or alternatively a fluidized bed dryer which additionally dries the fertilizer biosolids to less than 2 percent water content. On exit from the dryer the biosolids fertilizer is further sieved for size and separated for product, undersized and oversized granule groups. Undersized particles are recycled back to the inlet of the granulator. The oversized particles are sent to a hammer mill where they are crushed and then recycled to the granulator. After leaving the screening process the biosolids fertilizer granules are processed through the rotating cooler where the fertilizer containing organic is cooled. Optionally, the cooler can include an ozone generator that provides ozone for the coolant fertilizer. In the presence of ozone, odor-causing material complexes with oxygen and possible other molecules present in biosolids and substantially reduce or eliminate unpleasant odors. The fertilizer granules empty into the final polishing screens to remove undersized granules or dust created in the cooling process. After processing through the polishing screens, the product passes through a coating drum where a coating agent that inhibits dust formation is added. The biosolids fertilizer is then stored ready for bulk shipment or subsequent packaging. Alternatively, the granules can be subjected to an air polishing system that continuously recycles the hot air generated in the refrigeration process to the drying stage resulting in a reduction in the use of fuel and waste air for processing. Air drawn from screens and equipment is cleaned in a dust collector, cooled through a heat exchanger and reused as inlet air to the cooler. The heated air discharging from the cooler is again cleaned in a dust collector. Clean heated air is used as the input air for the rotary dryer. The system further preferably contains one or more screens for selecting beads of a predetermined size and a rotary cooler for cooling and polishing the sized beads. The system of the invention preferably comprising a dust control apparatus such as, for example, vacuum cleaners and luggage housings which collect dust from the granulator and also a water recovery system in which water extracted from biosolids during processing is recovered and recycled making the system very efficient.
[00093] In a preferred embodiment, process air is acid washed to remove any fugitive and especially vaporized odorants or gaseous ammonia. The captured ammonia, as an ammonium salt, is mixed back into the biosolids mixture prior to its entry into the reaction vessel or mixer, thereby increasing the efficiency of the entire system and maximizing the final nitrogen concentration in the finished fertilizer . Miscellaneous waste including dust, claimed or unspecified product and dry fertilizer that is too small or undersized or oversized material that is crushed in a mill or crushing apparatus or may include other additives, eg iron that a consumer may prefer may be added to make up the finished fertilizer they are added to an optional pugmill or mixer positioned downstream of the pressure vessel or directly to the granulator. During the granulation process, a stiffener or stiffeners that help to agglomerate the mixture and contribute to the hardness of the dry pellet or granule are added to the second pugmill or granulator. The stiffener or stiffeners are selected from the group comprised of attapulgite clay, lignin, industrial molasses, lignosulfonate, and alum among others or mixtures of these stiffeners as known to one skilled in the art.
[00094] Optionally, depending on customer requirements, additional plant nutrients, eg potash or other forms of potassium, eg potassium hydroxide or potassium sulphate, are preferably added to the pugmill or granulator to directly affect the formulation of fertilizer nutrient. Additional solid nutrients that can be added also comprise urea, thiosulfate, ammonium nitrate, urea ammonium nitrate (UAN), 10-34-0 liquid fertilizer, mono-ammonium phosphate, diammonium phosphate, zinc chloride, liquid ammonia, and /or potash. Also added to this second pugmill or granulator is any additional iron needed. Iron contributes an important and valuable plant nutrient to the fertilizer mix, serves as a granulation aid and as described in the invention above serves to reduce harmful odors associated with the use of community organic materials.
[00095] In addition, additional ammonia can be washed into the pugmill and granulator directly to complete the formation of the ammonium salt and to control the pH of the mixture and to facilitate the formation of the finished granule. The solids used to adjust the pH can also be primarily alkaline agents selected from the group comprised of calcium carbonate biosolids, sodium hydroxide, potassium hydroxide, calcium oxide, cement kiln dust, limestone kiln dust, Class C fly ash, Class F fly ash, multistage burner ash, alum, alum from water treatment and wood ash. These are added via screw conveyors at specific rates for each compound. Liquid additions also include pH adjusting materials such as acids, for example, phosphoric acid or sulfuric acid, or caustic solutions, for example, ammonium hydroxide, sodium hydroxide or potassium hydroxide. These are pumped at respective rates to the injection ring to enter the pugmill.
[00096] The fertilizer product of the present invention preferably has a pH between 4.5 and 7.5, more preferably between pH 5.0 and pH 7.0, and most preferably between pH 5.5 and pH 6.9. The remainder of the processing for forming such as in pellet or granule production includes standard fertilizer granulation technology especially for high volume yield plants. The granule or pellet product, especially in lower yield plants considered to be those less than 25 tons of product production per day, may involve more innovative technologies such as injection or extrusion followed by milling or spherulization of the pellet or granule or involves the simple discharge from a granulator or granulation pugmill. When a granulating granulator or pugmill is used, it is preferable to feed some recycle, as in dry seed material, i.e., dry fines and fines produced by the crusher or mill or under-spec or claim fertilizer product material, to the pugmill and the granulator to adjust the percentage moisture present in the mixture so that agglomeration or nucleation can occur resulting in granule formation.
[00097] Other preferred embodiments comprise adjustments to the processes disclosed herein. Modalities incorporate a pelletizer in place of the granulator in the process train. The pelletizer can include the step of drying to preferred dryness or the formed pellets then can be transferred to a dryer, preferably a fluid bed dryer to achieve preferred dryness. These other modalities may also incorporate adjustments to control pH, dryness, product nutrients, shape, concentrations, etc. to produce a variety of specific fertilizers for different plants such as roses, rhododendrons, and any other flowers, vegetables, herbs, as well as specialty crops such as fruits and vegetables and unrelated products such as cat litters. Adjustments can also be made according to the geographic area in which the product is to be applied, to vary, for example, nutrients that may be inherently or otherwise lacking in the location. Examples of such variations include the addition of calcium, potassium, phosphorus and metals such as magnesium, manganese, boron and zinc in different amounts.
[00098] Normal drying to final drying is conducted using a horizontal fluidized bed dryer, or a rotary drum dryer. Dry pellets or granules that are greater than 92 percent solids and preferably are greater than 95 percent solids and more preferably are greater than 98 percent and even more preferably are greater than 99 percent solids then are sized through one or more screens. The specification size can be varied depending on consumer requirements, however the suitable product range for sale is between 0.5mm and 4mm with the commercial range for normal sized fertilizer is between 2mm and 3mm. The present invention can also manufacture a minimum sized product suitable for use in golf course applications ranging from 0.5mm to 1.3mm. The appropriately sized material is separated and then cooled and then coated and then cooled in an apparatus, preferably a rotating drum, to less than 60°C (140°F), preferably to less than 49°C (120° F) and more preferably to less than 43°C (110°F). The cooling of the granule or pellet takes place optimally in a rotating drum apparatus using ambient air or cooled air such as from an ammonia evaporation cooler. Coating can take place in a coating vessel specifically for this purpose typically a rotating drum or a mixer. Alternatively, cooling and coating can be achieved in a single vessel that cools the material and mixes the coating agent with the granules. The coating is with a dust remover or glazing material that minimizes dust generation during transport, storage and application. The finished coated pellet or pellet is then transported to storage as a bio-organically enhanced inorganic ammonium fertilizer that contains high nitrogen content finished upon shipment from the manufacturing site. Appropriately coated or dried pellets or granules have a hardness of greater than 5 pounds of crush strength in order to resist dusting and handling during shipping, shipping, and application. Coating of dust remover or glazing material generally requires a higher temperature, typically 71°C to 105°C (160°F to 220°F), to maintain a molten condition for application to the coating apparatus.
[00099] The granule storage facility or deposit, commonly incorporating compartments or silos to contain the granules, must be dried to prevent agglomeration of the granules leading to degradation and destruction. The finished product is by manufacture a sterile fertilizer having substantially no detectable amount of viable microorganisms, such as E. coli or streptococci, or viruses harmful to animals or humans. With storage the product has substantially no viable microorganisms which means that the fertilizer is microbiologically safe and has no detectable amount or a detectable amount well below a limit for safe handling and the use of microorganisms that originate from the materials Organic. Although the fertilizer is made sterile during manufacture, the combination can be expected to have external aerial microorganisms or by microorganisms deposited by animal or other contamination during storage or use. In any case, as the fertilizer product is dry and predominantly inorganic ammonium salts will not support microorganism multiplication at a rate that could lead to a public or animal health problem.
[000100] The fertilizer of the present invention is preferably chemically adjusted to fit the needs of nitrogen fertilizer requirements containing significant amounts of phosphate, sulfur and iron to improve the target nitrogen (N) content between 8 and 18 percent by weight, and preferably 16 percent by weight allowing for significant commercial valuation.
[000101] Figures 1A-C and 2A-C provide schematic diagrams of embodiments of the present invention, wherein the process of these embodiments uses dehydrated municipal biosolids combined with additional plant nutrients, ammonium salt fertilizers, and binding agents. In this example, the organics to be treated are dehydrated municipal biosolids, often referred to as a "biosolids cake." These biosolids are distributed to the manufacturing facility where they are stored in a storage compartment or silo until the biosolids are ready to be conditioned. Conditioning initially occurs in a first pugmill by vigorous mixing or mixing with iron or another odor control agent, which converts the thixotropic biosolids to a pumpable mixture, paste, or paste-like mixture. Iron reacts with reduced sulfur compounds and other odorants present in biosolids. If phosphoric acid is added to this first pugmill it helps modify the odorants present in biosolids and contributes most of the phosphorus nutrient found in the final product. As the biosolids proceed through the equipment train additional plant nutrients can be infused into the mix. In this modality, the biosolids are optionally heated during their passage through the pugmill before being pumped into the first reaction vessel. In the preferred embodiment shown here one or two streams of sulfuric acid (in a concentration range of 68 percent to 105 percent sulfuric) are injected into the vessel where the mixture is acidified and liquefaction begins. Once the mixture leaves the first pressure vessel it is transferred under pressure to a second pressure vessel where the primary nitrogen infusion reaction takes place. In these figures, a washer injects ammonia (or other nitrogen source) as a gas or liquid. This reaction in both vessels is carefully controlled to optimize temperature, pressure, retention time, and pH, all of which can be determined empirically based on the organic input materials and the desired organic output content. Pressure vessels include a plurality of valves and controls that serve to automate the system. Additives can be used to control temperature, pressure, and pH and nutrient levels. The nitrogen source that is pumped into the pressure vessel comprises a base such as anhydrous ammonia (both liquid and vaporized) or aqueous ammonia. A mixture of organics and ammonium sulfate and ammonium phosphate (if phosphoric acid is used) is formed which becomes molecularly integrated in which the ammonium ions become electrically bonded with the amphoteric organic molecules from the biosolids thereby creating a slow release or improved nitrogen efficiency in the final fertilizer granule. Similarly, this electrical bonding can occur between sulfate and phosphate molecules and iron (or other useful plant metals such as magnesium, calcium, copper, manganese, boron or zinc) present in the mixture in this way making these molecules a nutrient of similar to the slow release or enhanced efficiency release state. This mixture is held in a stress condition for a retention period as determined by its retention time (which in turn is based on head pressure and release volume as described here) as the mixture moves through the pressure. The stress condition preferably includes elevated temperature, and/or elevated pressure. Elevated temperature is produced partially or entirely by the exothermic reaction of the components, which can increase the temperature of the mixture. In the preferred embodiment 100% of the elevated temperature is provided by the exothermic reaction. At these temperatures steam is generated from the mixture. This steam is allowed to exit the pressure vessel under valve-controlled release, achieving partial drying of the mixture. The release of moisture from the exothermic heat allows the use of less fossil fuels such as natural gas to dry the fertilizer granules. This reduces the formation of carbon dioxide or greenhouse gas by approximately 40% compared to producing heat-dried biosolids or producing standard commercial fertilizers such as urea. This chemical heat generation makes the fertilizer of this invention very green and environmentally friendly. The stress condition the biosolids pass into the pressure vessel and the retention period is controlled to result in the production of a mixture that is sterile and contains macromolecules hydrolyzed from the organics. Controlling the stress condition and retention period also results in the fusion of the ammonium ions formed with the organic molecules present creating an organic matrix which is a natural slow release property for nitrogen and other nutrients present, and the denaturation and/or hydrolysis of many macromolecules present in organics, such as proteins, plastics and other polymers. When such molecules are biologically active, this denaturation and/or hydrolysis makes them less active or inactive thus creating a safer product for public use or display. The retention time to induce the necessary fertilizer properties and biological inactivation are controlled by the continuous pumping and flow of organics to the pressure vessel. This continuous flow processing of the invention versus conventional batch processing of older plants aids in the high yields of this invention. Continuous flow also minimizes the problems associated with clogging the process that requires downtime to clear the clog.
[000102] The melt mixture of organic liquids flows from the pressure vessel and optionally is mixed with a stiffening agent or agents and possibly additional nutrients to finely adjust the fertilizer as desired. This mixture is further treated by granulation or extrusion into granules such as pellets or other smaller structures. The granules are dried in a rotary dryer and passed through one or more screens to separate oversized materials and undersized materials from appropriately sized materials. Oversized materials can be crushed in a crusher or mill. Subsequently, undersized materials and crushed oversized materials can be recycled to facilitate granulation of the fertilizer mixture. The resulting appropriately sized granules are then dried in the rotary cooler, sized, coated, chilled and stored. When a traditional granulator is used in the forming process, vaporized ammonia ammonia and recycle addition can take place. Water removed from the mixture as steam from the pressure vessel and from subsequent vessels as steam and/or water vapor can be condensed and preferably returned to the waste water treatment plant (WWTP), or can be treated and discharged to adjacent water resources, or to the atmosphere. Water that is retained from the capture of ammonia in the process emission air is returned to a process water containment vessel or alternatively may be contained in a separate tank for conversion to a sealable liquid that contains fertilizer from nitrogen. This liquid fertilizer can have its nutrient formulation directly altered by the addition of other nutrient compounds selected from the group: potash or other forms of potassium, eg potassium hydroxide or potassium sulphate, urea, thiosulphate, ammonium nitrate , urea ammonium nitrate (UAN), liquid fertilizer 10-340, monoammonium phosphate, diammonium phosphate, zinc chloride, liquid ammonia, potash, iron-containing compounds and or other traditional inorganic fertilizers.
[000103] For optimal process odor control and fertilizer odor optimization resulting from the present invention this process water can be treated with 25 percent to 50 percent liquid hydrogen peroxide to eliminate most of the chemical odors associated with this process water before being subsequently added to the biosolids mixture immediately before or in the first pugmill. Alternatively, odorous process water can be treated with gaseous ozone which is bubbled by the diffuser through the process water in this way also eliminating most of the odorant associated with this water.
[000104] In another embodiment a series of reaction vessels can be used to achieve the acid/base reactions described here. In a preferred embodiment of the present invention the sequence of two reactor vessels can be used. In an optional embodiment a reactor vessel combination for acidic reaction can be followed by ammonia conducted in a cross tube reactor. In another embodiment the reactions can be carried out following a first cross-tube reactor for the acidification of the biosolids mixture followed by ammonia conducted in a pressure vessel. Also described is an embodiment in which the acidification reaction is conducted in a first cross tube reactor followed by an ammonia reaction in a second cross tube reactor.
[000105] Another embodiment of the present invention can have the acidification of the biosolids mixture to partially or completely occur in the first pugmill. The partially or completely acidified biosolids mixture can then be treated by ammonia in a first reaction vessel thus eliminating the need for a second reaction vessel. If the mixture has been partially acidified then the acid/base reaction can be completed in this first vessel or the incomplete mixture transferred to a second reactor vessel (or cross tube reactor) for completion.
[000106] Another embodiment of the invention is directed to a system for manufacturing a product from organic materials treated according to the method of the invention as described herein. The combination of pressure, heat and ammonia treatment destroys or otherwise inactivates toxins and other hazardous compounds that are present in an otherwise contaminated organic material. The resulting product can be used as a fertilizer or other nutrient or support for plants and/or animals. The fertilizer product of this invention is of homogeneous construction containing multiple nutrients.
[000107] Fertilizers made by the methods of the invention optionally may include one or more of anionic and cationic chemicals, chelating agents, ion sequestering agents, metal ions, citric acid, amino acids, glutamic acid, histidine, lysine, glycine, peptides , proteins, sugars, saccharides and polysaccharides, iron, sulfur, phosphorus and nitrogen binding compounds and combinations thereof. Binding agents that contain nitrogen include, for example, amino acids, lysine, peptides, polypeptides, ammonium N. These agents can be used by plants even before they develop a nitrate N reduction system and are as a result very energy efficient. Ammonium N (NH4+) in the inventive fertilizer requires less of the stored metabolic energy of plants for incorporation into plant components. Plants can use either ammonium or nitrate N, but ammonium N is a more energy efficient form of nitrogen for plants and is less leachable. This means that more sugars formed by photosynthesis can be stored in grain or fruit as starch resulting in increased yield. Using ammonium nitrogen can save 10% to 17% of the photosynthetic energy that plants have stored.
[000108] Preferably, fertilizers of the invention, when applied to a crop, release nutrients such as nitrogen to the soil at a slower rate than such components are released by fertilizer containing non-organic fertilizers such as fertilizers that use urea as the source of nitrogen. Fertilizers of the invention preferably are supplemented with nutrients comprising one or more of nitrogen, phosphorus, potassium, sulfur, iron, manganese, magnesium, copper, calcium, selenium, boron, zinc and combinations thereof, and these nutrients are chelated or bonded in a manner electrostatics with the organic matter of the fertilizer. Fertilizers of the invention preferably are homogeneous in composition, non-hygroscopic and black or very dark in color. Crops in which the fertilizer of the invention is applied show improved soil tillage, resistance to heat stress and drought, and improved soil microecology compared to non-organic fertilizer. Preferably fertilizers have a hardness between 4 and 9 pounds, even more desirably between 6 and 8 pounds and/or a bulk density between 52 and 56 pounds/cubic foot. Still preferably, fertilizers have a content of 8 to 17% nitrogen, 0 to 10% phosphorus, 0 to 10% potassium, 5 to 20% sulfur 5 to 20%, 0 to 5% iron and from 5 to 20% organic. Preferably fertilizers of the invention, when applied to a crop, provide one or more nutrients to the crop sufficient for all or a portion (eg, half, a quarter) of a single growing season.
[000109] The fertilizer of the invention provides an increased nutrient intake by crops such as nitrogen. Crops show increased root growth and increased density, increased volume and biomass, and preferably increased number and/or size of seeds, fruits and/or flower. The ammonium ion negates the possibility of nitrogen losses through leaching and denitrification by soil bacteria which can be sizable in nitrogen fertilizers that do not contain ammonium compared to inorganic fertilizers. Preferably with crop application, the fertilizer does not lose more than 5% of its nitrogen (N) contained to the atmospheric environment with surface application to a dry soil and not more than 35% from a flooded soil. Preferably the fertilizer delivers nutrients such as, for example, iron, nitrogen, phosphorus, in a plant-available form compared to the non-organic fertilizer.
[000110] Preferably crops in which they have the applied fertilizer of the invention show improved efficiency and nutrient use, such as iron, retaining iron primarily in the form of ferrous ion available to the plant, and contributes to the pooling of carbon nutrient for production of crop in the soil column.
[000111] The following examples illustrate embodiments of the invention, but should not be regarded as limiting the scope of the invention. Examples Example 1
[000112] Wet community organics comprised of biosolids from a municipal wastewater plant are received at the fertilizer manufacturing plant of this invention at a percent solids of 16.0 percent. The plant is set to operate at a wet sludge processing rate of 220 wet tons per day. A portion of this 16% solids material was dried in a pre-dryer to 85% dry solids at a rate to produce sufficient 85% dry material to blend with the 16% material to produce a preferred percentage solids of 20 % to 26% but more preferably 22% to 24% solids. Additionally, an iron sulfate dry solids material was mixed in the same mixer sufficient to produce a 3% concentration of iron in the finished fertilizer. This conditioned organic mixture is then pumped into the first hydrolysis vessel where in the pressure vessel orifice it is mixed with 93% sulfuric acid in a pre-calculated amount to produce a degree of heat of hydration of 110°C (230 °F) and a total of 17% sulfur in the finished fertilizer. The contents of the first pressure vessel are vigorously mixed at a rate of 360 RPM for six minutes inside the vessel as the acidified mixture is gradually forced into the upper quarter of the vessel where it is discharged after six minutes of reaction in the first vessel. vase. In this first vessel, proteins contained from community organics are hydrolyzed to polypeptides of various lengths and monomeric amino acids. Other macro-organic compounds are also hydrolyzed to smaller molecular forms thereby increasing the fluidity of the vessel contents to preferably less than 1000 cP. This fluidized acidified mixture is then transferred under pressure to the bottom orifice of the second pressure vessel or an ammonia vessel where it is mixed with sufficient vaporized anhydrous ammonia to raise the temperature of the mixture to more than 150°C (300°F ) and the internal pressure of the second pot of more than 35 psi is sufficient to cause the nitrogen (N) concentration in the final resulting fertilizer formulation to between 16% and 17% nitrogen by dry weight of the finished product. The ammonia mixture is held in the second pressure vessel for six minutes of reaction time before being discharged through a valve-controlled orifice into the granulator. The molten mass or mixture discharged is slightly increased in viscosity compared to the discharge from the first pressure vessel but preferably less than 1200 cP. This discharged molten mass is under pressure and therefore when it enters the granulator it is sprayed into a receiving bed of crushed fertilizer material or undersized fertilizer material or dust fertilizer material collected from the various dust collectors contained in the process air treatment. The spray coats the receiving fertilizer material and gradually builds up a series of coatings or agglomerated material such that the granular fertilizer is produced in which the majority of the material is of the appropriate product size such as granules of diameter 1.7mm to 3 .0 mm (170 sgn to 300 sgn; “size guide number”) which are suitable for use in commercial agriculture. The granulator in this example also receives an amount of potash sufficient to make the final potassium concentration be 2% by dry weight of the finished product. The granulator also receives an amount of molasses sufficient to cause the hardness of the finished granules to reach a range of 5 lbs. To 8 lbs. Crush strength (eg from 0 to 2% by weight, preferably less than 1%). This material is then dried to greater than 98% solids in a rotary drum dryer and then sieved to one of three commercial sizes from 1.7mm to 1.9mm, 1.2mm to 1.4mm, and to 2.6mm to 3.0mm. All minor material is returned to the granulator as part of the recycle bed. All larger material is crushed in a chain mill and then returned to the granulator as part of the recycle. A portion of the appropriate sized product, preferably 2.6mm to 3.0mm for commercial product size, may also be returned to the recycle bed to maintain the mass balance of the production process. All steps of this process have been kept in this example under negative pressure so that no process dust or odors are released into the manufacturing environment. All process air was treated through a robust odor control system such that no harmful odors were noticed on the fence line of the manufacturing property. Washed nutrients such as ammonium, now ammonium sulfate, were returned to a process water tank where it was added to the first mixer to help control the solids and fluidity of the conditioned mixture entering the first pressure vessel. In this way the efficiency of the manufacturing process can be optimized so that the only discharges from the fertilizer manufacturing process are treated condensed water (from municipal organic material and any cooling water that may need to be discharged from the cooling system) together with the treated process air. In the fertilizer manufactured by this described process, the percentage of slow nitrogen release was 30% of the total nitrogen in the product. This slow-release Nitrogen is in the form of an organic matrix in which the positively charged ammonium ion is electrically bonded to a negative charge on organic compounds such as polypeptides and amino acids that comprise the matrix core. The product of this example of the invention contains a 99% dry granular fertilizer with a nutrient formulation of 16-1-2-17-3-16 (NPKS-Fe-Organic) by the dry weight of the finished granular in which 33% of the nitrogen is in a slow release form. Example 2. Ammonia Absorption
[000113] In this example the fertilizer was manufactured by a similar process with the difference that an amount of ammonia absorbing compound such as Nutrisphere-N (commercially available from Verdesian Life Sciences), a proprietary nitrogen binding agent , has been added to the granulator such that the slow release N component is increased up to 45% N from the standard 30% total N. This increases the commercial value of the fertilizer and makes 15% more of the nitrogen contained available at the later crop growth stages than 2 weeks following the original field application of the fertilizer product. Example 3. Nitrogen release profiles
[000114] Nitrogen release profiles of the organically modified ammonium sulphate of the invention are determined in comparison with traditional pure ammonium sulphate fertilizer and pure biosolids as controls. Firstly, ammonium sulfate is applied over sterilized sand in a laboratory environment (room temperature without sun, water or soil organisms) and adapted to permeate the sand over a period of time. As can be seen in Figure 6, about 90% of the AS nitrogen is released through the sand within about a week of application. In comparison, about 35% of the nitrogen from traditional biosolids is released which increases up to about 70% over the two weeks it remains. The invention's organically augmented ammonium sulfate releases about 60% of its nitrogen within the first week which increases up to about 70% over two weeks.
[000115] Further, a theoretical nitrogen release profile is determined for these same three fertilizer materials in normal soil. Soil is presumed to contain micro-organisms that break down that contain nitrogen molecules thereby releasing additional nitrogen into the soil. As can be seen in Figure 7, ammonium sulfate again releases its nitrogen content within the first week. Pure biosolids release only about 30% of their nitrogen in the first two weeks, which gradually increases to about 90% over a period of 26 weeks. However, organically modified ammonium sulfate prepared according to the processes of the invention releases a little less than 60% of its nitrogen over two weeks which gradually increases to about 90% over the next 26 weeks. Thus, organically modified ammonium sulfate fertilizer prepared according to the processes of the invention initially releases just over half of its nitrogen and slowly releases the remaining half over a period of weeks to months. This two-stage nitrogen release profile (eg dual release, two-stage release, combined fast/slow release) is characteristic of the fertilizers of the invention. Example 4. Ammonium nitrogen
[000116] A product of the invention contains 16% nitrogen primarily in the form of ammonium. Depending on the situation where the product nutrient is applied, this amount will provide sufficient nitrogen or the product can be supplemented by mixing with additional nitrogen sources. Usually when plants are fertilized, they have a high demand for nitrogen to trigger rapid growth and development. The product releases approximately 60% of its nitrogen immediately in the form of NH4+-N, which is readily available and useful to plants (see Figure 11). Ammonium N can be used by plants even before they develop a nitrate N reduction system that is also energy efficient. Efficient use of nitrogen early in growth produces more robust plants that have increased disease resistance and greater growth potential in all directions including root density, leaf number and vastness, and seed and flower production. The admission of nitrogen as ammonium negates the possibility of nitrogen losses through leaching and denitrification by soil bacteria that may be sizable. The balance of the nitrogen product becomes available through the natural slow release mechanism of bacterial action that can break the bonds between OM and nitrogen as shown in Figure 11. This system can be altered by variations in soil type, temperature, and other parameters.
[000117] A controlled nitrification study was carried out with the product of the invention (Anuvia), urea and urea plus agrotain. Results are shown in Figure 9 which demonstrates that the fertilizer product of the invention (Figure 9A) converts nitrogen more slowly than commercial urea (Figure 9B) or urea plus agrotain (urease inhibitor) (Figure 9C). Example 5.
[000118] Four female hormones and a common herbicide were quantitatively mixed with a wet municipal biosolids cake before the biosolids were processed by an embodiment of the invention. The combination of process stresses such as an extremely low pH of less than 0.1 pH in an environment temperature greater than 110°C (230°F) for six minutes followed by exposure to vaporized anhydrous ammonia under a pressure of 40 psi and a temperature of 200°C (390°F) for an additional six minutes, which causes a loss of greater than 96% of the ability to detect these endocrine disrupting compounds (see Figure 10). Such molecular destruction by the process of the present invention of bioactive compounds that can be found in municipal organic materials makes the resulting fertilizer product inherently safe. Example 6. Potassium
[000119] Plants require potassium (K) in secondary amounts only for nitrogen. Potassium in fertilizers is often referred to as potash and listed in fertilizer analyzes as K2O. However, plants capture and use only the potassium ion. Potassium impacts crop quality and is particularly important in starch and carbohydrate synthesis, making suitable potassium critical for high carbohydrate crops such as potatoes, sugar cane, sugar beets, citrus and grapes. It is an enzyme activator that helps plants withstand moisture stress and helps perennial crops like alfalfa prevent winter death by ensuring the plants have enough starch stored in their roots to last through the winter. Potassium, like nitrogen, also helps plants produce protein as they grow. Crop potash effects include: increased core weight and more cores per ear in corn; increased oil content in soybeans; improved cooking and milling quality in wheat. Potassium may be abundant in some soils, but as with nitrogen (N) and phosphorus (P), the problem is availability. Up to 98 percent potassium in soil is unavailable to plants in their existing form. The fertilizer product described here contains a modest amount of this essential element in the form of potassium cation (K+) but can be supplemented in the formulation or in a crop fertilization program by mixing with other blended fertilizers. Example 7. Sulfur
[000120] Sulfur is an essential nutrient in crop production and has been classified as a minor element, along with Mg and Ca, but is now more commonly considered “the 4th largest nutrient”. Some crops can collect both sulfur S and phosphorus. Sulfur has become more important as a limiting nutrient in crop production in recent years for several reasons. These include higher crop yields that require more sulfur, less sulfur impurities in modern fertilizers, less use of sulfur-containing pesticides, reduced industrial sulfur emissions to the atmosphere, and a greater consistency of sulfur requirements. Plants can only use sulphate S, which is susceptible to leaching as nitrate.
[000121] Sulfur serves many functions in plants. It is essential in the formation of amino acids, proteins and oils. It is necessary for the formation of chlorophyll, promotes nodulation in vegetables and is essential for the fixation of atmospheric nitrogen (N2), helps to develop and activate certain enzymes (nitrate reductase), and is a structural component of two of the 21 amino acids that form the protein. Sulfur also provides plant health benefits in crop production. The way the product distributes sulfur (SO4 = Sulfate ion) is the only way the plant can use it.
[000122] The plant essential sulphate sulfur in the product of the invention is both readily and slowly available to the plants and in a useful form. This is in contrast to other sulfur containing products which contain elemental sulfur which must be oxidized by soil bacteria to the form of sulfate in order for it to be used by plants. This process is affected by a number of factors including elemental sulfur particle size, soil temperature, soil pH, soil moisture and the activity of sulfur oxidizing organisms in the soil. Sulfur that binds with the organic matrix in the product is less leachable under excessive rain conditions than sulfur from ammonium sulphate. Example 8. Iron
[000123] Iron (Fe) is one of the essential micronutrients that include zinc (Zn), manganese (Mn), copper (Cu), molybdenum (Mo) and boron (B). Iron is involved in many biochemical processes in plants including photosynthesis, respiration (use of stored sugars), reduction-oxidation reactions, symbiotic nitrogen fixation by legumes (Rhizobia bacteria) and the formation of chlorophyll. Iron deficient plants are notoriously chlorotic and the severity of chlorosis varies with the genetics of the particular plant species. The problem develops once plants germinate and growth worsens as time passes. Plants can only use ferrous iron (Fe+2). Most of the iron in the soil is in the unavailable ferric form (Fe+3). When iron is added to the soil in an inorganic form such as ferrous sulfate (FeSO4), normal soil reactions quickly convert (oxidize) it to the ineffective iron form. High soil pH and low organic matter content contribute to iron availability and intake problems. Conditions in the rhizosphere (region around plant roots) have tremendous effects on Fe availability and intake and vary widely with varietal differences within the same species.
[000124] Over the years, many types of iron-containing fertilizers have been developed, but few have been both effective and economical. Soil applications have been particularly ineffective. High-cost chelated forms of iron have been the most effective, but economics have been a limiting factor. Foliar sprays or frequent applications of very acidic iron fertilizers have alleviated chlorosis but should be repeated several times during the growing season. Still, conditions remain and problems recur.
[000125] The ferrous iron sequestered in the product of the invention is less subject to undesirable soil oxidation reactions that convert to the form of unavailable ferric iron. The organic matrix of products provides an excellent vehicle to effectively distribute iron in the ferrous form that is useful to plants. Having iron available in a useful ferrous form contributes to nutrient carbon grouping, enhancing ion exchange, enhancing micro-ecology in the root zone, enhancing soil cultivation, and increasing plant resistance to heat stress and dry. Example 9. Lower Ammonia Volatilization and Higher Crop Yields
[000126] An ammonia volatilization study conducted by IFDC in two soils under winged and flooded land conditions, demonstrated that the fertilizer product of the invention had significantly less NH3 N volatilization loss than urea. In general, the fertilizer of the invention had similar NH3 N volatilization losses as ammonium sulfate in both soils and under both upland and flooded conditions. However, in upland soil, the fertilizer of the invention had significantly lower losses at 2.5% of N fertilizer applied, compared to ammonium sulfate at 3.2%. Compared with urea where the percentage loss of applied nitrogen due to NH3 N volatilization under upland conditions was 27 to 33%, the loss of NH3 N volatilization by the fertilizer of the invention was only 2.5 to 3% nitrogen fertilizer applied. Under flooded conditions the percentage of nitrogen loss applied from urea due to loss of NH3 N volatilization was 59% and 61% for the two soils, while losses of product of the invention were 26 percent and 32 percent. Field studies of rice fertilization in Arkansas showed an average yield advantage of 20 bushels per acre for a hybrid rice with the fertilizer of the invention compared to urea when applied to the soil surface 1 to 10 days before flooding. Example 10.
[000127] In this example, a higher percentage of slow nitrogen release is created. In Example 1 above the product of the invention contains 325 pounds of organic material per 1 ton of product. This one ton of product contains 16% nitrogen or 320 pounds of nitrogen per ton of product. Of these 320 pounds of nitrogen, 33% is slow release (105.6 pounds) as a result of the formation of organic matrix complexes in which the positively charged ammonium ions and the negatively charged sulfate ions are electrostatically bound with the opposite charges contained in the amphoteric organic molecules contributed by the organic materials of the community. In other words, the efficiency of slow-release nitrogen is 105.6 pounds of slow-release nitrogen for every 325 pounds of municipal organics contained in the final product mass, or 105. 6/325 equals 32.5 percent. With increasing total organic mass of the final fertilizer product with additional community organics such as biosolids, as in replacing other heavier fertilizer components, the two percent potassium mass in the product in Example 1, the amount of organics in the end product is increased to 433 pounds, which is an end product nutrient composition of 16-1-0-17-21. At an average efficiency of 32.5% that produces a new amount of slow release nitrogen of 140.7 pounds or an increase of 44.7 pounds of slow release nitrogen per ton of the product of this invention. The percentage of slow-release nitrogen in this example is increased from 33% to 140, 7/322.5 (2.5 pounds of N is contributed by an additional 40 pounds of organic = 43.6 percent. Substitutions are made for different amounts of potassium or the iron component in the fertilizer composition to produce the desired or specific amount of slow release nitrogen without changing the amount of total nitrogen added in the final product of the invention.
[000128] Other embodiments and uses of the invention will be apparent to those skilled in the art from consideration of the specification and practice of the invention disclosed herein. All references dictated herein, including all publications, US and foreign patents and patent applications such as US Patent No. 8,105,413; US Patent No. 7,662,205, US Patent No. 7,513,927, US Patent No. 7,662,206, US Patent No. 7,947,104, and US Patent No. 8,992,654, are specifically and entirely incorporated by reference. The term comprising, where used, is intended to include the terms consisting of and consisting essentially of. It is intended that the specification and examples be considered exemplary only with the actual scope and spirit of the invention indicated by the following claims.

权利要求:
Claims (12)
[0001]
1. Method for the manufacture of a fertilizer with a predetermined nutrient release profile characterized by the fact that it comprises: conditioning an amount of an organic material to a predetermined degree of moisture forming a mixture, in which the type and/or amount of organic material establishes the fertilizer's slow-release nutrient profile; transfer the mixture to a first vessel in which a concentrated acid is added creating an exothermic reaction, where the amount of acid added creates a predetermined temperature forming a liquid mixture, where the predetermined temperature is between 93 and 121°C and the mixture liquid has a viscosity of 4,000 cP or less; stir the acidified mixture for a first period of time; transfer the liquid mixture under pressure to a second vessel in which sufficient anhydrous ammonium is added to further increase the temperature and pressure of the liquid mixture so that the liquid mixture contains a predetermined amount of nitrogen, wherein the predetermined amount of nitrogen creates between 6 and 20% nitrogen in the fertilizer, and where the second pot has a pressure of between 2.04 and 10.2 atmospheres (between 30 and 150 psig) at a temperature of 121 to 232°C; stirring the liquid mixture in the second vessel for a second period of time so that the ammonium ions non-covalently bond to the organic compounds and other compounds in the fertilizer; and discharging the liquid mixture from the second pot to form fertilizer with a predetermined slow release profile, where the slow release profile is a profile of the release of one or more of nitrogen, phosphorus, potassium, sulfur, iron, organics and combinations of these.
[0002]
2. Method according to claim 1, characterized in that the nutrient release profile: i. in general corresponds to the growth requirements of a particular crop for one or more of nitrogen, phosphorus, potassium, sulfur, iron, organics and combinations thereof; or ii. comprises the rate, amount and/or differential release of one or more nutrients from the fertilizer.
[0003]
3. Method according to claim 1, characterized in that i. the organic material comprises one or more of municipal biosolids, heat-dried biosolids, pharmaceutical fermentation residues, microbial digestions of organic products, agricultural waste products, digested food products and food products, food by-products, animal manure, digested animal manure, organic biosolids, biosolids containing microorganisms, plant biosolids from wastewater, liquid organic fractions extracted from municipal solid waste, animal waste and digested animal waste, algae collected from eutrophic surface water sources, iron humates containing fulvic acids and/or humic, and combinations thereof; or ii. the predetermined degree of moisture comprises a percentage of solids from 15 to 30%; or iii. the aqueous liquid removed from the organic material is recycled.
[0004]
4. Method according to claim 1, characterized in that it further comprises adding an odor control agent to the conditioned organic material.
[0005]
5. Method according to claim 4, characterized in that the odor control agent comprises one or more of calcium ferrate, sodium ferrate, potassium ferrate, ferrous sulfate heptahydrate, rozenite, melanterite, ferric chloride, ferrous sulfate, ferrous sulfate monohydrate, hydrogen peroxide, ozone and salts, derivatives and combinations thereof.
[0006]
6. Method according to claim 1, characterized in that i. the concentrated acid comprises 90% or greater sulfuric acid or concentrated phosphoric acid; or ii. the amount of acid creates a temperature of 100°C or greater.
[0007]
7. Method according to claim 1, characterized in that i. the first time period is 2 to 20 minutes; or ii. the second time period is 2 minutes or greater, or 5 minutes or greater.
[0008]
8. Method according to claim 1, characterized in that i. the discharge comprises coating the liquid fertilizer in recycled fertilizer granules; or ii. the coated recycled fertilizer granules are dried; or iii. wherein, the organic material contains plastic and hair and the method does not require removing any of them prior to processing; or iv. the fertilizer is dried to a solids content of at least 98%.
[0009]
9. Method according to claim 1, characterized in that the liquid mixture: i. has a viscosity of 2000 cP or less; or ii. it has an increased viscosity after addition of anhydrous ammonium.
[0010]
10. Method according to claim 1, characterized in that it comprises i. adding a stiffening agent to the fertilizer selected from the group consisting of lignosulfonate, molasses, alum or a combination thereof; or ii. adding zinc sulfate and/or soluble forms of boron to the organic material, the mixture and/or the liquid mixture; or iii. add nutrients, peptides, vitamins, polypeptides, amino acids, saccharides, polysaccharides, herbicides and/or pesticides to the organic material, mixture and/or liquid mixture.
[0011]
11. Method according to claim 1, characterized in that it further comprises the addition of one or more agents that create and/or reduce that electrostatic state of the organic material to the organic material, the mixture and/or the liquid mixture , optionally, wherein the one or more agents comprise one or more of anionic and cationic chemicals, chelating agents, ion sequestering agents, metal ions, citric acid, amino acids, glutamic acid, histidine, lysine, glycine, peptides, proteins, sugars, saccharides and polysaccharides, iron, sulfur, phosphorus and nitrogen-binding compounds and combinations thereof.
[0012]
12. Method according to claim 1, characterized in that the fertilizer comprises granules, optionally further comprises selecting granules by size, optionally, wherein: i. selected granules are between 0.5 and 4 mm; or ii. selected granules that are larger than 4mm are crushed and combined with selected granules that are smaller than 0.5mm and comprise recycled fertilizer granules.

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EP3302782A4|2019-01-09|

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法律状态:
2020-04-07| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

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2021-01-12| B06A| Patent application procedure suspended [chapter 6.1 patent gazette]|

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2021-04-20| B25A| Requested transfer of rights approved|Owner name: ANUVIA PLANT NUTRIENTS HOLDINGS, INC. (US) |

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2021-07-06| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2021-09-08| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 06/06/2016, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

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申请号 | 申请日 | 专利标题

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US201562171541P| true| 2015-06-05|2015-06-05|

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US62/171,541|2015-06-05|

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PCT/US2016/036043|WO2016197119A1|2015-06-05|2016-06-06|High value organic containing fertilizers and methods of manufacture|

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