High value organically intensified inorganic fertilizers

专利摘要:
ORGANIC ENRICHED HIGH VALUE INORGANIC FERTILIZERS The invention is directed to the manufacture of fertilizer with commercial levels of nitrogen supplemented with organic substances, for example, 16-0.5-2-17-3-14 (NP-KS-Fe-organic, in dry weight). The process makes treating organic matter with concentrated acid which heats a fertilizer mixture causing the hydrolysis of various organic polymers that may be present. A mixture of the residue is subsequently sequentially injected with a nitrogen base under controlled conditions. The resulting sterilized and liquefied organic matter is then paid for on the recycled material to produce granulates in a granulator before final drying to greater than 98 percent solids. As the process allows for the controlled addition of acids and ammonia, the desired levels of components can be achieved. For example, fertilizers with a high nitrogen content can contain varying amounts of phosphate or iron. In addition, the process is scalable, odor controlled and safe, thus allowing the location of bio-solids processing facilities in any desired location, without affecting the environment or creating a nuisance for local communities. Furthermore, the fertilizer of the invention provides a (...) release profile.
公开号:BR112013025243B1
申请号:R112013025243-0
申请日:2012-03-28
公开日:2021-07-06
发明作者:Gary Dahms；James P. Carr；Jeffrey C. Burnham；Barry R. Jarrett
申请人:Anuvia Plant Nutrients Holdings, Inc.；
IPC主号:

专利说明:

Reference to Related Requests
This application claims priority to US Provisional Application No. 61/468,157, filed on March 28, 2011, to US Provisional Application No. if A 61/569,007 filed December 9, 2011 and to US Provisional Application No. 61/615,258 filed March 24, 2012, all of the same title and all of which are specifically and fully incorporated by reference. Background 1. Field of Invention
The present invention relates to methods, systems and processes for the manufacture of fertilizer and fertilizer product manufactured by these methods. In particular, the invention also relates to the manufacture of fertilizers with predetermined concentrations or absences of nitrogen, phosphate and/or potassium. 2. Description of Prior Art
Today, it is estimated that sludge is produced at a rate of more than 8 million dry metric tons annually or approximately 64 dry pounds of biosolids for every individual in the United States. The term sludge has been replaced by the term biosolid which includes all forms of urban waste, such as, for example, domestic sewage, agricultural and industrial organic waste, which is collected or otherwise sent for wastewater treatment, runoff from sewage, pharmaceutical waste including fermentation and processing waste, microbial digests, food waste and food by-products, animal manure, i manure from digested animals, organic sludge, organisms and micro- 3. i. "f organisms and all combinations thereof. Most * industrial waste is disposed of in municipal sludge or y *• ¥• otherwise disposed of in landfills or as may be common in the particular industry. . imagine, all forms of waste material can and * usually end up in municipal sludges including biologically active molecules such as pharmaceuticals, as well * as metabolized products, paper, plastics, metals and most forms of waste, 't
Biosolids are generally collected by municipalities through existing infrastructure such as sewers and other types of residential or industrial plumbing systems. The collected material is sent to one or more central facilities designated as wastewater treatment facilities. In these facilities, water is separated from solids and sent through purification procedures for recovery.
Solids are either burned or transported by truck I.' Go for burial or by boat for dumping into the ocean. Burning or incineration has become more common, in part, because of awareness of the dangers of unprocessed biosolids.
It is assumed that all biosolids are not only harmful chemical substances, but also bioactive compounds and pathogens. There are local, state and federal regulations 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 inefficient and extremely expensive.
Burning destroys most of the harmful materials present in biosolids, but the cost of damage to the environment is always tremendous. The incinerators have been built specifically to handle municipal waste. These incinerators create large amounts of contaminated smoke by spoiling the air within thousands of square kilometers around the facility. The smoke that is emitted contains any contaminants that are present in the biosolids, such as metals and other non-combustible components. These contaminants settle over fields and bodies of water creating ecological nightmares around the facility and sometimes over great distances downwind from the facility. Although burning can produce energy, energy production is highly inefficient requiring large amounts of biosolids to become economically viable. The amount of energy produced is always smaller compared to the amount of material incinerated. Even after burning, huge amounts of soot remain and need to be removed and discarded. Compared to the original biosolids, the soot is devoid of any positive impact on the environment in any way and is simply and unceremoniously buried or dumped in the ocean. Total burning negatively increases the impact 1 of the disposal of sewage sludge to the environment and for many years to come.
Biosolids that have been treated to some degree of processing are classified according to federal standards set by the United States Environmental Protection Agency (USEPA) as Class A or Class ;B. "Class A" biosolids are considered to be free of i. !: detectable pathogens and safe enough as a i • fertilizer for use in animal or human food. The 5 pathogens such as, for example, Salmonella II sp. bacteria, faecal coliform indicator bacteria, enteric viruses and viable helminth eggs are below detectable levels. When f" pathogens can be detected in the biosolids, USEPA has classified such treated biosolids as "Class B" implying that these are of a lower standard than the "Class A" treated biosolids. Because Class B biosolids contain pathogen indicators. - and therefore potential pathogens, they are restricted in the way in which they can be applied to animal or human food.
The Part 503 rule (Title 40 of the Code of Federal Regulations, Part 503, hereby incorporated by reference) lists six alternatives for treating biosolids so that they can be classified into
Class A in relation to pathogens. Alternative 1 requires the biosolids to be subjected to one of four temperature and time 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 is demonstrated that the process can reduce enteric viruses and viable helminth eggs and that the operating conditions used in the demonstration after the pathogen reduction demonstration is complete be maintained. Alternative 4 requires that, when treated in unknown processes, the biosolids be tested for pathogens at the time the biosolids are used. j discarded or, in certain situations, prepared for use or < t discard. Alternative 5 requires the biosolids to be treated in one of the processes to further reduce the 4 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 licensing authority. . ’
Biosolids from class A pathogens must also have a density of fecal coliforms less than 1000 most likely numbers (MPN) per gram of total solids (dry residue) or a density of Salmonella sp. less than 3 MPN per 4 grams of solids! total (dry residue) . Any of the same 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 dispensed in a bag or other container for use on the ground; or when biosolids or derived materials are prepared- to meet the requirements for Exceptional Quality biosolids.
All biosolids applied to the soil must comply. • J- the limit concentration in terms of pollutants, comprising the I. ten heavy metal pollutants: arsenic, cadmium, chromium, copper, lead, mercury, molybdenum, nickel, selehium and zinc. If the limit for any of them is exceeded, biosolids cannot be applied to the soil without incorporating significant restrictions. THE
Exceptional Quality (EQ) is a term used by the USEPA Guide, Part 503, rule 7, to characterize '•t' biosolids. t. that meet the limits of low pollutant and reduction of Class A pathogens (virtual absence of pathogens); and that have a reduced level of degradable compounds that attract vectors.
Biosolids that are merely dry have several disadvantages for agricultural use. Biosolids that have a low fertilization value typically have a nitrogen content of only about two to five percent. The volume is large and the costs per unit of nitrogen are high. > Heat-dried biosolids often have an unpleasant odor, especially • p <1 when wet. In addition, dry granules have low density and stiffness when mixed with other materials •j: commercial fertilizers, granules may segregate and disintegrate and may not spread evenly over the field with other denser ingredients. The unpleasant odor associated with the use of biosolids, unless properly treated, will remain present during subsequent processing of a nitrogen-rich fertilizer product and may continue to be present in the final product. This complicates locating suitable fertilizer processing facilities in locations that are not close to residential communities. Additionally, the greatest distance where biosolids . must be transported adds cost and logistics of disposal of this waste product. Another disadvantage to current biosolids intensified fertilizers is that bacterial action can continue when the material becomes wet and under storage conditions the temperature of the material can increase to the point of self-ignition. Therefore, except for special markets that value its organic content; to F. modification or filling of the soil in mixed fertilizers, there is a relatively poor demand for . e heat-dried biosolids products. In many cases, municipalities must pay freight costs or may offer other incentives to commercial producers to use the material. However, this is often even more economical than alternative disposal schemes. * s
The market value for agricultural fertilizers is mainly based on their nitrogen content. There is a need for an economical, safe and practical method of increasing the nitrogen content of biosolids" to a level approaching commercial mineral fertilizers, for example, eight to twenty-two percent. If such a biosolids fertilizer can be Then manufactured the total value of the biosolids products and the demand for the product would likely increase.Furthermore, a properly manufactured biosolids fertilizer will have an advantage in that much of its nitrogen will be of the slow release type. slow ,fr or controlled release is that in which the nutrient, eg nitrogen as in ammonium, phosphate and/or sulfate ions, becomes available in the soil column at rates b fr • slower than fast-available nutrients such as a from traditional fertilizers such as urea, ammonium sulfate and diammonium phosphate. Its &L' action. slower and/or prolonged nutrient availability in the column of Soil is much more 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, thus reducing the potential for environmental contamination and reducing the cost of using the fertilizer. . Manufactured traditional ii * 5 inorganic nitrogen fertilizers with slow release have a 5; price many times higher than common mineral nitrogen fertilizers. Under the scenario of producing fertilizers containing high nitrogen biosolids from their biosolids, municipalities would appreciate public and regulatory support for their biosolids disposal program. Such a program would ensure regular removal of your dry or dehydrated biosolids, for example, by recycling biosolids into high nitrogen fertilizers which could then be sold directly to £** the mature fertilizer distribution industry, thereby eliminating one of the biggest problems traditionally associated with biosolids treatment programs
Previous attempts have been made to achieve some of the same goals. US patents 20 Nos. 3,942,970, 3,655,395, 3,939,280, 4,304,588 and 4,519,831 describe processes for converting sewage biosolids into fertilizer. In each of the' same processes, a ' •* condensation product of urea/formaldehyde is formed on site with the biosolids. In addition, the processes require the manipulation of formaldehyde, a highly toxic lachrymatory agent suspected of being a carcinogen. ,
Other processes require costly process equipment and/or special conditions not readily incorporated into existing -1 sewage treatment facilities (see, Japanese Patent No. 58032638; French Patent No. 2,757,504).
A simple method to increase nitrogen in r 1 / r biosolids would be to mix commercial phi nitrogen fertilizer materials with wet biosolids prior to drying and granulation. There are only a few high nitrogen fertilizer materials that are economical for use in agriculture. Examples include: ammonia (82 percent by weight N), urea (46 percent by weight N), and ammonium nitrate (33.54 percent by weight N). Ammonia is highly volatile and subject to strict regulation of discharges to the atmosphere. Urea is a solid that absorbs moisture almost immediately and makes sludge harder to dry. Urea is also highly susceptible to decomposition to ammonia by microbes and enzymes in biosolids, if they are properly prepared, resulting in nitrogen loss and an odor problem. Ammonium nitrate is a strong oxidizer and can result in a potential explosion problem that virtually eliminated this fertilizer from the commercial market after the year 2000. All of these fertilizers have high nitrogen content, but are far from ideal for combining with biosolids in the absence of special processing.
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 disclose the use of acids with ammonium sulphate additions and do not address the issue of corrosion of steel process equipment under acidic conditions.
Over the past 30 years, stabilization I ' Alkaline biosolids has been a standard method and is successful in turning biosolids into beneficially A 1 1 (useful materials that can be used primarily as soil conditioning materials. Because of the same alkaline stabilized biosolids products have {high As calcium carbonate equivalents, they have been produced and marketed as agricultural liming materials or Ag-lime, commonly as a substitute for calcium carbonate in agricultural land management strategies. The value of the same materials has been restricted to just a few dollars per ton of product. However, the cost of transport is high, largely due to the material's significant water content. and geographically restricted to areas close to the source of their treatment.
Thus, there is a continuing need for practical 7 • ways to increase the economic value of sewage biosolids by increasing their nitrogen content and increasing their spreadability as well as a need to treat these materials that are converted into fertilizers. commodities with physical, chemical and nutrient properties that can command a significant value in the national and international market of commodity fertilizers. A series of US patents, US patents 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 from biosolids using a tubular cross reactor. Tennessee Valley Authority. Tubular, T-shaped, and cross-tubular reactors are defined by the IFDC in the Fertilizer Manual (1998), page 440 as: "The tubular reactor basically consists of a piece of corrosion-resistant tube (about 5-15 m in length). length) to which phosphoric acid, ammonia and often water are % simultaneously added to one end through a tubing configuration similar to a T, hence the name 'T reactor'." The T reactor was modified by the TVA to also accept an additional stream of sulfuric acid. * 5 through another tube inlet located opposite the phosphoric acid inlet, giving the unit a "cross" configuration and hence the name "I cross-tube reactor",
Both the IFDC Fertilizer Manual (1998) and the Fertilizer Technical Data Book (2000) refer p L to cross tube reactors. Tubular cross reactors 41 deliver a concentrated mixture to the granulator device and evaporate unwanted water from the fertilizer mixture more efficiently than other devices, but these references demonstrate a long felt need for improvement, indicating that one of the shortcomings of the tubular reactor 25 in cross is the formation of incrustations inside the é-; tube that can result in obstruction.
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 marked by problems related to the obstruction of the same narrow "tubular cross" reactor configurations ( relative to its length), the very short duration of reaction time in such "tubular cross reactors" and the difficulty of controlling the temperature and pressure of the reaction and retention time of the mixture within such tubular cross reactors. (These tubular cross reactors are narrow in contrast to their length, for example, up to six to eight inches in diameter and often 50 feet or more in length. of 10 organically improved ammonium sulphate often had to shut down and disassemble the cross-tube reactor or s due to blockage from the build-up of biosolids or destructive overheating in such reactors that commonly use Teflon® coating on the reaction side (inside ) of the reactor has been melted down or ruined.' Furthermore, the use of the tubular cross reactor has the distinct disadvantage of having very short reactor retention times (usually less than twenty seconds) which is a p I. advantage in the manufacture of traditional fertilizers such as ammonium sulphate, but it is a disadvantage when coupled with the simultaneous processing of biosolids. stability of untreated or inhomogeneous mixture as the three input materials pass through this reactor. Also limiting is the lack of control over atmospheric pressure within such tubular cross reactors since these reactors have an indeterminate discharge directly to the granulator. Related to this, but distinct from the lack of internal pressure control, 30 tubular cross reactors also have little or no temperature control over the mixture passing through the reactor.
U.S. Patent No. 4,743,287 to Robinson I describes a method of using two reaction vessels in sequence to incorporate organic biosolids. in low or medium F* concentration nitrogen fertilizers (a range of four percent by weight nitrogen to one ml. A maximum nitrogen concentration of ten percent by weight I ll). Robinson uses his first reaction vessel to achieve very low mixture pH values (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 4, r 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 (206.84 kPag) with relatively longer retention times when compared* to tubular cross reactors. However, Robinson fails to satisfy the need for a new and practical A** continuous flow method for manufacturing fertilizer products with high nitrogen content (greater than 8 percent by weight nitrogen) and containing biosolid under the advantages 1 L of reaction set temperatures, pressure and retention times. Furthermore, an urgent need exists for an effective, efficient and cost-effective process for the treatment of biosolids. t Invention Summary
The present invention overcomes the problems and disadvantages associated with current strategies and models and provides new tools and methods for the manufacture of fertilizers. .5
One embodiment of the invention is directed to methods for making a fertilizer comprising: the provision of an organic material which preferably contains biosolids, wherein the organic material has a solids content of, at least ten percent; optionally adding an odor control agent to the organic material to create the mixture; adding an acid to the mixture under a first pressure and elevated temperature for a first period of time forming a liquified mixture; adding ammonia to the liquefied mixture under a , , ...... . ....... . X . .. . second pressure and elevated temperature for a second period of time; and processing the liquefied J/r mixture to form the fertilizer. The phrase organic material • 'í includes all biosolids, but is not limited to biosolids such as organic biosolids, rr biosolids containing micro-organisms, municipal biosolids or 20 heat-dried biosolids and also includes pharmaceutical and laboratory processing and wastes from fermentation, S3 farm and agricultural residues, decaying and digested organic materials, harvested plants including cultivated culture materials such as fiber and silage- *r "r, from soybean and corn plants as well as wheat, bouillon and barley plants, algae and cyanobacteria that can be harvested from lakes or other bodies of water, bacteria, mold and fungi, industrial waste and its by-products, microbial, chemical and enzymatic digestion of organic products, food of animal and vegetable origin, food products s 4 and by-products, recycled fertilizers and all and combinations thereof. One element of the invention is that 'organic material containing plastic and hairs and similar material do not need to be removed before the process.
Preferably, the organic material is dehydrating or hydrated to a solids content of between 15 and 40 percent, more preferably the organic material has a percent dryness of 22 percent or less. 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 desirable percent dryness. Preferably, the organic material is hydrated with water recovered from the process from one or more method steps. 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, rhozenite, melanterite, iron chloride, ferrous sulfate, ferrous sulfate monohydrate, . hydrogen peroxide, ozone and .salts, r t 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 and the mixture is heated prior to addition of acid. Also preferably, heating is carried out in a first pressure vessel and the first pressure is maintained between 20 and 60 psig (137.90 and 413.68 kPag), the first temperature is between 66C (150F) and 127C (260F) and 30 the first time period and the first time period is between 3 minutes and 30 minutes. More preferably, the VV first temperature may be between 93C (200F) and (121C (250F) and the first time period may be between 5 minutes and 10 minutes. Preferably the viscosity of the heated acidified mixture is about 4,000 cP or less. The acid added to the mixture is preferably phosphoric acid, sulfuric acid or a combination thereof. After acidification, the liquified mixture is transferred to a second pressure vessel and, preferably, the ammonia is heated under pressure. * to form a gas before being added to the liquefied mixture.
The second preferred temperature is between 121C (250F) and 199C (390F), the second preferred time period is between 1 minute and 30 minutes and the preferred pressure within the 4-4 second pressure vessel is maintained between 50 and 200 psig (344.74 and 1378.95 kPag). The viscosity of the ammonia mixture is preferably about 1000 cP or less. The •Ã. processing the liquefied mixture comprises forming the usable 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 hardening agents may be added during processing such as, for example, lignosulfonate, molasses, alum or a combination thereof. Preferably processing is carried out 'em. a . '• . - 1 • j • ' ' • granulator to form granules and the granules are sized and granules between 0.5 and 4 mm are selected.
Preferably, granules larger than 4mm are further ground and combined with granules smaller than 0.5mm 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 also preferably comprise a dust control system that collects and recycle dust material created from processing. I
Another embodiment of the invention is directed to fertilizer manufactured by the methods of the invention. The fertilizer will typically contain hydrolyzed polymers of one or more of plastics, pharmaceutical compounds, antibiotics, hormones, hormone-like molecules, biologically active compounds, macromolecules, carbohydrates, acids. nucleic acids, fats, lipids, proteins and microorganisms that are present in biosolids. Preferably, the hydrolyzed polymers are amino acids, most of which are not destroyed during the processing method which supplements and substantially increases 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 10 and 30 percent , an iron* content between 0 and 10 percent and an organic compound content between 5 and 30 percent. Also preferably, the fertilizer has no or almost no unpleasant odors.
Another embodiment 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: the provision of an organic material containing biosolids in which the organic material has a content of solids of at least ten percent; optionally adding an odor control agent to the organic material to create the mixture; heating the mixture under a first pressure to a first temperature for a first period of time; adding a predetermined quantity of acid to the heated mixture, thereby creating an exothermic reaction and forming a liquified mixture; the addition. from a predetermined amount of ammonia to the mixture liquefied under a second pressure and heating 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 processing the liquefied mixture to form fertilizer with a predetermined content of one or more of nitrogen, phosphate, and potassium. The process of the invention may optionally further comprise one or more plant nutrients during processing. Such plant nutrients which may be added include, among others, to one or more of urea, ammonium nitrate, ammonium sulfate, monoammonium phosphate, diammonium phosphate, urea solution and ammonium nitrate, liquid urea, potash, iron oxide, 'soluble iron, iron chelate and combinations thereof. Process 25 preferably further comprises adding and one or more hardening agents during processing such as, for example, ferric oxides, attapulgira alum clay, industrial molasses, lignin, lignosulfonate, formaldehyde-urea polymerizer and combinations.
Another embodiment of the invention is directed to systems for the manufacture of a fertilizer comprising: a mixer that mixes the biosolids with an odor control agent; a first reaction or pressure vessel in which the mixed biosolids 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 reaction or pressure vessel in which the liquid 10 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 granulator in which the ammonia-containing liquid is mixed with preformed granules and heated to form dry fertilizer granules.
Preferably, the ammonia source is liquefied or gas under pressure and the first and second reaction or pressure vessels each contain a stirrer. Systems may also include a screening process to select product sized fertilizer granules and one or more cooling and coating devices to reduce temperature and control dust prior to storage. -Optionally, the cooler can include an ozone generator that provides ozone to the fertilizer and is cooled to eliminate or at least substantially reduce unpleasant odors. t
Preferably, the systems also comprise a carrier for transporting the biosolids to the mixer and another carrier for transporting the mixed biosolids to the first reaction or pressure vessel; a piping system that transports acidified biosolids from the first reaction or pressure vessel to the second reaction or pressure vessel, ammonia to the second reaction or pressure vessel; and disperses the liquid with ammonia into the granulator. The .C systems • preferred still comprise one or more screens for selection • . - : r I of granules of a predetermined size and a cooler. rk . 4 rotary for the cooling and polishing of '' 'f sized granules and a dust control device that collects and recycles dust from a granulator and a water recovery system through which water extracted from biosolids during processing is recovered and recycled. In certain embodiments, the first and/or second t reaction or pressure vessel may be a tubular cross reactor or both reaction and pressure vessels are tubular cross reactors. The process can be carried out as a continuous or batch process. j
Another embodiment of the invention is directed to methods of manufacturing a product comprising: the provision of an organic material in which the organic material has a 1 content. ’ £ solids of at least ten percent; the addition ;of an acid to the organic material under a first pressure and ’ ' ' H..' elevated temperature for a first period of ‘time - ’ J; forming the liquefied mixture; adding ammonia to the liquefied mixture under a second pressure and elevated temperature b fc for a second period of time; and processing the b, liquefied mixture to form the fertilizer. Preferably the organic material is a plant or bacterial material and also preferably the plant or bacterial 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, the first pressure there is between 20 and 60 psig (137.90 and 413.68 kPag), the elevated temperature is between 66C (150F) and 127C (260F) and the first time period is between 3 minutes and 30 <minutes. Also preferably, the second pressure and elevated temperature for a second period of time are, respectively, 50 and 200 psig (344.74 and 1378.95 kPag) and between 121C (250F) and 199C (390F), between 1 minute J and 30 minutes. Preferably the product is a fertilizer.
Another embodiment of the invention is directed to the fertilizer manufactured by the methods of the invention. Preferably, the fertilizers of the invention have both slow and fast nitrogen release profiles so that a percentage of available nitrogen is released to the soil after application of the fertilizer, preferably from 10% to 70% and a second slower release representing about 30% to 90% of the available nitrogen toe from the fertilizer releases to the soil over a period of weeks and months. Preferably, nitrogen release is programmed to match the growing needs of crops or plants. 4, -5
Other embodiments and advantages of the invention are set forth in part in the description that follows, and in part may be obvious from this description or may be learned from the practice of this invention. I Description of Figures
Figure 1. Flowchart of the Biosolid Fertilizer Installation of an Invention modality.
Figure 2. Flowchart of the Biosolid Fertilizer Installation of another modality of the Invention.
Figure 3. Schematic of a Modified Ammonium Sulfate Process;
Figure 4. Physical and chemical characteristics of an organically modified ammonium sulfate fertilizer I of an embodiment of the invention. j
Figure 5. Nitrogen release curve of ammonium sulfate fertilized V-plants showing the percentage of nitrogen released to the soil over several weeks.
Figure 6. Nitrogen release curve showing the percentage of nitrogen released to the soil over several •R days for ammonium sulphate (AS), the inventive organically modified ammonium sulphate (VITAG)- and conventional biomass ( MILORGANITE).
Figure 7. Academic nitrogen release curve for plants fertilized with ammonium sulphate, the inventive organically modified ammonium sulphate, and biosolids showing the percent nitrogen released to the soil over several weeks. Description of the Invention
All countries and populated regions around the world create waste in the form of organic materials. The I phrase organic material includes, but is not limited to, biosolids such as organic biosolids, biosolids containing micro-organisms, municipal biosolids, and heat-dried biosolids and also includes laboratory processing and i. pharmaceutical and fermentation of wastes, agricultural and farm wastes, digested organic materials ;e . decaying, harvested plant and plant-like materials such as algae including blue/green algae, bacteria, t including blue/green bacteria, cyanobacteria | (eg blue/green, red, black), mold and figs, industrial wastes and their by-products, microbial, chemical and enzymatic digests from organic products, TV. animal and vegetable foods, food products and by-products, animal manure, digested and processed animal manure, recycled fertilizers and>all combinations thereof. The disposal of organic waste materials represents a bigger problem as well as the expenses for all communities. Traditional disposal methods involve burial, burial at sea or incineration. Each of the same options compound the problem by creating unsustainable amounts of pollution that foul the community as well as the planet. New techniques have been developed and involve heat treatment* to inactivate microorganisms and other potential contaminants that can result in a product that can be like a low-value fertilizer. While these techniques are ecologically sound, they are not understood, in large part, because the product is of such low value that there is little or no commercial incentive for communities to change the traditional philosophy of burying and burning and no background that allows for the creation of safe processing facilities.
It has surprisingly been found that high value fertilizers can be efficiently manufactured from organic materials, including but not limited to raw and semi-processed biosolids, agricultural materials and industrial waste. The process of the invention destroys not only potentially harmful micro-organisms, | but . L r , i hydrolyses many polymers including forms of biopolymers (eg DNA, proteins, carbohydrates, toxins, antibiotics, hormones, etc.), forms of composite materials and even forms of plastics. The resulting fertilizer product is of high value and also contains hydrolyzed monomers (eg amino acids, sugars, etc.) that are beneficial and desirable for a fertilizer. The process of the invention also allows the production of t F fertilizer with pre-selected amounts of each of the fertilizer components including, among others, the F r concentrations of nitrogen, phosphorus, potassium, sulfur, p iron and organics. ‘
One embodiment of the invention is directed to methods of manufacturing a fertilizer. A schematic of the general process * of the invention is described in Figure 3. The method comprises the provision of organic material which may contain biosolids or other organic material to which an odor control agent is optionally added, which itself may be used as an important plant nutrient in the final fertilizer product, to reduce or eliminate odors that may be present from organic material or other components of the starting materials. The resulting bd* mixture, which may contain recycled added water from other steps of the method, is thoroughly mixed and heated to a predetermined temperature for a period of time before initiating the critical acid/base reactions that occur in a reaction or hydrolysis vessel. To this heated material is added an acid which exothermically reacts A* with the organic material and increases both temperature and pressure. During this time, preferably two to ten minutes, the components are mostly or fully liquefied. To the material. A heated liquefied, which optionally can be transferred 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 the temperature and pressure. The ammonia and liquefied biosolids are held for a short period of time under these conditions, preferably two to ten minutes, and then processed, preferably into fertilizer granules.
The ammonia reaction can be carried out to completion whereby all or almost all acid is reacted in such a way that little or no residual acid remains. The combination of almost any acid produces a salt or molten salt (a partially ammoniated mixture) (eg, with sulfuric acid, the salt produced is ammonium sulphate). Preferably, after the ammonia salt has melted, the proportions are about 20/80, about 25/75, about 30/70, about 35/65, about 40/60, about 45/55, about about 50/50, about 55/45, about 60/40, about 65/35, about 70/30, about 75/25, and about 80/20. Salt formation can be determined in real time by . L' measurement of the pfi of the mixture. Preferred pH values are between 6.2 and pH 7.0. Alternatively, it is sometimes preferable to partially ammoniate the acid mixture in the reactor and complete the ammonia in a second pugmill type mixer or in the granulation process. J
An advantage of this invention is that, because the organic materials are liquefied, the liquid can be more easily transported, as needed, through tubes preferably using pressure differentials, as compared to any solid, semi-solid or thixotropic material. The liquefied organic materials 1 can also be applied more uniformly to the acceptor material in the granulator thus allowing the formation of a more uniformly shaped spherical shaped granule 4. The biosolids are preferably fully liquefied, although the majority liquefied is sufficient. Preferably, the liquid has a characteristic flow arrangement, little or no tendency to disperse and relatively high incompressibility.
The viscosity of the organic starting material is typically in excess of 100,000 cP and typically 150,000 • -1 at room temperature and does not change significantly even at elevated temperatures typical of a processing facility. For comparative purposes, at near ambient temperatures, molasses possess'; 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 olive oil has a viscosity of about 81 cP. , '-1 I' b. - With the addition of acid and heating according to the invention, the viscosity of the organic material drops to a range of about 1,000 to 10,000 cP and preferably to less than 4,000 cP, more preferably to less than ;3,000 cP, most preferably less than 2,000 cP and more > preferably less than 1,000 cP. With the addition of ammonia and the temperature increase added from the resulting exothermic reaction, the viscosity decays to a (range of 500 to 4,000 cP and preferably 2,000 cP or ijienes, more preferably to 1,000 cP or less and most preferably to 750 cP or less and more preferably *500 cP or less. Furthermore, the problems typically associated with solid debris that are normally present in organic material such as biosolids, with debris such as plastics and hairs, are eliminated as all such material is also hydrolyzed.
The low viscosity material of the invention has z-7, . . i a substantially reduced energy requirement for transport and processing compared to conventional materials. No organic or biological material remains, so problems and inefficiencies commonly associated with clogging or otherwise blocking by transporting solid debris from one area to another and thus necessitating system shutdown for maintenance are eliminated. No solids or semi-solids are present, which would otherwise increase equipment wear and thus shorten equipment life. In addition, solid organic materials including, for example, plastics and hair, well known to cause blockages in conventional processing, are completely broken down and hydrolyzed into their monomeric components. The acidic reaction hydrolyzes many polymers that may be present including plastics, hairs and biologically active compounds (naturally present or artificially created) and breaks down and destroys many, almost all and preferably all macromolecules and micro-organisms that may be present. This increases the r ’ «I ' « safety for process workers and further simplifies .f. 1 5 and increases the efficiency of any cleaning or maintenance of the b" * . • • > system that may be periodically needed.) This hydrolysis further increases the safety of fertilizer use í 6; resulting in comparison to other fertilizer products containing organic substances such as those done in >$10 alkaline biosolids stabilization processes.;
Another advantage of the invention is that, because the process can be easily contained, the need for dust and odor control devices is minimized. Processing steps are closed and under negative pressure and no steps are carried out in open or areas exposed to the environment or the environment of the installation. Control agents. - - odors are preferably added initially, but can optionally be easily added at any stage of the process. Alternatively or in addition to other odor control processing, the granules may be exposed to ozone during formation and/or [cooling. Ozone will substantially reduce or F .5 will eliminate unpleasant fertilizer odors. Furthermore, the invention represents a significant improvement over conventional fertilizer manufacturing practices in which a large manufacturing facility is located as far away from communities as possible, thus requiring input materials to be , there! shipped over long distances to operate the 30 facility. A good example of this problem was the biosolids to fertilizer conversion facility located in Helena, Arkansas, which practiced the manufacturing processes taught in the US Patents US. r, 5,984,992, 6,159,263, 6,758,879 and 7,128,880 and used biosolids that were transported by. all the way :Í- 4 from New York City. 1
Another advantage of the invention is that, because the acid and ammonia are added in a controlled manner, the final fertilizer components 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 sulfuric acid, 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 cultures in need. Fertilizers are cultivated in areas known to be rich in phosphate, sulfur, potassium or other elements. Fertilization with conventional fertilizers, although necessary, typically 4 r r' aggravates the contamination. Fertilizers produced by the *'''>'b'' methods of the present invention would not only overcome such problems, but could be adapted for use in conjunction with a specific type of soil or the specific need of a selected type of crop. .
Furthermore, the process of the invention allows for fertilizer supplementation during processing with additional ingredients.
Another advantage of the invention is that it is easily carried out on a large scale, with continues processing and in k automation. No significant retention time is needed, therefore no delays, so processing continues from beginning to end without interruption as may be necessary when the material needs to be incubated for days, as is common for some types of «« H* processing of conventional comb biosolids into composting or alkaline stabilization processes; Furthermore, the process is not dependent on a particular quantity of material. The process of the invention is scalable for any amount of organic material. This is highly preferred, at least, because most municipal regions vary in size and therefore the amounts of organic materials such as biosolids produced per day vary widely. Furthermore, the amounts are expected to vary over time. What's more, each step of the process can be performed in full automation including accounting for the necessary variation per day over time. '
Another advantage of the invention is that it allows the colocation of facilities for processing organic materials such as biosolids with treatment facilities. The biosolids can then be taken directly from the wastewater treatment facilities for processing, thus minimizing the transport and potential spillage of potentially harmful compounds. Another preferred embodiment is to be located close enough to the wastewater treatment plant to be connected by a screw conveyor or conveyor belt or a sewage sludge pumping system. Alternatively, another preferred embodiment is to be located adjacent to the wastewater facility. The aim of the present invention is to place the treatment facility as close to the wastewater facility as possible. In addition, the present invention eliminates the cost of transportation by locating the physical equipment needed to carry out the manufacturing process adjacent to or near the source of biosolids such as municipal wastewater treatment facilities. The manufacturing facilities of the invention preferably allow adjacent storage facilities. Again, by being adjacent, transport logistics are simplified or eliminated, thus reducing product transport costs as well as the cost of transporting organic input materials such as biosolids. Furthermore, the processes of the invention have the advantage that they can be connected with other production facilities. Those facilities may be associated with an unrelated commercial enterprise such as, for example, the production of nylon or steel. And in these two industries, hot ammonium sulfate is created as a by-product of manufacturing the product. Additionally and more commonly, co-location close to a commercial company that creates excess heat, such as in a furnace or furnace, would advantageously allow the use of that excess heat by the present invention as in replacing the need for fossil fuels such as natural gas or | by co-generating electricity by using said excess heat. By placing a processing plant of the invention in these types of places, unwanted by-products such as 1/*• ammonium sulphate need not be discarded, but can be directly used in the manufacture of fertilizer according to the present invention. 1
Another advantage of the invention is that because the process minimizes the amount of water and energy (eg electrical) required and the amount of waste by-products formed, compared to conventional processing, the fabrication can be scaled there to meet the size needs of the community. in particular in which the facility is located., This retrofit project for a fertilizer fabrication/biosolids processing facility that "can process smaller quantities of biosolids (eg less than 3 tons per hour of dehydrated biosolids) , r Y or scaled for larger installations (eg, up to 10 to 12 tons per hour or more) In a preferred j modality, the optimum size is between 6 and 8 tons per hour when biosolids are standardized to a percentage solids of 25. The amount of biosolids processed per hour depends on the percentage of solids in the * biosolids. nt in moisture the amount of biosolids that can be processed per hour increases proportionally. This scaling feature reduces cost, allows for the standardization of interchangeable equipment and increases the efficiency of operational logistics, as well as decreasing overall responsibility. Organic materials that can be processed in accordance with the invention include, among others, biosolids. Types of biosolids include municipal biosolids, domestic sewage, farm and agricultural wastes, animal manures, digested and processed animal manures, organic biosolids from recycled biosolids fertilizers, biosolids containing micro-organisms and heat-dried biosolids. Other organic materials that can be processed according to method 1* • J • . , ,b r of the invention include, but are not limited to, pharmaceutical and laboratory processing and fermentation wastes, industrial organic wastes, microbial materials, decaying and digested organic materials, farm and agricultural wastes, Á materials. . harvested plants such as algae including blue/green jalgae -,** blue/green algae and other aquatic plants and waterborne organic debris, bacteria including blue/green bacteria and cyanobacteria (eg blue/green, red, black) , slime, insects and biomass I • ' * . 1 from insects (eg body part, manure), mold and fungi, industrial waste and its by-products, microbial, chemical and enzymatic digests from organic products, food, food products and food by-products € and their combination. In addition to conventional biosolids, 5 most all organic materials can be processed by the methods of the invention including spoiled or otherwise rotten food products such as, among others, meat, fish and agricultural products, as well as 7. plastics and household waste that contains carbon and b * recyclables.
Another advantage of the invention is that organic materials and even certain non-organic materials, which are otherwise difficult to dispose of, can be processed in accordance with the invention as a method of transformation into a otherwise useful product. shape, would be V material. / "Residual A occupying space in a pu landfill in the ocean. As a non-limiting example, the alga is K' removed from the surface or otherwise collected from water bodies for aesthetic purposes as well. as for|health jj of the plants and animals that inhabit the environment.
Often, this alga can be contaminated with natural toxins or toxic compounds absorbed or metabolized and concentrated within the alga from the environment.
By processing the seaweed according to the methods of the invention, the seaweed can be converted to fertilizer and, more importantly, have the toxins destroyed or otherwise • 'X kl. disabled. Furthermore, algae and other plants or bacteria can be intentionally cultivated over a contaminated area and harvested to be processed in accordance with X. the invention. Furthermore, as toxin contamination is a matter of concentration, materials generated from the processes of the invention can be added to other processed materials and sufficiently diluted so as not to present a hazard. This process of recovery of Ji ‘ , y.' earth or water can be carried out with a variety of 3g plants, bacteria and insects with the collected organisms, $ processed according to the invention and made non-toxic .. . . . or otherwise harmless. Therefore, the process of the invention can be applied to treated or untreated soil, humus and most any biomass including p-cellular components, sedimentary organic matter and biotic materials.
The organic material is preferably dehydrated or hydrated to a solids content of between 10 and 40 percent, more preferably between 20 and 30 percent, and most preferably between 22 and 25 percent. The optimum solid content of a particular organic material can also be determined empirically or experimentally. 0 organic material received for processing according to 1/; invention will typically have lower solids content than the optimum level. Preferably, the organic material of sJ. insufficient solids content can be adjusted to the desired concentration by mixing with "dry" organic material with a solids concentration of 7% to 95 percent and preferably 85 to 92 percent. The "dry" organic materials 1' can be available through third party sources or can be produced with the organic material t-, 2 available through heat drying. Heat drying >’ processes include heated screw conveyor, disc dryers, rotary dryers, * paddle dryers/mixers, fluid bed dryers and other commercially available processes/equipment. The dry organic materials and the organic material of insufficient solids concentration will be mixed * in a mixing vase to achieve the ideal solids content as determined empirically or . experimentally. The mixing vessel may be a pugmill type mixer, a screw mixer, a mixing conveyor, a multi-shaft mixer, a horizontal paddle mixer, a mixer. .f. high shear or other high viscosity i ' ' r y commercial sludge mixer. Less preferably, the organic material of insufficient solids content can be adjusted to a 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 require hydration and, where necessary, additional water. .7 S' is preferably added from collected water • ( during other processing steps. This water use
Recycled U further adds to the efficiency and economic benefits of the invention. If necessary during inbound processing, the organic material can be conditioned by injecting steam, water and/or heat (eg thixotropic effect) to activate or increase flow or movement. In these initial steps, the organic material can be mixed with chemical additives such as oxidizing agents, i for initial odor control and to prepare biosolids for pressure vessel reaction. For example, biosolids can be infused with black or agricultural grade phosphoric acid to minimize odors. In this example, the 'A'- ►f phosphoric acid added here will change the final concentration of phosphate in the fertilizer product. The amount of phosphate added to the product at this stage can be as little as . r * ”1 0.5 percent and as much as 6 percent. In addition to odor minimization, phosphoric acid adds a valuable nutrient component to the fertilizer product.
Preferably, the odor control agent is added to the starting organic material to be processed, although an or. more odor control agents can be added at any time during processing, including during granulation and cooling. Preferred odor control agents include, but are not limited to, calcium ferrate, sodium ferrate, potassium ferrate, ferrous sulfate heptahydrate, rozenite, melanterite, iron chloride, ferrous sulfate, sulfate, .7. ; ferrous monohydrate, hydrogen peroxide and/or ozone, £ i -v as well as various other salts, derivatives and combinations % of these. 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, ii. by weight of mixture or granules, up to 6 percent of ¥. mixture or granules and is preferably about 0.05%, 0.1%, 0.25%, 0.5%, 0.75%, 1.0%, 1.5% or 2.0%. | The organic material, odor control agent and possibly water recycle are delivered to a mixing vessel where they are mixed and can form a thixotropic slurry which is pumped or easily transported. The mixing vessel may be a pugmill type mixer, a screw mixing conveyor, a multi-shaft mixer, a horizontal paddle mixer, a high shear mixer, or another high viscosity commercial sludge mixer. Pugmill-type mixers, blenders, and mixers are mixing chambers that have either blade-shaped mixing elements mounted on a shaft or powerfully driven shafts that rotate at a variable but controlled speed. that divide, mix, remix and redivide the materials to be %* mixed several times per second to obtain a complete and uniform mix with a reliable consistency. *
Alternatively, the mixing vessel, to achieve solids concentration, and the mixing vessel, which stops conditioning with the recycling of water, acid, odor control agents or other additives, can be combined in a single suitably sized mixer. to give a 'd. desired energy and mixing time. j
This mixture is preferably heated by indirect heat Y such as a heated screw conveyor, paddle mixer or disk dryer or direct heating such as steam injection, to a temperature required for proper reaction in the next stage. acidification process. The temperature required is determined by the type II and concentration of acid used as well as the type e. , r concentration of the mixture of organic materials. Heating the mixture preferably involves continuously mixing or stirring the mixture within the mixing vessel and possibly heating the vessel itself. Therefore,. for k to reach a desired mixing temperature, more or less 1’1 heat may be needed depending in part on the composition of the vessel material. Preferably, heating is carried out for a holding time period which is equivalent to the time required to reach the desired temperature α-V* or mixing can be maintained for long periods of time. Preferred time periods, which include heating time, are between 1 and 30 minutes, more preferably between 3 and 15 minutes, most preferably. d between 5 and 10-minutes (or any combination of these ranges). Furthermore, heating times can also be dependent on the amount of mixture being heated. Preferred is a heating time that is about f'i 30 equivalent to the time it takes to reach the desired temperature z V t * A. Less preferably, heating can be achieved through direct injection of steam or heated 1 Js e-gases into a mixing vessel or piping system. In the preferred embodiment, acid is added to the heated mixture at the inlet of the first pressure vessel, creating an exothermic reaction, thereby causing further heating. Acid is added to the mixture by direct injection into a pressure vessel or injection at the outlet of the vessel. 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 pH 4.0 negative to pH 2.0 positive. As is known to those of skill in the art, with 'very strong aqueous acids there are too few water molecules' to disassociate the acid completely. As a consequence, the .V true pH is much lower than an actual measurement. A negative pH indicates that the pH calculation would be a negative log molarity where the hydrogen ion molarity is greater than 1. Preferred pH values for the acids used are, for example, pH 2.0 or less, ft * f pH 1.0 or less, pH 0.8 or less, pH minus 1.0 L or less, pH minus 2.0 or less. Preferred acids include, but are not limited to, hydrochloric acid, 'boric acid, hypochlorous acid, perchloric acid, • acid, '' • , ''1 V 1 J II carbonic acid, phosphoric acid, sulfuric acid, nitric acid, F hydrofluoric acid, carboxylic acid and its derivatives, è 'b .' 4 f- mixtures and combinations thereof. quantity of organic materials being treated and/or the desired result, which includes, but is not limited to one or more of, the range of a predetermined temperature or pressure or liquefaction of the mixture. little or no build-up of calcium silicate, insoluble phosphate compounds or other insoluble compounds in pipes, a typical problem with conventional sewage sludge processing facilities.The addition of the acid causes an exothermic reaction that heats up and increases the pressure are from the container. This pressure which upon the beginning of the reaction is in ambient. and can, in fact, be maintained at ambient or at a desired pressure throughout the acidification process through monitored or controlled ventilation. Alternatively, the pressure may be allowed to increase with increasing temperature due to the exothermic heat of the dilution reaction. Such pressures can reach a range greater than 60 psig (413.68 kPag). by ventilation control or in the absence of ventilation.
The temperature of the mixture preferably rises to or above 66C (150F) such as, for example, stops at or above 82C (180F) or 93C (200F) and more preferably is at or above 104C (220F), HOC ( 230F), 116C (240F), 121C (250F), 127C (260F), 132C (270F), 137C (280F),; 143C i. £ (290F), 149C (300F), 163C (325F) or at or above 177C (350F). This acidification can be carried out without pressure in the reactor by allowing the release of air from the container during acidification, however, in the preferred mode, A' to facilitate the transport of the acidified mixture inside the second vessel at pressure in the first vessel or acidification vessel will be maintained above the pressure achieved in the second vessel. The acidification process is carried out for a retention time of between 3 minutes minutes with a preferred time of between 4 minutes and 8 minutes.
The subsequent addition of ammonia base, preferably in a second pressure vessel, further affects the temperature of the mixture, preferably »; increasing the temperature to or above 132C (270F) such as 138C (280F) or 143C (290F), more preferably to % or above 149C (300F), more preferably to or above 154C (310F), 160C (320F) ), 166C (330F) or 171C (340F) and more preferably at or above 177C (350F) such as, for example, at or above 182C (360F), 188C (370F), 191C (375F), 193C (38CF ), 199C (390F), 204C (400F/210C (410F), 216C (420F), 221 (430F), 227C (440F) or < 232C (45OF) Preferably, heating is carried out for a retention time period which is equivalent to the 4 time required to reach the desired temperature and allow V t to complete reactions. Preferred reaction time periods, which may include exothermic heat time, are between 1 and 30 minutes, more preferably between 3 and minutes , more preferably between 5 and 10 minutes or any combinations of these ranges. Furthermore, the reaction times may also be dependent on the constituents and/or constitution. the amount of mixture that is reacted and/or the amount and/or type of acid added. The reactions take place in closed vessel vessels and the pressure in the - N headspace of the vessel vessel increases accordingly.
Pressures can again be regulated with pressure relief valves and are preferably maintained between 5 psig and 250 psig (34.47 and 1723.69 kPag), T more preferably between 30 psig and 150 psig (206.84 and 1034.21 kPag ) and more preferably between 40 and 10Opsig (275.79 and 689.47 kPag). Preferred pressures include, but are not 827.37, 861.84, 896.32, 965.27, 1034.21, 1103.16, 1172.11, 1206.58, 1241.06, 1310.00, 1378, 95, 14p.90, 1516.85, 1551.32, 1585.79, 1654.74 and 1723.69 kPag. j£
After the acid has reacted at the desired time, at temperature and pressure, the acidified mixture is discharged from the acid pressure vessel and . f transferred to a second pressure vessel. In the second pressure vessel, ammonia is injected into the mixture such as i inlet of the second pressure vessel or directly into the interior of the second pressure vessel. The amount and form of ammonia added are determined by one of ordinary skill in the art, from the amount of acidified mixture or organic materials that are treated and the / desired result, which includes, but is not limited to, one or 20 more among, the achievement of a predetermined temperature or pressure or liquefaction of the mixture. The addition of ammonia increases the temperature of the mixture releasing steam which increases the headspace pressure within the second pressure vessel. Pressures can again be regulated with pressure relief valves and are preferably maintained between 50 psig and 200 psig (344.73 and 1723.69 kPag), more preferably between 75 and 150 psig (517.11 and 1034.21 kPag) and most preferably between 10Opsig and 130psig 689.48 and 896.32 kPag) (or any combinations of these ranges). Preferably, the ammonia addition is carried out for a retention time period that is equivalent to the time required to inject the ammonia and complete the ammonia reactions. Preferred time periods are between 1 and 30 minutes, more preferably between 3 minutes. and 15 A minutes and more preferably between 5 and 10 minutes (or % any combinations of these ranges). Furthermore, the time to inject ammonia and complete the ammonia reactions may be dependent on the amount of acidified mixture present and/or the amount and/or form of ammonia added. The pH at this point is preferably from about -1 0.5 is about 7.5 and more preferably from about i-6.0 to about 7.0.
The processes of the present invention with biosolids and other forms of organic materials produce a fertilizer that is preferably followed to withstand and work with and preferably meet and/or exceed the minimum requirements for USEPA Class A biosolids. The fertilizer product is preferably sterilized and the biological and chemical contaminants are at least partially and preferably completely hydrolyzed and biological agents or organisms are denatured to the point of inactivation and/or destruction. Typical biological or 4'-chemical 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 of the same. The present invention preferably includes a stress that is conditioned on a predetermined retention period that creates stress conditions which > meet or . exceed those associated with traditional autoclaving materials. This autoclave effect destroys and/or inactivates or simply sterilizes the material • 5V organic. Microorganisms in organic material including, for example, bacteria, viruses, fungi, parasites, parasite eggs, bacterial and fungal spores and 1 >. combinations thereof, are destroyed and/or inactivated. In addition, the processes of the invention are preferably designed to hydrolyze macromolecules such as proteins, nucleic acids, lipids, fats, carbohydrates and combinations thereof and/or other E.I. 5 . , biologically active substances that may J be present. $
At any time during the method steps, one or more hardening agents may be added to the mixture. Preferred hardening agents include, but are limited to, ferric oxides, attapulgite alum clay, industrial molasses, lignin, lignosulfonate, urea formaldehyde polymerizer and combinations thereof.
At the desired time, which can be determined empirically or experimentally, the liquid is processed into the fertilizer. Preferably, the processing involves transfer to a granulator for dewatering and forming dry fertilizer granules. Preferred processing is in a granulator that contains 60 to 88 weight percent old granules and the granules dryness preferably with heat to greater than 90 percent solids and preferably 98 to 99 percent solids or more. Preferably, the water extracted from the granules is collected with a part recycled in the process steps and the remainder is treated for discharge. The granules. y are typically very hot during the aridity process and optionally can be allowed to cool by transfer to a room refrigeration apparatus £ or refrigeration. During refrigeration, ozone can be injected into the refrigerator as an odor control measure. The preferred amounts of ozone to be injected 10 are from 0.01% to . 5% by weight of the í granules. refrigeration, more preferably from 0.1% to 2% and more preferably from about 0.5% to 1%. Preferably, ozone is introduced into the refrigeration apparatus by spraying. ! 15 Once dry and formed and optionally after cooling, the beads are molded and the preferred bead size is 0.5mm to 4mm. Most preferred are the . 1 : " * " 4 standard fertilizer granules of about 2.8 1 mm and especially "mini" granules of about 1 mm. . »
One or more commercially available hardening agents can be added to the granulator. Preferred hardening agents include, but are not limited to lignosulfonate, lignin, molasses or a combination thereof. Granules larger than 4 mm and smaller than 0.5 mm fcrf are recycled in the granulator. Granules of the desired size are further processed by coating with one or more available dust control agents. Preferably, granules larger than 4 mm are crushed and mixed with granules smaller than 0.5-30 mm and everything is recycled in the granulator.
The invention preferably provides both dust and odor control systems to ensure acceptance by the manufacturing plant community and facilitate meeting USEPA standards as well as making the 'Z process more efficient by capturing and incorporating valid nitrogen or * ' IV other potential and/or fugitive plant nutrients from the plant's processed air. |
Another embodiment of the invention is the fertilizer manufactured by the methods of the invention. The chemical and physical characteristics of an organically modified ammonium sulphate fertilizer of a preferred embodiment of the invention are listed in Figure 4. The Fertilizer from . Organic materials such as biosolids can be pulverized either in blocks or are preferably in the form of granules which are of a predetermined size and are resistant to crushing after polishing compared to unpolished granules. Additionally, preferred .f granules have a smooth exterior with some holes or slits and circular or oval shape. Preferably, the fertilizer contains no or 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. The hydrolyzed polymers form polymer monomers which accumulate in the product and are preferably amino acids. Jr; The process of the invention preferably results in the production of granules or pellets of USEPA Class A fertilizer product. of aridity, hardness and chemical quality adequate to produce a controlled release of high - 1 . V... I nitrogen is a valid (eg slow release or í; J 5 double release) commercial fertilizer product that is; able to compete in the national and international market against traditional inorganic fertilizers. A commercial high nitrogen fertilizer preferably has more than 8 percent dry weight nitrogen of the finished fertilizer and more preferably at least 16 percent dry weight nitrogen of the finished fertilizer. ,The characteristic of . Class refers to the microbiological quality of the product » finished fertilizer, which meets the microbiological standards Class t
The US Environmental Protection Agency for J. . s I a product containing municipal biosolids as defined in 40 C.F.R. § 503. Furthermore, the fertilizer of the present invention meets or exceeds this coit standard based on the stress condition and retention time using, 1 . therefore, to ensure that the associated USEPA Vector Attraction Patterns are met (90 percent solids or more in the finished product), the finished fertilizer granule is optimized for minimum X water content which increases the characteristic of hardness and eliminates the f 25 water in relation to the transport of the finished fertilizer. , LAUGH
The percent solids of the finished product is preferably greater than 92 percent solids, more preferably greater than 97 percent solids and more preferably greater than 99 percent solids.
Biosolids treated according to the processes of the invention typically contain low levels of metals* such as arsenic, cadmium, copper,. lead, mercury, molybdenum, • •, j. ► v* -. B . I nickel, selenium and/or zinc. Low levels are levels below that are considered harmful and below the Standard 5 for Outstanding Quality ("EQ") for metals as published by USEPA for products containing municipal biosolids. Therefore, by exceeding the J-USEPA regulation and hydrolyzing conditions of the hydrolyzachlor or pressure vessel for macromolecules (eg, personal pharmaceutical products such as antibiotics or hormones or hormone-like substances), the resulting fertilizer is safe for use in and around agriculture, plants and animals and is exceptionally safe for workers to handle during processing, handling, distribution and sales. : Since the fertilizer product produced contains both biosolids and a desired high nitrogen content, a preferred embodiment results in a variety of nutrient-specific formula fertilizers of which the following are typical: 16-0.5-0-18- 3-15 or 16-0.5- 2-17-3-14 (Nitrogen-Phosphorus-Potassium-Sulphur-Iron-
Organic materials) a slow-release granular fertilizer that is at least 99 percent dry and exceeds the US Environmental Protection Agency's Class A (USÉPA) and Exceptional Quality (EQ) requirements. The 16 percent controlled-release organic nitrogen component helps bind *V nitrogen in the root zone when and where it's needed. For example, the nitrogen in the ammonium ion, because it is bound to biosolids components, slowly migrates through - the root zone and... becomes available to the plant rather than being volatilized or V. lost to the water table below from the root zone; As a result, it can be absorbed into the plant 5 slowly over time. j
The fertilizer product can be adapted to a desirable content of elemental components. Preferably the fertilizer has a nitrogen content of between 6 and 20 percent, more preferably from 8 to 18 percent, a phosphate content of between 0 and 10 percent, more preferably from zero to 5 percent, a potassium content of between 0 and 5 percent, more preferably from one to four percent, a sulfur content of $ between 10 and 30 percent, more preferably from 20 percent, a iron content of between 0 and 10 percent, more preferably from one to four percent and an organic content of between 5 and 30 percent, more preferably from 10 to 20 percent (or any combinations of these ranges) . i
The fertilizer product contains nitrogen in the form of ammonium ions non-covalently bound to organic A' compounds and other chemical compounds in the fertilizer. Unlike < ’ unlike ammonium sulfate fertilizer, b< |í ions. bound ammonia are not all immediately released into the soil after application. Instead, there is an immediate release of a pool of nitrogen into the soil that represents a 4 r f from about 30 to 60% of the available nitrogen from r • , . j. - ' fertilizer. This rapid release is typically over a period of one to two weeks, being slower than a conventional ammonium sulfate fertilizer which typically releases 90% or more of its available nitrogen into the soil in about 5 to 10 days, however it is slightly faster than or equal to the nitrogen release from conventional pure biosolids fertilizers. During the following days and weeks, the volume of nitrogen i' remaining from the fertilizers of the invention is gradually released into the soil. Sun, heat, water and/or microbes in the soil act on the fertilizer and slowly break down the •L. ionic bonds releasing available nitrogen to plant roots. Preferably, nitrogen release is from about 1% to 5% per week and: more preferably from about 2% to 4% per week. 3'
A small amount of nitrogen can be covalently bound to the fertilizer compounds and thereby remain unavailable to the plant.
Preferably, this amount of unavailable nitrogen f* «y 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 unavailable with conventional fertilizers.
The dual release fertilizers of the 'A*' invention allow a single application of fertilizer that provides a cake of nitrogen for growing and growing plants such as commercial crops (eg fruits, vegetables, grains, trees) then a quantity continued preferably over all or part, give a t growing season (eg see figure 7): This minimizes the number of fertilizer applications required per crop which provides substantial savings in application expense.
Another embodiment of the invention is directed to a process for manufacturing a fertilizer with a predetermined content of one or more of nitrogen, phosphate and/or potassium. The processing of organic materials * * proceeds as described here in which the selected acid is of the type and quantity desired in the final fertilizer product. For example, using a set amount of phosphoric acid will result in a set amount of 4 t' of phosphate in the final fertilizer product. Through 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 • ' L acid, one can pre-select the content of the product in the fertilizer 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, urea, liquid, potash, iron oxide, soluble iron , chelated iron, micronutrients similar to magnesium, I manganese, copper, zinc, molybdenum or boron and combinations f. of the same. ;
Another embodiment of the invention is directed to a system for manufacturing a fertilizer. The invention comprises a mixer which mixes the organic component containing biosolids, optionally with an odor control agent. The mixture is then heated either in this mixer or in a separate heating vessel. Heating the mixture preferably involves mixing or continuous stirring during the addition of calofat through J . indirect heating eg heated vessel walls or heated mixers or direct heating eg steam injection or heated air. The heated 1<1** 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 conditioned acidic slurry slurry. An agitator/mixer is incorporated inside the first pot of. pressure. Optional heating elements that can be external to or internal to the vessel may also be incorporated into the pressure vessel. The acid can be mixed directly with the heated biosolids in the first pressure vessel or, preferably, the acid and heated biosolids are combined in a mixing tee and added together to the pressure vessel. Inside the pressure vessel the built-up heat and pressure is continued for a period of time to form a liquid from the slurry-like slurry 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 so as to avoid or minimize the possibility of sludge V material remaining in the conduit. Also preferably, the acidified liquid mixture R1 is combined in a mixing tee with the ammonia from an ammonia source, preferably liquid ammonia and forcibly injected together into the second pressure vessel. Preferably, the liquid mixture is forced through the conduit by gas therein; which is added to the system behind the liquid mix to ensure that all of the liquid mix is transferred to the second vessel. Preferably, the gas, which may be air or another gaseous compound or mixture, is purged by means of a relief valve in the second vessel. - i
Within the second pressure vessel, the acidified and nitrogen fortified liquid mixture exothermically heats to 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 is vaporized under pressure. Also preferred is a system whereby the first and second pressure vessels each contain a stirrer or other mechanism which mixes in a manner 1/* continues mixing. Alternatively, the first and second pressure vessels can be the same. After ammonia, the £M mixture is transferred to a pugmill or granulator mixer where steam and water vapor are released and the ammoniated liquid is mixed with preformed granules (commonly referred to as "recycle") to form or shape the new fertilizer granules. These granules 1 are then heated in a rotary dryer or fluidizable bed dryer to form dried 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 headspace pressure above the biosolids in this pressure vessel. The system 1b also preferably contains a conveyor (e.g. pump or (conveyor screw, conveyor) for transporting biosolids to the mixer and another pump for transporting the mixed biosolids to the first pressure vessel; a pressurized piping system that transports the acidified biosolids from the first pressure vessel to the second pressure vessel, the ammonia into the second pressure vessel, and disperses the ammoniated liquid to the granulator. carried out, without the need to interrupt the JF' and continuous flow of biosolids in and out of the pressure vessels.
From or incorporated into the granulator, it is preferably a rotary drier or alternatively a fluidizable bed drier which additionally dries the sewage sludge fertilizer to less than 1 per certain water content. After leaving the dryer, the fe’ biosolids fertilizer is further selected by size and separated by product into undersized and oversized granular groups. The undersized particles's are q . r recycled back to the inlet of the second pugmill mixer. The oversized particles are sent to a hammer mill where they are crushed and then * recycled. After leaving the screening process, the biosolids fertilizer granules are processed through the ► rotary cooler where the biosolids fertilizer is * cooled. Optionally, the chiller can include a -1 ozone generator that provides ozone for the cooling fertilizer. In the presence of ozone, complexes of materials that cause odor with oxygen and other possible molecules present in biosolids and which substantially reduce or eliminate unpleasant odors. Fertilizer granules * empty into the final polishing screens to remove undersized granules or dust created in the y cooling process. After processing through the polishing machines, the product passes through a coating drum where a coating agent that inhibits the formation of dust is added. The biosolids fertilizer is then stored ready for bulk shipment or subsequent packaging. Alternatively, the 4 granules can be subjected to an air polishing system that continuously recycles the hot air generated in the cooling process to the aridity stage which results in a reduction in fuel and waste usage of air for processing. Air taken 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 that discharges from the cooler is again cleaned in a dust collector. The heated, clean air is used as ã - q k ’• • 4. h air inlet to the rotary dryer. The system preferably also contains one or more screens for selecting beads of "1,•' 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, vacuums and bag filters which collect dust from the granulator and also a water recovery system whereby the water extracted from of biosolids during processing is recovered and recycled making the system very efficient.
In a preferred embodiment, the process air is acidic and purified to remove any fugitive odors and especially vaporized or gaseous ammonia. The captured ammonia, since an ammonia 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 residues include dust, non-spec or reclaimed product and dry fertilizer which is very small or undersized or oversized material which is crushed in a crushing or grinding apparatus or may include other additives by. example, iron that a customer would prefer can be added to the finished fertilizer composition can be added to a mixer; pugmill type mixer or mixer positioned downstream from the pressure vessel or directly inside the rt granulator. During the granulation process, an í’. f ' r : . hardener or .. hardeners which help to agglomerate the mixture and contribute to the hardness of the dry pellet or granule is added to the second mixer type pugmill type mixer or granulator. The hardener or hardeners are selected from the group comprised of clays. • .... ... ' attapulgite, lignin, industrial molasses and alum among others or mixtures of these hardeners as known to one skilled in the art. .
Optionally, depending on customer requirements, ....... ... / additional plant nutrients, eg potash or other forms of potassium, eg potassium hydroxide is preferably added in the type-mixer type mixer. pugmill or granulator. The solid 'X nutrients that can be added also comprise urea, ammonium nitrate, monoammonium phosphate, T-diammonium phosphate, zinc chloride, and/or potash. Any additional J iron required is also added to this second pugmill mixer type mixer. Iron contributes 'T"' to an important and valuable plant nutrient for the L fertilizer mix.
Additionally, additional ammonia can be sprayed into the pugmill mixer and into the 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 for - . - r • ' “ ’ • - v . ' » • • - - adjust the pH may also be mainly L') alkaline agents selected from the group comprising 4 calcium carbonate, sodium hydroxide, calcium oxide, cement kiln dust, lime kiln dust, 20 Class C fly ash, Class F fly ash, multi-stage burner oil, alum, alum biosolids from water treatment and wood ash. each compound. Liquid additions 25 also include pH adjusting materials such as acids, e.g., phosphoric acid or sulfuric acid, or caustic solutions, e.g., sodium hydroxide. These are pumped at respective rates to the injection ring in order to enter the pugmill type mixer. ; The fertilizer product of the present invention preferably has a pH of between 5.0 and 7.0, more preferably between a pH of 5.8 and a pH of 7.0 and | more preferably between pH 6.2 and pH 6.9. The remainder of the T processing to molding, whereas in i pellet or granule production includes granulation technology of 1' standard fertilizer especially for plants with- high volume production,. Pellet or granule product, especially in plants with small production, considered as that production of products of less than 25 tons per day, may involve more innovative technologies such as injection or extrusion followed by milling or spherulization of the %. pellet or granule or involves simple discharge from a granulator or pugmill type granulation mixer. £
When a granulating pugmill type granulator or mixer is used, it is preferable to feed some recycling, such as dry seed material, i.e., * dry fines and fines produced by crushing or milling or $ material of under-specification or fertilizing product claim, within of the 5e pugmill mixer of the granulator to adjust the percentage of moisture present in the mixture so that agglomeration or nucleation can occur ;< t K resulting in granular formation. j
Other preferred embodiments comprise adjustments to the processes described herein. The modalities incorporate a pelletizer in place of the granulator in the preparation of the process, hj
The pelletizer can include the aridity step to aridity j. or the formed pellets can then be transferred to a dryer, preferably a fluidizable bed dryer to achieve the preferred dryness. These and other modalities may also incorporate adjustments to control pH, aridity, product nutrients, format, concentrations, and so on. to produce a plethora of •J specific fertilizers for different taiè plants such as roses, rhododendrons and any other flowers, vegetables, * herbs, as well as products such as gravel for cat crates. Adjustments can also be made according to '<• the geographical area in which the product is applied, to vary, for example, nutrients that may be inherently or otherwise lost in location. Examples of such variations include the addition of calcium, potassium or phosphorus •> in different amounts. f
Normal drying to final drying is conducted using a horizontal fluidized bed dryer or a rotary drum dryer. Dry pellets or granules 1 which are more than 92 percent solids and preferably are more than 95 percent solids and i. more preferably is greater than 98 percent and even more preferably is greater than 99 percent of the solids are then sized through an or; more screens. Size specification can be varied depending on customer requirements however suitable product range for sale is between 0.5mm and 4mm <with 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 which are in the range from 0.5mm to 1.3mm. The appropriate sized material is •. b separated and then cooled and then coated and then cooled in a . apparatus, preferably a rotating drum, to less than 60C (140F), preferably; to less than 49C (120F) and more preferably to less than 43C (110F). Cooling of the granule or pellet optimally takes place in a rotating drum apparatus using ambient air or air cooled from an ammonia evaporation cooler. Coating may take place in a coating vessel specifically for that purpose, typically in a rotating drum or in a mixer. Alternatively, cooling and coating can be - n carried out - in a single vessel which cools the material and mixes the coating agent with the granules. The coating is with a dedusting agent or glass material that minimizes dust generation during transport, storage and application.' The finished coated granule or pellet is then transported to storage as the finished bio-organic high nitrogen containing inorganic ammonium fertilizer to sea transport from the manufacturing site. Appropriately coated and dried pellets or granules have a hardness greater than 5 pounds of breaking strength in order to resist dust and handling during transport, shipping and application. Coating to prevent dust or glass material often requires a higher temperature, often 71-105C (160 to 220F), to maintain a molten condition for application to the coating apparatus.
The granule storage facility or bin, generally incorporating bins or silos to contain the granules, must be dried to prevent agglomeration of the granules leading to degradation and destruction. The finished product is, upon manufacture, a sterile fertilizer having substantially no detectable amount of viable microorganisms, such as E. coli or streptococci, harmful to animals or . - There are human beings. Substantially no viable microorganism means that the fertilizer is microbially safe and has no detectable amount or a detectable amount t J well below a threshold for safe handling and use A',b h of microorganisms that originate from biosolids. for
Although the fertilizer is made sterile during manufacture, contamination can be expected from airborne microorganisms or by microorganisms deposited by the animal or other contamination during storage or use. In any case, since the fertilizer product is dry and predominantly inorganic ammonium salts will not * support micro-organism multiplication at a rate that would lead to a public health problem. ••
During normal operations, equipment from the * facility for periodic decommissioning will be required for inspection, repair or replacement. This is done, to * different degrees depending on specific situations. In one mode, deactivations are automatic as in an automated command sequence provided by the plant's control processor; in another mode, deactivations are performed manually.
If a limited deactivation of the process; is required for a single piece of equipment, the flow of X biosolids into the reactor vessel would stop the material in the lines before the first pressure vessel is evacuated, r. into the organic blend mixer(s). Material in pressure vessels and associated piping is evacuated using valve and alternating piping systems and air pressure to the 'recycle' bed of granules in b ’ •*. granulator or if not available for an emergency storage tank system provided for such events. In the pressure vessel, after mixing fertilizer; drops F below the normal discharge point, an discharge bypass valve closes the pressure vessel's normal discharge seal. The bypass valve at the bottom of the pressure vessel then shifts allowing the compressed air entering the void space of the pressure vessel to force the remaining material into the return fertilizer mixing line. If additional cleaning is required, the process water is then injected into the pressure vessel y « - • followed by compressed air purging the water. Cleaning the granulator, dryer and all subsequent equipment is carried out by carrying them out until the vessels are clean. ’
The fertilizer of the present invention is preferably chemically adjusted to meet the requirements of a high nitrogen fertilizer containing significant amounts of phosphate, sulfur and iron to enhance the target nitrogen (N) content between 8 and 18 percent by weight and preferably 16 percent by weight allowing for significant commercial K-valuation. '
Figures 1 and 2 provide schematic diagrams of embodiments of the present invention, the process of these embodiments using biosolids. municipal dehydrated ’ ' , '' ' í. combined with additional plant nutrients, ammonium salt fertilizers and binding agents. In this example, the biosolids to be treated are dehydrated biosolids, often referred to as >r a "biosolids pie". These biosolids! are distributed to the manufacturing facility where they are stored in a warehouse until the biosolids are ready to be conditioned. Conditioning takes place .z. initially in a first pugmill mixer put a vigorous mix or blend with iron or other odor control agent along with optional oxidizing agents which convert the thixotropic biosolids to a pumpable mixture, paste or paste-like mixture. • Iron and/or oxidizing agent reacts with reduced sulfur compounds and other odorants present in biosolids. If — i, phosphoric acid is added to this first pugmill mixer, it aids in modifying the f odorants present in biosolids and contributes most of the phosphorus nutrients found in the final product.<Seen As the biosolids proceed through the equipment train, additional plant nutrients can be infused into the mixture. In this modality, the biosolids are heated during their passage through the pugmill type mixer before being pumped into the first reaction vessel. In the preferred embodiment shown here, two streams of sulfuric acid (in a concentration range of 68 percent to 105 percent sulfuric acid) are injected into the vessel where the mixture is acidified and liquefaction begins. Once the e 4 mixture exists in the first pressure vessel, it is transferred under pressure into a second pressure vessel where the main nitrogen infusion reaction takes place. In this figure, a sprayer injects ammonia (or other source of nitrogen) as a gas or liquid. This reaction on. both vessels is carefully controlled to optimize the • • r • r • . ru X' " I temperature, pressure, retention time, pH and nitrogen, 5 all of which can be determined empirically on the basis of input sludge materials and arb content, - desired output of treated and dried sludge. The 4 1 • 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 source is nitrogen that is pumped into the pressure vessel comprises a base such as anhydrous or aqueous ammonia. A mixture of biosolids and 1 • , • , •' ( • • I _ r. , • ' r ' • ammonium sulfate and ammonium phosphate is formed which is formed „ becomes molecularly integrated by the fact that the ammonium ions become electrically bonded to the amphoteric organic molecules of the biosolids thereby creating a slow release or controlled release of nitrogen in the final fertilizer granule. it can occur between sulphate and phosphate and iron molecules present in the mixture thus rendering these nutrient molecules similar to the state of a slow release or controlled release. This mixture is r maintained in a stress condition for a period of r' retention as determined by its retention time (which in turn is based on the main pressure and volume as described here) as the mixture moves through the pressure vessel. The stress condition preferably includes high temperature and/or high pressure. 4
Elevated temperature is produced partially or entirely by the exothermic reaction of the components, which can increase the temperature of the mixture. At these temperatures, steam is generated from the mixture. This steam is allowed to exit the pressure vessel under controlled release of valve 5, partially drying the mixture. The stress condition to which the biosolids are subjected in the pressure vessel and the retention period are controlled so as to result in the production of a mixture which is sterile and which contains hydrolyzed macromolecules of the biosolids. Control of the stress condition and retention period also results in the fusion of the ammonium ion formed with the organic molecules present creating a natural slow release property for the nitrogen present and after denaturation and/or hydrolysis of many macromolecules 15 present in biosolids, such as proteins, plastics and 4 - b other polymers. When such molecules are biologically active, this denaturation and/or hydrolysis makes them less active or inactive, thus creating a safer mixture for use and exposure to the public. The retention time to induce the necessary fertilizer properties and biological inactivation are controlled by the continuous pumping and flow of the biosolids into the pressure vessel. This continuous flow processing of the invention versus the traditional batch process of 25 older plants aids in the high production of this invention. The continuous flow also minimizes the problems associated with clogging the process by requiring downtime to release the clog.
The new mixture of liquid biosolids flows. pressure vessel and optionally mixed with a hardening agent or agents and possibly additional nutrients to make an exact fertilizer adjustment as desired. That mixture is further treated by granulation or extrusion into granules such as pellets or other similar structures. The granules are dried in a rotary dryer and passed through one or more sieves to separate oversized materials and undersized materials from appropriately sized materials. Oversized materials can be broken up in a crusher or mill. Subsequently, the r undersized materials and the broken oversized • s‘D' materials can be recycled í to facilitate granulation of the fertilizer mixture. Appropriately sized granules: resulting ’are then dried in a rotary cooler, sized, coated, cooled and stored. When a traditional granulator is used in the molding process, vaporized ammonia ammonia and recycle addition can take place. Water removed from the mixture as steam from the pressure vessel and subsequent vessels as steam and/or water vapor can be condensed and preferably returned to the wastewater treatment plant (WWTP) or can be treated and discharged into the water resources adjacent to or within the. atmosphere. The water that is retained from the capture of ammonia. in the atmospheric emission of the process is r returned to a process water containment vessel, í- r , • • V ' For optimal control of process odor and optimization of fertilizer odor resulting from the present invention,' esta er A 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 it is subsequently added to the biosolids mixture immediately before or in the first one, * pugmill type mixer. Alternatively, odorous process water can be treated with gaseous ozone, which is bubbled by the diffuser through the process water, thereby also eliminating most of the odor associated with this water.
In another embodiment, a series of reaction vessels can be used to carry out the acid/base reactions described here. In a preferred embodiment of the present invention, the two reactor vessel sequence may be used. In an optional embodiment, a reactor vessel combination for the acid reaction may be followed by ammonia conducted in a tubular reactor in oruz. Alternatively, in another embodiment, the reactions could be carried out following a first tubular cross reactor for the acidification of the biosolids mixture followed by ammonia conducted in a pressure vessel.
Also described is an embodiment whereby the acidification reaction is conducted in a first tubular cross reactor followed by an ammonia reaction in a second tubular cross reactor. ;
Another embodiment of the present invention can cause acidification of the biosolids mixture to occur partially or completely in the first pugmill mixer. The mixture of partially or completely acidified biosolids could then be treated by ammonia in a first reaction vessel. If the mixture was partially acidified, the acid/base reaction could then be completed in this first vessel or the incomplete mixture transferred to a second reactor vessel (or tubular cross reactor) for completion. there
Another embodiment of the invention is directed to a system J 4 for manufacturing a product from organic materials J treated according to the method of the invention as described herein. The combination of pressure, f, heat and ammonia treatment destroys or otherwise inactivates the 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 or in other industry such as, for example, the construction or rearing of y ; , _ J. habitat.
Examples a. below illustrate embodiments of the invention, but should not be seen as limiting the scope of the invention, f Examples Example 1
In up to 900 grams of raw biosolids with a solids content of 16 percent were added 15 grams of process water, 38.6 grams of iron sulfate and 21.8 grams of phosphoric acid. was carefully mixed (10 rpm) to a viscosity of about 25 1,250 cP and then heated in an agitated pressure vessel to about 54C (130F) and vented to maintain pressure.... , *. atmospheric 0 psig (0 kPag, ambient). 411.4 grams of 93 percent sulfuric acid was added to the heated mixture and allowed to reach the maximum temperature for 5-30 minutes. The temperature of the mixture rose to about 104C (220F) and the vessel was vented to maintain atmospheric pressure at 0 psig (0 kPag). Viscosity varies from 750cP to 3630cP dependent on induced shear rates. Example2
In up to 730 grams of raw biosolids with uriji solids content of 23.5 percent were added 56 grams of process water, 45.9 grams of iron sulfate and 25.9 grams of phosphoric acid. The mixture was heated in an agitated pressure vessel to 54C (130F) and vented to maintain an atmospheric pressure of 101,325 kPa. 490.1 grams of 93 percent sulfuric acid was added to the heated mixture and allowed to reach maximum temperature and pressure for 5 minutes. The temperature of a mixture rose >1 ♦ " I f * <' ' " V to about 116C (241F) and the pressure to a maximum of 377.11 kPa. At the maximum pressure, 165 grams of ammonia was added and the mixture combined with ammonia allowed to reach maximum temperature and pressure for 5 minutes after which the temperature rose to 183°C (362°F) and the pressure rose to 866.64 kPa. "THE Example3
Up to 720 grams of biosolids with a pH of *6.7 and a solids content of 24.5 percent were added 50 grams of process water and 47.2 grams of iron sulfate. The mixture was carefully mixed and then heated in an agitated pressure vessel until it reached about 54C (130F) and a maximum pressure of 280.58 kPa. 503.9 grams of 93 percent sulfuric acid was added to the heated and pressurized mixture. The temperature of the mixture rose to 114°C (238°F) and the pressure to a maximum of 501.22 kPa. After 5 minutes and at maximum pressure, 170 grams of ammonia was added and the combined ammonia mixture was allowed to reach maximum temperature and pressure for 5 minutes after which time the temperature of a mixture rose to 180°C (360°F) and pressure to 852.85 kPa. The J' liquefied mixture was then sprayed into a ¥ granulator and the entire mixture was dried. The resulting A - T. mixture in the granulator contained about 80 percent by weight of recycled fertilizer granules. The granules were sized to about 2 to 4 mm in size and tested for content. Granules i were found to contain 16(N)-2(P)-0(K)-175(S)-1(Fe)-15(Org). * Example 4
Up to 720 grams of biosolids having a pH of 6.45 and a solids content of 23 percent were added 100 grams of process water and 146 grams of FC sulfate. iron. The mixture was carefully mixed and then heated in an agitated pressure vessel until it reached about 54C (130F), and a maximum pressure of 259.90 kPa. 406 grams of 93 percent sulfuric acid was added to the heated and pressurized mixture. The temperature of the mixture rose to 111C (232F) and the pressure to a maximum of 335.74 kPa. After 5 minutes at maximum pressure, 166 grams of ammonia was added and the combined ammonia mixture was allowed to reach maximum temperature and pressure for 5 minutes after which time the temperature of the mixture rose to 176°C (348°F) and the pressure to 832°C. 16 kPa. The liquefied mixture was then sprayed into a granulator and at 1h. entire mixture was dried. The resulting mixture in the granulator contained about 80 percent by weight of the recycled fertilizer granules. The granules were sized to about 2 to 4 mm in size e. tested Dt for content. The granules were found to contain 16(N)-7'0(P)-0(K)-175(S)-3(Fe)-15(Org). there Example 5
Up to 600 grams of biosolids with a pH of 6.54 and HY a solids content of 23 percent were added 130 grams of process water and 158.9 grams of iron sulfate. The mixture was mixed thoroughly and then AF. t heated in an agitated pressure vessel until reaching about 54C (130F) and a maximum pressure of 246.11 kPa. ,511.7 grams of 93 percent sulfuric acid was added to the heated and pressurized mixture. The temperature of the mixture rose to 118C (244F) and the pressure to a maximum of 418.48 * kPa. After 5 minutes and at maximum pressure, 183 grams of ammonia was added and the combined ammonia mixture was allowed to reach maximum temperature and pressure; for 54 minutes after which time the temperature of the mixture rose to 175°C (3347°F) and the pressure to 839.06. kPa. The liquefied mixture was sprayed into a granulator and the entire mixture was dried. The resulting mixture in the granulator contained about 80 percent by weight ’ recycled fertilizer granules. The granules were sized T to about 2 to 4 mm in size and tested for content. The analyzed granules were found to contain 16(N)f-0(P)-2(K) -185(S)-3(Fe)-13(Org). Example 6
The nitrogen release profiles of the organically modified ammonium sulphate of the invention are determined in comparison to traditional pure ammonium sulphate fertilizer and pure biosolids as a control. First, the ammonium sulfate is applied over (sterilized sand in a laboratory environment (room temperatures with no sun, water or soil organisms) and allowed to permeate the sand for a period of time. As seen in Figure 5, about 90% of the nitrogen in the 1 * V 4 pure ammonium sulfate fertilizer travels through the V sand within less than a week. pure ammonium (AS), pure biosolids (MILORGANITE) and organically modified ammonium sulfate of the invention (VITAG). one week of application. By comparison, about 35% of the nitrogen in traditional biosolids) is • r • é , is released which increased to about 70% over two h, b ••• . d , weeks where he remained. The organically increased ammonium sulfate rC of the invention released about 60% of this nitrogen within the first week which increased by about 70% over the course of two weeks. 1 r: ' . . ' J-
Also, a theoretical nitrogen release profile is determined for these same three fertilizing materials in normal soil. The soil is presumed to contain microorganisms that break down nitrogen-containing molecules thereby releasing additional nitrogen into the soil. As seen in Figure 7, ammonium sulfate again releases its nitrogen content within the first week. Pure biosolids release only about 30% of this nitrogen in the first two weeks,* which gradually increases to about 90% over a period of 26 weeks. Nonetheless, . organically modified ammonium sulphate prepared according to the processes of the invention releases just under 60% of its nitrogen over two weeks which gradually increased to about 90% over the next 26 weeks. Thus, the organically modified ammonium sulfate fertilizer prepared according to the processes of the invention initially releases little more than half of its nitrogen e. fr 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.
Other embodiments and uses of the invention will be apparent from those skilled in the art from the consideration of the descriptive report and practice of the invention described herein. All references cited herein, including all publications, US and foreign patents and patent applications, are specifically and fully incorporated by reference. The term comprising, where already used, is intended to include the terms consisting of and consisting essentially of. It is expected that the descriptive report and the examples will be considered exemplary only to the true scope and spirit of the invention indicated by the appended claims.

权利要求:
Claims (27)
[0001]
1. Method for producing a fertilizer characterized in that it comprises: providing an organic material containing bio-solids wherein the organic material has a content of at least ten percent solids; add an odor control agent to the organic material to create a mixture; add an acid to the mixture under a first pressure and first high temperature for a first period of time, forming a liquefied mixture, where the first pressure is 0 to 60 psig, the first high temperature is 66o C (150F) to 127o C (260F) and the liquefied mixture has a viscosity of 4,000 cP or less; add ammonia to the liquefied mixture under a second pressure and a second high temperature for a second period of time, where the second pressure is 50 to 200 psig and the second high temperature is between 121oC (250F) and 199oC (390F) , and the pressure inside the pressure vessel is 50 to 200 psig, and process the liquefied mixture to form the fertilizer.
[0002]
2. Method according to claim 1, characterized in that the biosolids comprise one or more of municipal biosolids, hot-dried biosolids, pharmaceutical fermentation residues; product of microbial digestion of organic products, food products, food by-products, animal manure, digested organic fertilizers, organic biosolids, biosolids containing microorganisms, and combinations thereof.
[0003]
3. Method according to claim 1, characterized in that the organic material still contains plastic and hair and the method does not need to remove any of these before processing.
[0004]
4. Method according to claim 1, characterized in that the organic material is dehydrated or hydrated to a content of between 15 and 40 percent solids.
[0005]
5. Method according to claim 4, characterized in that the organic material has a dryness content of less than 22%.
[0006]
6. Method according to claim 4, characterized in that a portion of the organic material is dehydrated to a dryness greater than 70 or 85 percent, and that the portion is mixed with the remaining portion of the organic material to achieve a Desired percentage dryness.
[0007]
7. Method according to claim 4, characterized in that the organic material is hydrated with process water recovered from one or more steps of the method.
[0008]
8. Method according to claim 1, characterized in that the odor control agent is selected from the group consisting of calcium ferrate, sodium ferrate, potassium ferrate, ferrous sulfate heptahydrate, rozenite, melanterite, ferric chloride, ferrous sulfate, hydrated ferrous sulfate, hydrogen peroxide, ozone and salts, derivatives and combinations thereof.
[0009]
9. Method according to claim 1, characterized in that the mixture of organic material with the odor control agent is a thixotropic mixture.
[0010]
10. Method according to claim 1, characterized in that the mixture is heated before adding the acid.
[0011]
11. Method according to claim 1, characterized in that the heating is carried out in a first pressure vessel and the first pressure is maintained between 20 and 60 psig.
[0012]
12. Method according to claim 1, characterized in that the first period of time is between 3 minutes and 30 minutes.
[0013]
13. Method according to claim 1, characterized in that the first temperature is between 93°C (200F) and 121°C (250F) and the first time period is between 5 minutes and 10 minutes.
[0014]
14. Method according to claim 1, characterized in that the acid is phosphoric acid, sulfuric acid, or a combination thereof.
[0015]
15. Method according to claim 1, characterized in that the liquefied mixture is transferred to a second pressure vessel.
[0016]
16. Method according to claim 1, characterized in that the ammonia is heated under pressure to form a gas, before being added to the liquefied mixture.
[0017]
17. Method according to claim 1, characterized in that the second period of time is between 1 minute and 30 minutes.
[0018]
18. Method according to claim 1, characterized in that after the addition of ammonia the liquefied mixture has a viscosity of 1000 cP or less.
[0019]
19. Method according to claim 1, characterized in that the processing comprises drying the liquefied mixture to a content greater than 92 percent solids;
[0020]
20. Method according to claim 19, characterized in that the solids content is at least 98%.
[0021]
21. Method according to claim 1, characterized in that it further comprises the addition of a hardening agent during processing.
[0022]
22. Method according to claim 21, characterized in that the hardening agent is ligno-sulfonate, molasses, alum or a combination thereof.
[0023]
23. Method according to claim 1, characterized in that the processing is carried out in a granulator in order to form granules.
[0024]
24. Method according to claim 23, characterized in that the granules are sized and granules comprised between 0.5 and 4 mm selected.
[0025]
25. Method according to claim 23, characterized in that granules larger than 4 mm are crushed and combined with granules smaller than 0.5 mm, both are recycled during processing.
[0026]
26. Method according to claim 1, characterized in that each step of the method is carried out in a continuous process.
[0027]
27. Method according to claim 1, characterized in that it further comprises a dust control system that accumulates dust created by processing.

类似技术:

---

公开号 | 公开日 | 专利标题

---

BR112013025243B1|2021-07-06|High value organically intensified inorganic fertilizers

---

US9586869B1|2017-03-07|Bioorganically-augmented high value fertilizer

---

CA2678548C|2013-04-23|Process for treating sludge and manufacturing bioorganically-augmented high nitrogen-containing inorganic fertilizer

---

AU2016271517B2|2018-08-02|High value organic containing fertilizers and methods of manufacture

---

US9695092B2|2017-07-04|Process for treating sludge and manufacturing bioorganically-augmented high nitrogen-containing inorganic fertilizer

同族专利:

---

公开号 | 公开日

---

AU2012236575A1|2013-11-07|

---

EP2691355A2|2014-02-05|

---

JP2014518828A|2014-08-07|

---

WO2012135317A3|2014-05-01|

---

BR112013025243A2|2016-12-27|

---

MX2013011195A|2014-06-11|

---

DK2691355T3|2021-10-25|

---

PE20141991A1|2014-12-18|

---

CO6821919A2|2013-12-31|

---

JP6096171B2|2017-03-15|

---

WO2012135317A2|2012-10-04|

---

EP2691355A4|2015-04-29|

---

US20170232419A1|2017-08-17|

---

US20150191399A1|2015-07-09|

---

CA2848071C|2017-04-25|

---

MX356057B|2018-05-10|

---

US20120247164A1|2012-10-04|

---

PL2691355T3|2021-12-27|

---

US8992654B2|2015-03-31|

---

CL2013002797A1|2014-07-25|

---

RU2013145625A|2015-05-10|

---

JP2017052696A|2017-03-16|

---

CN104245631A|2014-12-24|

---

CA2848071A1|2012-10-04|

---

ES2894369T3|2022-02-14|

---

EP2691355B1|2021-08-25|

引用文献:

---

公开号 | 申请日 | 公开日 | 申请人 | 专利标题

---

---

US2026969A|1932-05-13|1936-01-07|Oliver United Filters Inc|Method for treatment of sewage|

---

US2568901A|1947-05-03|1951-09-25|Commerical Solvents Corp|Process for producing ammonium nitrate|

---

US2755176A|1952-11-03|1956-07-17|Swift & Co|Plant food manufacture|

---

US2800457A|1953-06-30|1957-07-23|Ncr Co|Oil-containing microscopic capsules and method of making them|

---

BE530009A|1953-06-30|

---

US2902342A|1955-01-27|1959-09-01|Jr Bernard J Kerley|Method and apparatus for producing ammonium salts|

---

US3050383A|1958-07-10|1962-08-21|Phillips Petroleum Co|Fertilizer|

---

US3111404A|1961-11-06|1963-11-19|Concho Petroleum Company|Method of forming a granular ammonium humate fertilizer|

---

DE1484838A1|1964-02-04|1969-06-04|Metallgesellschaft Ag|Process for the treatment of centrifugate, which falls during the dewatering of sewage sludge by means of decanting centrifuges|

---

US3475154A|1964-11-30|1969-10-28|Dainippon Toryo Kk|Plural coated pellet form products and process of making|

---

US3304588A|1965-03-18|1967-02-21|Nat Eng Co|Apparatus for conditioning granular material using rotating spokes and aerating cleats|

---

US3259482A|1965-10-14|1966-07-05|Archer Daniels Midland Co|Slow release fertilizer with a plurality of epoxy/polyester resin coatings|

---

US3264088A|1965-12-08|1966-08-02|Archer Daniels Midland Co|Slow release fertilizer granule having a plurality of epoxy resin coatings|

---

US3264089A|1965-12-10|1966-08-02|Archer Daniels Midland Co|Slow release fertilizer granule having a plurality of urethane resin coatings|

---

US3476683A|1967-05-23|1969-11-04|Johan Ragnar Liljegren|Methods of separating inorganic impurities from sewage and of making a soil improving composition from the impurities separated|

---

US3655395A|1969-01-10|1972-04-11|John N Karnemaat|Process for treating waste materials|

---

GB1323676A|1969-07-09|1973-07-18|Int Combustion Holdings Ltd|Composting material|

---

CA965966A|1970-01-08|1975-04-15|Jesse R. Conner|Land improvement with waste materials|

---

ES390653A1|1970-04-28|1974-03-16|Fuji Photo Film Co Ltd|Process for the production of oily liquid-containing microcapsules and the microcapsules produced thereby|

---

FR2133115A6|1971-04-08|1972-11-24|Ciba Geigy Ag|Coated sodium chlorate compsns - herbicides with less risk of spontaneous combustion|

---

US3915853A|1971-08-25|1975-10-28|Egon Luck|Sewage treatment|

---

US3942970A|1971-11-08|1976-03-09|Orgonics, Inc.|Process for treating sewage sludge and fertilizer products thereof|

---

US4249929A|1972-10-25|1981-02-10|Franz Kneer|Method of digesting organic wastes|

---

US4028240A|1973-10-15|1977-06-07|Manchak Frank|Method and apparatus for treating sumps|

---

US4001140A|1974-07-10|1977-01-04|Ncr Corporation|Capsule manufacture|

---

US3960718A|1974-08-05|1976-06-01|Lebo Willis R|Method and apparatus for treating liquid sewage and waste|

---

US3966450A|1974-08-12|1976-06-29|Fmc Corporation|Animal waste odor treatment|

---

US3939280A|1974-08-30|1976-02-17|General Environmental Systems Co., Inc.|Process for treating animal waste|

---

DE2523628A1|1975-05-28|1976-12-02|Rheinische Kalksteinwerke|Prepn. of fertiliser contg. lime by concn. of sewage slurry - mixing with quicklime and granulating|

---

US4076515A|1975-07-09|1978-02-28|Rickard M David|Method for treatment of digester supernatant and other streams in wastewater treatment facilities|

---

FR2320266B1|1975-08-06|1979-03-30|Quienot Jean|

---

US4108771A|1975-12-23|1978-08-22|Weiss & Co.|Elimination of odors from organic wastes|

---

US4154593A|1976-08-27|1979-05-15|Mississippi Chemical Corporation|Process for granulating ammonium phosphate containing fertilizers|

---

US4100103A|1976-12-30|1978-07-11|Ncr Corporation|Capsule manufacture|

---

UST969002I4|1977-07-25|1978-04-04|Tennessee Valley Authority|Granular ammonium phosphate sulfate and urea-ammonium phosphate sulfate using a common pipe-cross reactor|

---

GR66833B|1977-10-19|1981-05-04|Stablex Ag|

---

JPS5832638B2|1977-11-16|1983-07-14|Kurimoto Iron Works|

---

US4180459A|1977-12-16|1979-12-25|Industrial Filter & Pump Mfg. Co.|Process of making agricultural product from organic sewage sludge|

---

DE2757561C2|1977-12-23|1987-03-26|Degussa Ag, 6000 Frankfurt|Process for deodorizing sludge|

---

DE2800915B1|1978-01-10|1978-09-21|Bernhard Debbeler|Process for the preparation and pasteurization of sewage sludge with the addition of CaO|

---

US4219347A|1978-09-05|1980-08-26|Union Oil Company Of California|Multicomponent soil supplement|

---

DE2850607C2|1978-11-22|1983-11-17|Wilhelm Roediger Gmbh + Co, 6450 Hanau|Process for further dewatering and sanitizing sewage sludge|

---

DE2920525A1|1979-05-21|1980-12-04|Bayer Ag|METHOD FOR THE PRODUCTION OF POLYADDITION PRODUCTS FROM ISOCYANATES AND DENATURED BIOMASSES AND THE USE THEREOF AS REACTIVE FILLER AND AS PLANT NUTRIENTS AND METHOD FOR THE PRODUCTION OF PLATES OR MOLDED DISPOSITIONS OF THE POLAND|

---

US4405354A|1980-04-02|1983-09-20|Uniscope, Inc.|Elimination of odors from waste material|

---

WO1981002888A1|1980-04-03|1981-10-15|Oxfam|Treatment of activated or humus sludge|

---

US4304588A|1980-05-05|1981-12-08|Moore Jr William P|Foliar feed compositions|

---

US4306978A|1980-07-14|1981-12-22|Willow Technology, Inc.|Method for lime stabilization of wastewater treatment plant sludges|

---

US4652295A|1980-11-24|1987-03-24|Alfrey Norval K|Fertilizer manufacture|

---

US4377486A|1980-12-24|1983-03-22|Wrc Processing Company|Organic sludge dewatering process|

---

US4377406A|1981-07-20|1983-03-22|Tennessee Valley Authority|Ammonium polyphosphate sulfate fertilizers from wet-process phosphoric acid|

---

US4500428A|1982-09-30|1985-02-19|Process Research Development & Management, Inc.|Method for the treatment of wastewater sludge|

---

US4554002A|1983-05-16|1985-11-19|N-Viro Energy Systems Ltd.|Beneficiating waste sludges for agricultural use and product made thereby|

---

US4514307A|1983-07-26|1985-04-30|Conversion Systems, Inc.|Method of stabilizing organic waste|

---

US4619684A|1983-10-03|1986-10-28|Tennessee Valley Authority|Pressure reactor for producing diammonium phosphate|

---

US4519831A|1983-10-17|1985-05-28|Hawkeye Chemical Company|Method of converting sewage sludge to fertilizer|

---

IT1210488B|1983-11-21|1989-09-14|Ecodeco Sist Srl|ORGANIC SLUDGE SANITATION PROCESS.|

---

SE8400043L|1984-01-04|1985-07-05|Purac Ab|PROCEDURE FOR THE PREPARATION OF A COMPOSIBLE MIXTURE OF SLAM FROM WASTE WASTE WASTE PURIFICATION DEVICE FOR THE USE OF THE MIXTURE|

---

US4601863A|1984-02-09|1986-07-22|Kanzaki Paper Manufacturing Co., Ltd.|Process for producing powder of microcapsules|

---

US4743287A|1984-09-24|1988-05-10|Robinson Elmo C|Fertilizer and method|

---

DE3544451C1|1985-12-16|1987-01-15|Ashland Suedchemie Kernfest|Process for producing a water-permeable coating on granular, water-soluble substances and its application|

---

US4655932A|1986-02-10|1987-04-07|Don Roslonski|Method and apparatus for the disintegration and destruction of hazardous and toxic sludge materials|

---

US4711659A|1986-08-18|1987-12-08|Moore William P|Attrition resistant controlled release fertilizers|

---

US4793927A|1987-01-27|1988-12-27|Tulane Medical Center Of Tulane Univ.|Method of treating sewage|

---

DK169066B1|1987-02-27|1994-08-08|N Viro Energy Systems Ltd|Process for the treatment of sewage sludge|

---

US4781842A|1987-02-27|1988-11-01|N-Viro Energy Systems Ltd.|Method of treating wastewater sludge|

---

DE3816989A1|1987-08-05|1989-02-16|Peroxid Chemie Gmbh|DETERMINATION OF CLEANING SLUDGE|

---

US5087375A|1987-10-21|1992-02-11|Aggio Recovery|Method for producing insoluble industrial raw material from waste|

---

US4792349A|1987-11-03|1988-12-20|Tennessee Valley Authority|Fertilizer values from galvanizer waste|

---

US4902431A|1988-01-28|1990-02-20|N-Viro Energy Systems Ltd.|Method for treating wastewater sludge|

---

GB8829024D0|1988-08-11|1989-01-25|Newtech Mfg Pty|Process for treating organic material sewage sludge treatment|

---

US5051031A|1988-10-12|1991-09-24|American Fly Ash Company|Method of treating municipal sewage sludge and product produced thereby|

---

US5125951A|1989-02-13|1992-06-30|Westinghouse Electric Corp.|Process for producing a dried fertilizer from sewage sludge|

---

US5238480A|1989-06-29|1993-08-24|Vigoro Industries, Inc.|Fertilizer compositions and method of making such compositions|

---

US5807724A|1989-08-07|1998-09-15|Resnick; Joseph A.|Degradation of petroleum hydrocarbons with organisms encapsulated in wax|

---

US5147563A|1989-09-01|1992-09-15|Long Enterprises, Inc.|Sewage sludge treatment with gas injection|

---

US5360465A|1989-09-29|1994-11-01|Georgia-Pacific Corporation|Particulate fertilizer dust control|

---

US5443613A|1989-11-06|1995-08-22|Robinson; Elmo C.|Method for producing suspension fertilizer|

---

CA2025031A1|1989-11-06|1991-05-07|Elmo C. Robinson|Method and apparatus for producing organic based fertilizer in continuous process|

---

US5069801A|1990-02-26|1991-12-03|Bio Gro Systems, Incorporated|Indirect heat drying and simultaneous pelletization of sludge|

---

NL9000614A|1990-03-16|1991-10-16|Memon Bv|METHOD FOR PREPARING GRANULAR FERTILIZER FROM MANURE|

---

US5102556A|1990-03-30|1992-04-07|Union Oil Company Of California|Method for rendering ferric hydroxide sludges recyclable|

---

US5013458A|1990-04-06|1991-05-07|Rdp Company|Process and apparatus for pathogen reduction in waste|

---

CA2084881C|1990-06-08|1998-01-06|John Cunningham|Controlled-release microbe nutrients and method for bioremediation|

---

US4997572A|1990-06-29|1991-03-05|Willow Technology, Inc.|High rate method for alkaline stabilization, beneficiating and pelletizing of wastewater treatment plant sludges|

---

US5417861A|1990-11-30|1995-05-23|N-Viro International Corporation|Process to stabilize bioorganic, raw or treated wastewater sludge|

---

US5135664A|1990-11-30|1992-08-04|N-Viro Energy Systems Ltd.|Method for treating wastewater sludge|

---

US5275733A|1990-11-30|1994-01-04|N-Viro Energy Systems Ltd.|Process to stabilize wastewater sludge|

---

US5057009A|1991-01-11|1991-10-15|Wisconsin Electric Power Company|Lightweight aggregate from flyash and sewage sludge|

---

US5346527A|1991-01-22|1994-09-13|L & G Rehbein, Inc.|Soil treatment|

---

EP0573478B1|1991-02-27|1996-05-08|Interlicense Den Haag B.V.|Process for separate treatment and disposal of mixtures of solid and liquid organic waste materials|

---

US5556445A|1991-04-08|1996-09-17|Mark K. Quinn|Steam treatment of municipal solid waste|

---

US5356540A|1991-05-20|1994-10-18|Texaco Inc.|Pumpable aqueous slurries of sewage sludge|

---

DE4127459C2|1991-08-20|1993-07-29|Aglukon Spezialduenger Gmbh, 4000 Duesseldorf, De|

---

US5186840A|1991-08-26|1993-02-16|Rdp Company|Process for treating sewage sludge|

---

US5252116A|1991-09-03|1993-10-12|Trg International Waste Management, Ltd.|Organic base fertilizer from municipal sewage sludge|

---

US5183577A|1992-01-06|1993-02-02|Zimpro Passavant Environmental Systems, Inc.|Process for treatment of wastewater containing inorganic ammonium salts|

---

US5435923A|1992-03-20|1995-07-25|Bio Gro Systems, Inc.|Method for the treatment of sewage sludge and the like|

---

US5259977A|1992-03-20|1993-11-09|Bio Gro Systems, Inc.|Method and apparatus for the treatment of sewage sludge and the like|

---

US5422015A|1992-07-30|1995-06-06|Hondo Chemical, Inc.|Pathogenic waste treatment|

---

JP2812640B2|1992-07-31|1998-10-22|シャープ株式会社|Wastewater treatment device and wastewater treatment method|

---

US5385673A|1992-09-08|1995-01-31|Hazen And Sawyer, P.C.|Method of treating wastewater biosolids|

---

EP0701543A4|1993-05-07|1997-10-22|Univ New England|Improved fertilizer coating process|

---

US5409605A|1993-08-05|1995-04-25|Chemical Lime Company|Apparatus and method for treating waste sludge|

---

US5500044A|1993-10-15|1996-03-19|Greengrove Corporation|Process for forming aggregate; and product|

---

US5679129A|1993-12-15|1997-10-21|Clemson University|Encapsulated fertilizers and pesticides and process|

---

US5466273A|1994-04-28|1995-11-14|Connell; Larry V.|Method of treating organic material|

---

US5635069A|1994-07-22|1997-06-03|Boss Edward E|Process for treating a waste sludge of biological solids|

---

US5554279A|1994-09-26|1996-09-10|Rdp Company|Apparatus for treatment of sewage sludge|

---

US5733355A|1994-09-29|1998-03-31|Susumu Hibino|Bacterial Preparation for agricultural use|

---

FR2732335B1|1995-03-31|1997-06-27|Omnium Traitement Valorisa|SLUDGE STABILIZATION PROCESS|

---

US5603842A|1995-04-18|1997-02-18|Amsco, Incorporated|Process for treatment of sludge|

---

US5724758A|1995-04-27|1998-03-10|Eastman Kodak Company|Device and method for producing lenticular images with motion|

---

US5681481A|1995-05-18|1997-10-28|Rdp Company|Process and apparatus for liquid sludge stabilization|

---

US5593591A|1995-06-07|1997-01-14|Unipure Corporation|Production of dry, free flowing solids from bio-waste sludge|

---

DE19521502A1|1995-06-13|1996-12-19|Basf Ag|Enveloped fertilizer granules|

---

CN1040096C|1995-08-17|1998-10-07|郑州乐喜施磷复肥技术研究推广中心|Releasion controlled fertilizer|

---

SG73986A1|1995-08-30|2000-07-18|Ohio Med College|Method for treating bioorganic and wastewater sludges|

---

US5853450A|1995-09-22|1998-12-29|Medical College Of Ohio|Method for treating bioorganic and wastewater sludges|

---

FR2740448B1|1995-10-25|1998-01-09|Kaltenbach Thuring Sa|PROCESS AND PLANT FOR MANUFACTURING FERTILIZERS FROM ORGANIC BY-PRODUCTS|

---

US5772721A|1995-11-21|1998-06-30|Kazemzadeh; Massoud|Process for producing odorless organic and semi-organic fertilizer|

---

US5862610A|1995-12-28|1999-01-26|Atara Corporation|Method for coating dry pellets made of waste bio-solids with waste bio-solids|

---

US5916448A|1996-08-23|1999-06-29|Hazen & Sawyer P.C.|Chemical conditioning of liquid and semi-liquid sludge for dewatering, odor control, pathogen control, nutrient enhancement of the residual, and handling characteristics|

---

US6051411A|1996-09-20|2000-04-18|National Research Council Of Canada|Microorganisms immobilized in chitosan crosslinked with lignosulphonate for purification of waste water|

---

US5906750A|1996-09-26|1999-05-25|Haase; Richard Alan|Method for dewatering of sludge|

---

FR2755959B1|1996-11-18|1998-12-24|Kaltenbach Thuring Sa|REACTOR, PROCESS AND PLANT FOR THE MANUFACTURE OF AMMONIA SALTS|

---

FR2757504A1|1996-12-23|1998-06-26|Europ D Engrais|Preparation of organo-mineral fertilisers|

---

GB9700015D0|1997-01-02|1997-02-19|R3 Management Limited|Treating sewage or like sludge|

---

US6103191A|1997-01-29|2000-08-15|Riverside County Eastern Municipal Water District|Continuous flow pasteurization of sewage sludge|

---

EP0867422A3|1997-03-26|1999-10-13|Central Glass Company, Limited|Coated granular fertilizer and method for producing same|

---

US5984992A|1997-05-07|1999-11-16|Unity, Inc.|Sewage sludge recycling with a pipe cross-reactor|

---

IL121073A|1997-06-13|2000-07-16|Contrix Ltd|Method for production of controlled release chemicals by encapsulation|

---

US6966941B1|1997-09-09|2005-11-22|Ber Systems, Inc.|Sewage sludge treatment|

---

US6409788B1|1998-01-23|2002-06-25|Crystal Peak Farms|Methods for producing fertilizers and feed supplements from agricultural and industrial wastes|

---

EP1064106B1|1998-03-18|2003-07-16|Technologies Inc. Biosphere|Method for bio-refining organic waste material to produce denatured and sterile nutrient products|

---

US6287846B1|1998-04-16|2001-09-11|Board Of Trustees Operating Michigan State University|Method and compositions for providing a chemical to a microorganism|

---

US5993505A|1998-05-22|1999-11-30|Oms Investments, Inc.|Controlled release fertilizer compositions and processes for the preparation thereof|

---

US6165550A|1998-07-23|2000-12-26|Bayer Corporation|Symmetrical Polyurea-urethane fertilizer encapsulation|

---

US6256902B1|1998-11-03|2001-07-10|John R. Flaherty|Apparatus and method for desiccating and deagglomerating wet, particulate materials|

---

WO2001000344A1|1999-06-30|2001-01-04|Bechtel Bwxt Idaho, Llc|Encapsulation method for maintaining biodecontamination activity|

---

US6325035B1|1999-09-30|2001-12-04|Caterpillar Inc.|Method and apparatus for starting an engine using capacitor supplied voltage|

---

JP2001129597A|1999-11-02|2001-05-15|Tankatsu:Kk|Method for deodorizing treatment of sludge and sludge composted granular soil|

---

WO2001036082A1|1999-11-15|2001-05-25|Energy Engineering International Ltd.|A fluidized bed apparatus|

---

AU1168201A|1999-11-15|2001-05-30|Energy Engineering International Ltd.|A fluidized bed apparatus|

---

US6406510B1|1999-12-09|2002-06-18|Unified Environmental Services Group, Llc|Methods for treating wastewater sludge|

---

US6461399B1|1999-12-10|2002-10-08|Larry V. Connell|Organic material based uniprill fertilizer|

---

US6409789B1|2000-02-07|2002-06-25|R. Gene Gilbert|Organic biosolid waste treatment process for resource transformation, regeneration, and utilization|

---

AU3766801A|2000-03-13|2001-09-24|Energy Engineering Internat Pt|A process for producing particulate products|

---

US6852142B2|2000-06-01|2005-02-08|Green Technologies, Inc.|Organic-based fertilizer|

---

US6398840B1|2000-06-08|2002-06-04|Pedro Orta-Castro|Process for treating sludge|

---

US6623650B2|2000-10-18|2003-09-23|R3 Management Limited|Processes and apparatus for treating sewage or like sludge|

---

US6841515B2|2001-01-22|2005-01-11|Unified Enviromental Services Group, L.L.C.|Production and use of biosolid granules|

---

JP2002248454A|2001-02-22|2002-09-03|Daiichi Shizai Kk|Treating apparatus for organic waste|

---

US6752849B2|2001-08-08|2004-06-22|N-Viro International Corporation|Method for disinfecting and stabilizing organic wastes with mineral by-products|

---

US20030089151A1|2001-08-08|2003-05-15|Logan Terry J.|Method for disinfecting and stabilizing organic wastes with mineral by-products|

---

US6752848B2|2001-08-08|2004-06-22|N-Viro International Corporation|Method for disinfecting and stabilizing organic wastes with mineral by-products|

---

WO2003037827A1|2001-11-02|2003-05-08|Oliver & Jann Ltd|A process for deodorizing and disinfecting a bioorganic material|

---

WO2003045851A1|2001-11-29|2003-06-05|Corporation Biolix|Method for stabilizing and conditioning town and industrial wastewater sludge|

---

US6878179B2|2001-12-31|2005-04-12|Microbes, Inc.|Fertilizer compositions and methods of making and using same|

---

DE50207432D1|2002-02-16|2006-08-17|Trumpf Werkzeugmaschinen Gmbh|Machine for the thermal cutting of workpieces, in particular by means of laser|

---

US6666154B2|2002-04-12|2003-12-23|N-Viro International Corporation|Methods for controlling ignitability of organic waste with mineral by-products|

---

US6716360B2|2002-04-16|2004-04-06|Eau-Viron Incorporated|Method and apparatus for treating waste streams|

---

WO2003091160A2|2002-04-26|2003-11-06|The Indian Institute Of Technology, Bombay|Process for treatment of organic wastes|

---

US20040065127A1|2002-10-07|2004-04-08|Connell Larry V.|Method of dewatering and preparing organic waste material for conversion into fertilizers|

---

WO2004056721A1|2002-12-19|2004-07-08|Bluewater Investments, Inc.|Methods of controlling chemical self-heating of organic-containing materials|

---

US7128880B2|2002-12-19|2006-10-31|Environmental Technologies Capital Partners Llc|Organic recycling with a pipe-cross or tubular reactor|

---

US20040177664A1|2003-03-13|2004-09-16|Roland Hale|Production of a high quality organic-based fertilizer|

---

SE525083C2|2003-04-23|2004-11-23|Kemira Kemi Ab|Way to treat mucus|

---

CN1856455A|2003-05-27|2006-11-01|环境技术资本合伙有限公司|Reclaiming of organics with metal|

---

CN1860085A|2003-05-27|2006-11-08|环境技术资本合伙有限公司|Liquid fertilizer incorporating biosolids and high concentrations of ammonium|

---

WO2004106267A2|2003-05-27|2004-12-09|Environmental Technologies Capital Partners, Llc|Organic recycling with metal addition|

---

US20050005660A1|2003-05-27|2005-01-13|Burnham Jeffrey C.|Liquid fertilizer incorporating biosolids and high concentrations of ammonium|

---

US8105413B2|2005-02-23|2012-01-31|Vitag Corporation|Manufacturing of bioorganic-augmented high nitrogen-containing inorganic fertilizer|

---

US8192519B2|2005-03-09|2012-06-05|Vitag Corporation|Beneficiated, heat-dried biosolid pellets|

---

US7662205B2|2005-03-09|2010-02-16|Vitag Corporation|Processes to beneficiate heat-dried biosolid pellets|

---

AU2006292505B2|2005-09-15|2011-09-22|Anuvia Plant Nutrients Holdings, Inc.|Organic containing sludge to fertilizer alkaline conversion process|

---

US20070257715A1|2005-12-30|2007-11-08|Semerdzhiev Krasimir P|System and method for abstract configuration|

---

CN101687720B|2007-02-16|2014-02-12|维塔格控股有限责任公司|Process for treating sludge and manufacturing bioorganically-augmented high nitrogen-containing inorganic fertilizer|

---

WO2010139346A1|2009-06-04|2010-12-09|MAX-PLANCK-Gesellschaft zur Förderung der Wissenschaften e.V.|A method for the manufacture of a silicon polytype material|US9695092B2|2006-02-23|2017-07-04|Anuvia Plant Nutrients Corporation|Process for treating sludge and manufacturing bioorganically-augmented high nitrogen-containing inorganic fertilizer|

---

US9272468B1|2008-04-03|2016-03-01|Purdue Research Foundation|Apparatus and method for producing biobased carriers from byproducts of biomass processing|

---

EP2809631B1|2012-02-03|2018-11-28|Unity Fertilizer LLC|Systems and methods for converting and processing organic sludges for multi-nutrient single accreted granule enhanced efficiency fertilizer production|

---

WO2014074770A2|2012-11-09|2014-05-15|Heliae Development, Llc|Balanced mixotrophy methods|

---

WO2014074772A1|2012-11-09|2014-05-15|Heliae Development, Llc|Mixotrophic, phototrophic, and heterotrophic combination methods and systems|

---

US9133068B2|2012-11-26|2015-09-15|Neo Energy, Llc|System and method for producing fertilizer from organic waste|

---

US9199885B2|2013-03-15|2015-12-01|The Administrators Of The Tulane Educational Fund|Utilization of iron salts to stabilize and/or disinfect biosolids|

---

MY179142A|2013-06-21|2020-10-28|Elemental Digest Ltd|Organic waste processing|

---

AU2013399657B2|2013-09-03|2016-11-10|The Dirt Merchant, Inc.|Organic composition for use with plants|

---

US8968440B1|2014-02-05|2015-03-03|Phosfix Fertilizer & Soil Amendment LLC|Fertilizer production|

---

US20150251962A1|2014-03-07|2015-09-10|The Mosaic Company|Fertilizer compositions containing micronutrients and methods for preparing the same|

---

WO2016077954A1|2014-11-17|2016-05-26|East China University Of Science And Technology|Biopesticide compositions and methods for their preparation and use|

---

US9386774B2|2014-12-16|2016-07-12|Heliae Development, Llc|Application of mixotrophic chlorella for the improved yield and quality of solanaceae plants|

---

CN104513325B|2014-12-16|2018-01-09|武汉华士特工业生物技术开发有限公司|A kind of mixed acid, discoloration method and pectin extraction method|

---

EP3302782A4|2015-06-05|2019-01-09|Anuvia Plant Nutrients Holdings, LLC|High value organic containing fertilizers and methods of manufacture|

---

US10384982B2|2015-09-09|2019-08-20|Planet Found Energy Development, LLC|Waste material processing system|

---

US9955697B2|2016-03-30|2018-05-01|One Earth Organics, Llc|Weed control and fertilizer|

---

US11078128B2|2016-03-30|2021-08-03|One Earth Organics, Llc|Weed control and fertilizer|

---

CN107098779A|2017-04-28|2017-08-29|南京明珠肥料有限责任公司|It is a kind of to improve the water-soluble fertilizer containing amino acid of soil|

---

KR101989796B1|2017-06-30|2019-06-17|지에스칼텍스 주식회사|A preparation method of modified lignin and fertilizer composition comprising the modified lignin|

---

CN107311805A|2017-07-07|2017-11-03|芜湖玖荣生物科技有限公司|A kind of rose compoiste fertilizer|

---

CN107500865A|2017-08-29|2017-12-22|四川绵竹市佳鑫氨基酸厂|A kind of preparation method for the nutrition fertilizer for preventing plant leaf blade disease from occurring|

---

US20190127287A1|2017-11-01|2019-05-02|Atcom Fertilizers|System and method for manufacturing a fertilizer from animal manure|

---

US10701941B2|2017-11-10|2020-07-07|Heliae Development, Llc|Biomass compositions|

---

CN109095448B|2018-07-27|2020-01-14|佛山市三水雄鹰铝表面技术创新中心有限公司|Recovery system and method for recovering agricultural compound fertilizer from aluminum industry slag-reducing polishing solution|

---

WO2020037242A1|2018-08-16|2020-02-20|Anuvia Plant Nutrients Holdings, Llc|Reactive inorganic coatings for agricultural fertilizers|

---

US20200148605A1|2018-11-14|2020-05-14|Anuvia Plant Nutrients Corporation|Delivery of Bioactive Molecules in Coatings or Surface Layers of Organically Enhanced Inorganic Fertilizers|

---

US10723665B1|2019-02-20|2020-07-28|Premiere Fertilizer Systems, Llc|Poultry litter-based fertilizer and a method for making the poultry litter-based fertilizer from poultry litter|

---

DE102019211960A1|2019-08-08|2021-02-11|Glatt Ingenieurtechnik Gesellschaft mit beschränkter Haftung|Process for the production of fertilizer granules|

---

DE102019211961A1|2019-08-08|2021-02-11|Glatt Ingenieurtechnik Gesellschaft mit beschränkter Haftung|Device for the production of fertilizer granules|

---

DE102019211954A1|2019-08-08|2021-02-11|Glatt Ingenieurtechnik Gesellschaft mit beschränkter Haftung|Process for the production of fertilizer granules|

法律状态:
2017-05-23| B25D| Requested change of name of applicant approved|Owner name: ANUVIA PLANT NUTRIENTS HOLDINGS LLC (US) |

---

2018-04-03| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

---

2019-07-23| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

---

2020-04-22| B07A| Application suspended after technical examination (opinion) [chapter 7.1 patent gazette]|

---

2020-12-08| B07A| Application suspended after technical examination (opinion) [chapter 7.1 patent gazette]|

---

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

---

2021-05-18| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

---

2021-07-06| 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 28/03/2012, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

---

申请号 | 申请日 | 专利标题

---

US201161468157P| true| 2011-03-28|2011-03-28|

---

US61/468,157|2011-03-28|

---

US201161569007P| true| 2011-12-09|2011-12-09|

---

US61/569,007|2011-12-09|

---

US201261615258P| true| 2012-03-24|2012-03-24|

---

US61/615,258|2012-03-24|

---

PCT/US2012/030895|WO2012135317A2|2011-03-28|2012-03-28|High value organic-enhanced inorganic fertilizers|

---