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    • 专利摘要:
    CONTROLLED RELEASE NITROGEN FERTILIZER USING BIOCARBON AS A RENEWABLE SUPPORT MATRIX. The invention relates to an ecofertilizer that comprises a granular controlled release nitrogen fertilizer based on organic urea using biochar as a renewable support matrix. It also concerns a process for the production of a controlled-release nitrogen fertilizer, such as the ecofertilizer of this invention. Biochar is obtained by pyrolysis at low temperature at 300 ° C, from agricultural residues; and is used as a renewable matrix for nitrogen impregnation. Subsequently, the urea impregnated in the biochar is encapsulated using a biodegradable polymer. Encapsulation was performed using a precipitation method. The controlled-release nitrogen fertilizer developed showed substantially complete nitrogen availability as a plant nutrient.
    公开号:BR112015013462B1
    申请号:R112015013462-9
    申请日:2012-12-12
    公开日:2021-03-16
    发明作者:Rodrigo Javier Navia Diez；Robinson Eugenio Betancourt Astete；María Cristina Diez Jerez；Noelia Zoila Sepúlveda Ramírez；Gustavo Aner Curaqueo Fuentes；Mara Ximena Cea Lemus；Claudio Andrés Toro Aedo；Aixa González Ruiz；María Eugenia González Quijón
    申请人:Universidad De La Frontera；
    IPC主号:
    专利说明:

    FIELD OF THE INVENTION
    [001] The invention has application in the production of fertilizers, particularly in the production of nitrogen fertilizer of controlled release by impregnation of urea in biochar.
    [002] The invention relates to an ecofertilizer comprising a urea-based granular controlled release nitrogen fertilizer using biochar as a renewable support matrix, and the production process thereof. The biochar is obtained by pyrolysis in low temperature at 300 ° C, using residual biomass as raw material.
    [003] The ecofertilizer of the invention fulfills new peculiarities, in relation to the nitrogen capture efficiency for specific cultivars, effectively promoting the slow nitrogen release in up to 30 days. This controlled nitrogen release from the biochar matrix also increases the yield of two wheat cultivars tested on a field scale by up to 20%. BACKGROUND OF THE INVENTION
    [004] Fertilization is one of the main elements of crop production; it can accelerate the growth of the plant, both its aerial and radical parts. It can also alter the nutritional composition of the tissues, with effects on the level of reserves, the capacity of fixation and resistance to water, stress caused by cold and diseases, among others.
    [005] Regarding the main fertilizers used in agriculture, the global consumption of nitrogen (N), phosphorus (P) and potassium (K) in 2005/06 was, respectively, 93.2, 37.1 and 25, 8 Mt y-1, respectively (IFA, 2007). 55% of nutrients were used for cereal production, 12% for oilseed crops, 11% for pasture, 11% for commodities, 6% for tuber plants and only 5% for fruit and vegetable production.
    [006] In this context, nitrogen is the most widely applied plant nutrient. It has often been pointed out for its adverse effects on the environment, as well as on human and animal health. The estimated global consumption of nitrogen fertilizer by agriculture in 2000 was 85.5 Tg, of which 60% was used for cereal production. However, only 33% of the total N applied for cereal production is actually removed from the grain. This implies that the overall efficiency of using N for food production is low. This leads to significant economic losses that are becoming ever greater due to the continuous increase in nitrogen fertilizer prices as a result of the shortage of fossil fuels.
    [007] Especially, urea is a solid nitrogen fertilizer widely used for agricultural production, due to its low cost. After being applied to the soil, it can be quickly hydrolyzed to NH3 and CO2 by urease in the soil, followed by the formation of NO3 through nitrification. In agriculture, urea accounts for more than half of the N fertilizer applied, and this comprises 40% of the annual global consumption of urea. However, the recovery of N by cultures from urea is often as low as 30 to 40%, with a potentially high environmental cost associated with N losses through NH3 volatilization, NO3 leaching and N2O emission.
    [008] These losses are the result of many chemical, physical and biological processes, the magnitude of which is affected by several factors, such as: temperature, soil pH, cation exchange capacity (CEC), organic matter and dose coverage and fertilization site.
    [009] One way to improve the yield of nutrients and, specifically, the efficiency of the use of nitrogen, while reducing environmental hazards, is by using controlled release fertilizers (CRF). CRFs have been known for several decades. A major focus on research on CRFs remains today focused on environmental protection issues. CRFs are designed to gradually release nutrient content and to match a plant's nutrient requirements. This ensures an improved fertilization efficiency by minimizing the losses between application and absorption, thus avoiding losses due to flow, leaching and volatilization of N.
    [010] The literature describes CRFs as a nuclear and granular nutrient material containing at least one water-soluble fertilizer compound and a substantially insoluble coating applied to the core material. The fertilizer composition is structured to provide a Gaussian nutrient release rate curve over time, with the maximum release rate occurring between 1 and 18 months after exposure of the fertilizer composition to moisture, according to US6139597 (Tijsma et al. 2000). In addition, the European Committee for Standardization (CEN) establishes that a fertilizer can be described as being of slow or controlled release if the release of nutrients, under defined conditions, including that of a temperature of 25 ° C, meets all of the following criteria, a) not more than 15% in 24 hours, b) not more than 75% in 28 days and c) release equal to at least 75% in the established release period.
    [011] The release of nutrients in conventional fertilization (for example, with urea) lasts from 30 to 60 days, which in a crop cultivation cycle over 100 to 120 days means that fertilizers must be applied 2 or 3 times. In comparison, CRFs release their nutrients slowly and gradually throughout the entire season of vegetation and, consequently, they need to be applied only once, which greatly reduces the consumption of time and energy.
    [012] Nowadays, the development of CFRs is an important research topic, focusing mainly on obtaining a system in which a fertilizer granule is encapsulated, that is, it is coated with an inert layer. However, the use of coating materials can result in high production costs and even contamination of the soil after its release into the soil. CRF values are 3 to 4 times more expensive than conventional fertilizers, this is the main reason for their limited use. However, these costs can be offset by a decrease in application and purchase of fertilizers.
    [013] To solve these problems, conventional fertilizers are mixed with organic agricultural and industrial residues and with polymeric materials, forming a mixture rich in N and with high quality organic fertilizer.
    [014] Biochar is among these products, it is a material rich in carbon obtained from the incomplete combustion of lignocellulosic biomass in the absence of oxygen and low temperatures. In recent years, the application of biochar as a soil corrective has attracted worldwide interest. This practice is positioned as a new approach to promote a significant dissipation of carbon dioxide (CO2) in terrestrial ecosystems in the long term. In addition, the production of biochar and its subsequent application to the soil could provide benefits in terms of soil fertility and crop production.
    [015] Along with the benefits described above, this material has certain characteristics, such as increased adsorption capacity of organic and inorganic polluting compounds compared to other forms of organic matter. It also has a greater cation exchange capacity and negative surface charge. Due to these characteristics, biochar is currently positioned as a low-cost adsorbent compared to activated carbon.
    [016] Despite the benefits that come with adding biochar to the soil, some patents and studies suggest modifying this material before it is incorporated into the soil. These modifications include the addition of one or more nutrients through a direct mixing, encapsulation and / or pelletizing process, among others.
    [017] United States Patent No. 5,676,727, to Radlein et al. has disclosed a process to produce slow-release organic nitrogen fertilizers from products obtained from instant biomass pyrolysis. They proposed using a chemical reaction to combine a nitrogen compound containing the NH2 group with the pyrolysis products. The bio-oil obtained in the process contains high concentrations of carbonyl, carboxyl and phenolic functional groups, and it is likely that these groups are largely responsible for the reaction with ammonia. This invention consists of using bio-oil and N-rich charcoal derived from the rapid pyrolysis process by formulating an efficient biodegradable slow-release nitrogen fertilizer.
    [018] Likewise, other works have used pyrolysed peanut shell pellets in mild conditions at 400 ° C, to develop a slow-release nitrogen fertilizer. In this study, conditions and principles similar to those proposed by Radlein et al. they're used. This charcoal also provided the base material for further addition of nutrient by the pyrolysis reaction of the oil with urea to add more bioavailable nitrogen. However, the reactivity of the products used in the development of CRFs will depend on the raw material used in the pyrolysis, as well as on the operational conditions of the reactor.
    [019] WO / 2005/054154, from Kotaka, disclosed a method for obtaining nitrogen fertilizers, considering the use of charcoal as an adsorbent. The method includes the fermentation of organic matter from agricultural residues to produce ammonia gas, which is subsequently adsorbed by charcoal. The resulting product is used as a nitrogen fertilizer.
    [020] Another method for obtaining a slow-release fertilizer considers the mixture of ammonium superphosphate granules and potassium chloride, water, gypsum (CaSO4-2H2O) and charcoal. Plaster provides a high resistance to the product; and it also makes it possible to pellet the mixture. Furthermore, due to the high surface area presented by charcoal, it tends to smooth the release rate by the concentration of extra fertilizer absorption when the release rate is high and by the release or desorption of the fertilizer when the release rate is low.
    [021] Other ways of obtaining nitrogen-enriched charcoal are by chemical modifications of the charcoals already formed by thermo-chemical treatment of common raw material. These latter procedures involve reactions with various reagents that introduce nitrogen groups, as well as with reaction sequences. For example, the oxidation of carbon preceding the reaction with ammonia or its derivatives (ammonium carbonate, hydrazine, hydroxylamine and urea) with the carboxyl groups that occurs naturally in charcoal or with the artificial introduction by perforic oxidation, or nitration of carbon followed by hydrogenation of the introduced nitro groups.
    [022] Much attention is being paid to the amoxidation of charcoal, which consists of the direct reaction of the active carbons with the mixture of air and ammonia. Depending on the method used, the nitrogen content of charcoal varies, as does the chemical nature of the nitrogen groups.
    [023] This practice has been described in the formulation of the slow-release nitrogen fertilizer based on charcoal using the chemical reaction between a nitrogen source and lignocellulosic matrices. However, this method has been used today to get the activated carbons through the introduction of the nitrogen group.
    [024] Basically, the mechanism of action of the CRF includes a system in a granule (conventional fertilizers), which is encapsulated or coated. After a fertilizer application, the water penetrates through the membrane in a granule. Then, the nutrients are dissolved and the resulting osmotic pressure causes a partial rupture of the membrane, which allows the release of the active compounds into the soil.
    [025] In recent years, CRF production has focused mainly on obtaining organic fertilizers of a certain particle size and on specific physical-chemical characteristics. Recent studies have shown a trend towards the production of biochar based fertilizers incorporating nitrogen in a process of direct mixing, encapsulation and / or pelletizing.
    [026] Various materials have been found to be suitable for encapsulation or coating purposes. The most important of these includes wax and sulfur and organic polymers, such as polyolefins, polyethylene, pine kraft lignin, cellulose acetate and sodium alginate, among others. SUMMARY OF THE INVENTION
    [027] The invention relates to an ecofertilizer which comprises a granular controlled release nitrogen fertilizer based on organic urea using biochar as a renewable support matrix. It also concerns a process for the production of a controlled-release nitrogen fertilizer, such as the ecofertilizer of this invention.
    [028] Biochar is obtained by pyrolysis at low temperature at 300 ° C, from agricultural residues; and is used as a renewable matrix for nitrogen impregnation. Subsequently, the urea impregnated in the biochar is encapsulated using a biodegradable polymer. Encapsulation was performed using a precipitation method. The controlled-release nitrogen fertilizer developed showed substantially complete nitrogen availability as a plant nutrient. BRIEF DESCRIPTION OF THE FIGURES
    [029] Figure 1: Scheme of the process of the present invention.
    [030] Figure 2: Distribution of field tests (T0-T3, TS) in two experimental locations.
    [031] Figure 3: Proportion of the percentage of components of the encapsulated mixture.
    [032] Figure 4: Nitrogen stability of the encapsulated mixture for 6 months.
    [033] Figure 5: Concentration of ammonium (NH4 +) release in deionized water from the encapsulated mixture at 25 ° C and at 100 rpm.
    [034] Figure 6: Ammonium (NH4 +) release percentage in deionized water from the encapsulated mixture at 25 ° C and 100 rpm.
    [035] Figure 7: Results of the test of ecofertilizer applications in two different cultivars (Mg ha-1). DETAILED DESCRIPTION OF THE FIGURES
    [036] Figure 1: The diagram illustrates the introduction of biochar material with a particle size of less than 5 mm, preferably <2 mm to marmite (1); the introduction of urea to marmite (2); the introduction of water to the marmite (3); the suspended biochar particles (4); suspended urea granules (5); a mixer (6) and a thermocouple (7) to monitor the process temperature between 100 ° C and 200 ° C, more preferably at 150 ° C in said pot. After a period of time between 1 hour and 12 hours, more preferably 8 hours from the impregnation process, the solution is removed from the marmite (8) and then the nitrogen-impregnated biochar is filtered from the aqueous solution (9) . The nitrogen content in the biochar in this process was determined (10) and then the biochar impregnated with nitrogen and 5% sodium alginate solution were mixed (11) at a mixing ratio (11) of 3: 1 (p / v). The mixture is transferred to the PVC cylinder with openings (12) about 4 mm in diameter. The solution is mixed to keep mixing and dripping constant. After that, the sample is precipitated in 0.5 M CaCl2 (13). The spherical granules were left in the CaCl2 solution for 10 minutes to ensure complete gelation. After completing the gelation, the granules were separated from the CaCl2 solution (14). Finally, the granules are filtered and washed twice with distilled water (15) and then the granules were dried at room temperature overnight to constant weight (16). DETAILS OF THE INVENTION
    [037] The object of the present invention is the development of a granular organic controlled nitrogen release fertilizer comprising a nitrogen source, a support matrix and a biodegradable polymer encapsulation or coating in a biodegradable polymer.
    [038] In a particular embodiment of the invention, the granular organic controlled nitrogen release fertilizer preferably uses urea as a nitrogen source, but there are other sources of nitrogen that can be used.
    [039] In another embodiment of the invention, the support matrix is biochar. In a more preferred embodiment, the biochar is in the form of particles smaller than 5 mm, more preferably smaller than 2 mm.
    [040] Another embodiment of the invention regards sodium alginate as a biodegradable polymer encapsulation or coating medium.
    [041] The invention also considers the process for the production of the granulated organic controlled nitrogen fertilizer, in which the said process comprises the following steps: a) obtaining biochar by slow pyrolysis from a biomass source; b) impregnation of the biochar obtained in the previous step with a nitrogen source, producing particles of biochar impregnated with nitrogen; c) coating or encapsulation of the biochar particles impregnated with nitrogen with a biodegradable polymer.
    [042] In step a) of the process, biochar is obtained by pyrolysis under low temperature from a biomass source. Preferably, the temperature of the pyrolysis varies between 300 ° C and 600 ° C, more preferably between 300 ° C and 500 ° C. In another embodiment, pyrolysis is carried out for a period of time between 100 and 400 minutes, more preferably between 120 and 315 minutes. In another more specific modality, the source of biomass is oat hulls. In another embodiment, the particle size of the biochar obtained by pyrolysis under low temperature is reduced to a size less than 5 mm, preferably less than 2 mm.
    [043] In step b) of the process, the impregnation of the biochar with a nitrogen source is carried out in the liquid phase. The impregnation reaction is carried out in an appropriate reactor at a temperature between 100 ° C and 200 ° C, more preferably at 150 ° C. The impregnation reaction is carried out with constant stirring for a period of time between 1 hour and 12 hours, more preferably for 8 hours. In a more particular embodiment, the solvent used as a liquid phase is a polar solvent. In a more preferred embodiment, the solvent used is water. For the impregnation reaction, the sources of biochar and nitrogen are present in a weight ratio of biochar: nitrogen source from 2: 1 to 1: 2, more preferably equal to 1: 1. In a more specific embodiment, the polar solvent is present in a weight ratio of biochar: nitrogen source: polar solvent from 1: 1: 1 to 1: 1: 10, and more preferably from 1: 1: 5. Other different ratios are also included in the present invention, for example, the weight ratio of biochar: nitrogen source: polar solvent can be from 1: 2: 10 to 1: 2: 1, from 2: 1: 10 to 2 : 1: 1.
    [044] Finally, when the time period of the reaction to impregnation ends, the mixture is allowed to cool to room temperature and the reaction gases are released. Once the reaction gases have been released, the polar solvent is separated by filtration, obtaining biochar particles impregnated with nitrogen.
    [045] In the final step c), the nitrogen-impregnated biochar particles obtained in the previous step are encapsulated or coated with a biodegradable polymer. In a more preferred embodiment, the biodegradable polymer is sodium alginate, although the present invention also encompasses the use of other biodegradable polymers, including cellulose acetate and ethyl acetate (both using formamide as the solvent). In a more specific embodiment, the biodegradable polymer is dissolved in a suitable solvent, for example, water. The ratio of biodegradable polymer: solvent ranges from 1: 100 (1% by weight) to 1:10 (10% by weight), more preferably 1:20 (i.e., 5% by weight). The biodegradable polymer / solvent mixture is mixed with the nitrogen-impregnated biochar particles obtained in the previous step, in a ratio (of nitrogen-impregnated biochar particles) :( biodegradable polymer / solvent) of 10: 1 (volume by weight) to 1: 1 (weight: volume), more preferably 3: 1 (weight: volume). The mixture formed is added dropwise to a CaCl2 solution, allowing the drops to form gelled granules. In a more specific embodiment, the gelled granules have a size between 1 and 5 mm, more preferably, between 2 and 3 mm. Finally, the gelled granules are dried at room temperature overnight. APPLICATION EXAMPLES Biochar production
    [046] The process used to obtain biochar was slow pyrolysis. The carbonization experiment was carried out in a pyrolyzer capable of processing 5 kg of raw material. The reactor was purged with N2 in a flow of 5 L min-1. Oat hulls were used for the production of biochar, and the pyrolysis temperature was 300 ° C, the time to reach Tmax was 195 min, the processing time for Tmax was 120 min and the total pyrolysis time was 315 min . The mass balance of the slow pyrolysis process is shown in table 1.
    [047] Table 1. Mass balance of the slow pyrolysis process of pyrolysed oat hulls at 300 ° C.

    [048] The biochar obtained from the slow pyrolysis of oat hulls at 300 ° C (BO300) was characterized physically and chemically (table 2).
    [049] Table 2. Physical and chemical characterization of BO300.

    Nitrogen impregnation into biochar using urea as a nitrogen source
    [050] The biochar impregnation process (BO300) was carried out in 60 liter liters (Figure 1). In the process, urea was used as a source of nitrogen. Before the reaction, the particle size of the BO300 was reduced to <2 mm.
    [051] The reaction temperature was 150 ° C and was monitored with a thermocouple. The biochar impregnation was carried out in liquid phase, using water as a solvent; the proportions used were respectively 1: 1: 5 of biochar: nitrogen: water. The process parameters are shown in table 3. The reaction was carried out at 150 ° C for 8 h with constant agitation. After cooling and releasing the reaction gases, the solvent was separated by filtration.
    [052] Table 3. Parameters and their intervals used in the biochar urea impregnation process (BO300)

    [053] The total nitrogen levels of the solid and liquid phase samples were then determined by the Kjeldahl method for total nitrogen (APHA, 1998). The moisture content of the solid phase was measured by drying the sample in an oven at 100 + 5 ° C for about 24 h. Encapsulation of the mixture between biochar impregnated with nitrogen and sodium alginate (SA)
    [054] The sodium alginate (SA) solution (Aldrich Chemical) was prepared by dissolving the solid polymer in distilled water, and the concentration of the solution was equal to 5% by weight. This was followed by the mixture of biochar (non-dry solid) with the SA. The mixing ratio was 3: 1 (w / v) of biochar and SA, respectively.
    [055] The resulting mixture was placed in a PVC cylinder with openings about 4 mm in diameter at the bottom, the mixture was stirred vigorously until uniform and then slowly dripped into a 0.5 M CaCl2 solution. , where the drops formed white granules immediately due to the immediate crosslinking of the sodium alginate in the drop with Ca2 +. The spherical granules were left in the CaCl2 solution for 10 minutes to ensure complete gelation and then separated from the solution. The encapsulated mixture was dried at room temperature overnight. Stability of nitrogen content at the time of encapsulation
    [056] To study the stability of the encapsulated nitrogen content at certain time intervals (1, 5, 15 and 30 days and 6 months) an encapsulated mixture sample was collected and the total nitrogen content was measured by the Kjeldahl method. Ammonium release from water-encapsulated mixture
    [057] To study the release behavior of the encapsulated mixture in water, the following experiment was carried out: 1 g of encapsulated mixture was mixed with 200 mL of deionized water and kept in a properly covered beaker and incubated in an orbital shaker at 100 rpm for different periods at 25 ° C. All of the following tests were performed in triplicate, and the mean value was considered as a result. At certain time intervals (1, 5, 10, 15, 20, 25 and 30 days), 100 mL of aqueous solution was removed to determine the nitrogen content, and an additional 100 mL of water was injected into the vials to maintain a constant amount of solvent. The amount of N in the aqueous medium was estimated using the Kjeldahl method. Application in field tests
    [058] Two different types of soil were selected to carry out the field test of the developed ecofertilizer. In figure 2, the description of the ecofertilizer field tests is shown. Results Nitrogen impregnation on biochar using urea as a nitrogen source
    [059] The result of the total nitrogen content shown in table 4 shows an increase in the total nitrogen content in the BO300 after the impregnation process. The high temperature (150 ° C) impregnation process indicated a significant increase in the total nitrogen content.
    [060] As for moisture, the nitrogen-impregnated biochar was dried at 105 + 5 ° C for about 24 h, resulting in a moisture content equal to 50.43%.
    [061] Table 4. Total nitrogen content in the solid and liquid phases after the amoxidation process.
    Encapsulation of the mixture between nitrogen-impregnated biochar and sodium alginate (SA)
    [062] Once the moisture percentage was obtained, the mixture of the biochar impregnated with nitrogen and sodium alginate was carried out; the mixing ratio was set at 3: 1 (w / v).
    [063] The resulting mixture was placed in a cylinder with openings about 4 mm in diameter and, by means of dripping, the sample was precipitated in a 0.5 M CaCl2 solution. The spherical granules were left in the CaCl2 solution. for 10 minutes to ensure complete gelation and then they were separated from the solution, washed twice with distilled water and dried at room temperature overnight. Finally, the proportion of the components of the encapsulated is shown in figure 3. While the average diameters of the dry samples were 2 to 3 mm. Stability of the nitrogen content of the encapsulated mixture
    [064] The nitrogen content stability has been assessed over time to rule out the NH3 volatilization loss of the encapsulated mixture. It can be seen from figure 4 that the nitrogen content is constant during the evaluated time. It is observed that, on the first day, the total nitrogen content is equal to 12.09% ± 1.98 and, on the thirtieth day, the nitrogen content remained at 13.24 + 1.23%. Ammonium release test from water-encapsulated mixture
    [065] One of the most important characteristics of the encapsulated mixture prepared by the method of the present invention was its slow release property. Figure 5 shows the slow release behaviors of the ammonium from the mixture encapsulated in deionized water. It is observed in the figure that the release of NH4 + during the first 10 days shows an exponential behavior and then decreases abruptly. From figure 6, it can be seen that, on day 5, 17.90% of NH4 + was released, between day 5 and day 15, 36.68% was released and, on day 30, 39.59% NH4 + was released. DETAILED DISCUSSION OF THE INVENTION Nitrogen impregnation on biochar using urea as a nitrogen source
    [066] The reaction of the biochar with urea at an elevated temperature (150 ° C) showed greater enrichment of nitrogen than the biochar (18.97 + 1.8). Other studies used the same nitrogen source, but at a higher temperature (300 ° C), reporting values between 13 and 16.7% of total nitrogen content in charcoal.
    [067] This increase in nitrogen content could be explained by the presence of urea by-products after thermal decomposition. The nitrogen is likely to be in the form of amides, free NH and NH2, NH and bound NH2 or NH4 + species.
    [068] All the results so far suggest that the chemistry of the reaction of coal with urea is very complex, not only because of the heterogeneity of the structure of charcoal, but also due to the variety of N reagents that can arise from urea and that can react independently with coal. Encapsulation of the mixture between biochar impregnated with nitrogen and sodium alginate (SA)
    [069] In recent years, several studies have devoted attention to the preparation and use of polysaccharide superabsorbents due to their biodegradability, biocompatibility, renewability and non-toxicity. In particular, sodium alginate (SA) is a natural renewable and biodegradable polymer that is used in a variety of commercial applications, due to its gelatinization capacity.
    [070] The precipitation technique of SA in CaCl2 has been widely described for those obtained from the CRF. Basically, the method consists of the crosslinking between Na + and Ca2 +. The stability of the spherical granules depends on the SA and the Ca2 + concentration of the solutions. However, a disadvantage in using CaCl2 as a precipitation bath is the need to change the CaCl2 solution at certain intervals. Stability of the nitrogen content of the encapsulated mixture over time
    [071] Before the release of the encapsulated mixture test, it was necessary to assess the stability of the nitrogen content over time and to rule out the loss of NH3, as, for example, due to volatilization, then knowing the initial concentration of the encapsulated mixture to be used , one also has the idea of the period of time that the final product can be stored, once produced. According to the values obtained, no difference was observed between the total nitrogen content on the first day and on the thirtieth day (12.09 + 1.98% and 13.24 + 1.23%, respectively).
    [072] The literature does not report the evaluation of the stability of the active ingredient in the CRF as over time. But she mentions that the viability of the CRF depends on the storage conditions, such as temperature and humidity, among others, as well as on the polymeric material used in the formulation. Ammonium release test from water-encapsulated mixture
    [073] CRFs are a nuclear and granular nutrient material containing at least one water-soluble fertilizer compound and a substantially water-insoluble coating applied to the core material. The fertilizer composition is structured to provide a Gaussian nutrient release rate curve over time, with the maximum release rate occurring between 1 and 18 months after exposure of the fertilizer composition to moisture. However, the release time depends on the environmental conditions and the properties of the polymers used to formulate the CRF.
    [074] According to the data obtained for the release of NH4 + from the mixture encapsulated in deionized water at 25 ° C, release does not follow this behavior, since the release of NH4 + during the first 10 days presents an exponential behavior and, in then it decreases abruptly. This behavior is expected to be maintained in the soil, with the difference that the release is slower compared to deionized water.
    [075] With the sum of the NH4 + release being less than 15% on the 3rd day and not above 75% on the thirtieth day, this indicates that the slow release characteristic of the encapsulated mixture prepared in the present invention is in accordance with the standard of slow release fertilizers from the European Committee for Standardization (CEN).
    [076] As for conventional CRF, the use of a double coating in the preparation of slow-release urea has been reported. The fertilizer was prepared by urea containing cross-linked (poly) acrylic acid (PAAU) (outer coating), polystyrene (PS) (inner coating) and urea granule (core) with a total nitrogen content equal to 33.6%, whose NH4 + release rate was 100% in 18 days under the same conditions used in these studies. It should be noted that the stability of the mixture encapsulated in the liquid medium and under stirring was equal to about 15 days. Field testing
    [077] In Figure 7, the effect of ecofertilizer application on two different cultivars (Mg ha-1) was tested, namely, on wheat (Triticum aestivum) a) cultivating Crac at the experimental site Maquehue and B) cultivating Impulso at the site experimental El Retiro. The nitrogen content of the encapsulated mixture after application in the field test was, on average, equal to 1.62%.
    权利要求:
    Claims (17)
    [0001]
    1. Process for the production of a controlled-release nitrogen fertilizer CHARACTERIZED because it comprises the steps of: a) obtaining biochar by pyrolysis at a temperature between 300 ° C and 600 ° C from a biomass source; b) impregnating the biochar obtained in the previous step with urea used as a source of nitrogen, producing particles of biochar impregnated with nitrogen; where the biochar and the nitrogen source are present in a weight ratio of biochar to nitrogen source from 2: 1 to 1: 2; where the impregnation of biochar as a source of nitrogen is carried out in the liquid phase and at a temperature between 100 ° C and 200 ° C; c) coating or encapsulating the biochar particles impregnated with nitrogen with a biodegradable polymer selected from sodium alginate, cellulose acetate and ethyl acetate.
    [0002]
    2. Process for the production of a controlled-release nitrogen fertilizer, according to claim 1, CHARACTERIZED by the fact that, in step a) of the process, the biochar is obtained by pyrolysis from a biomass source at a temperature between 300 ° C and 500 ° C.
    [0003]
    3. Process for the production of a controlled-release nitrogen fertilizer, according to claim 1 or 2, CHARACTERIZED by the fact that, in step a) of the process, pyrolysis is carried out for a period of time between 100 and 400 minutes .
    [0004]
    4. Process for the production of a controlled-release nitrogen fertilizer, according to claim 3, CHARACTERIZED by the fact that, in step a) of the process, the pyrolysis is carried out for a period of time between 120 and 315 minutes.
    [0005]
    5. Process for the production of a controlled-release nitrogen fertilizer, according to claim 1, CHARACTERIZED by the fact that the source of biomass is selected from pine husks and oat husks.
    [0006]
    6. Process for the production of a controlled-release nitrogen fertilizer, according to claim 1, CHARACTERIZED by the fact that, in step a) of the process, the size of the biochar obtained is reduced to less than 5 mm.
    [0007]
    7. Process for the production of a controlled-release nitrogen fertilizer, according to claim 6, CHARACTERIZED by the fact that, in step a) of the process, the size of the biochar obtained is reduced to less than 2 mm.
    [0008]
    8. Process for the production of a controlled-release nitrogen fertilizer, according to claim 1, CHARACTERIZED by the fact that, in step b), the impregnation reaction is carried out at a temperature of 150 ° C.
    [0009]
    9. Process for the production of a controlled-release nitrogen fertilizer, according to claim 1, CHARACTERIZED by the fact that, in step b), the impregnation reaction is carried out under constant agitation for a period of time between 1 hour and 12 hours.
    [0010]
    10. Process for the production of a controlled-release nitrogen fertilizer, according to claim 1, CHARACTERIZED by the fact that, in step b) in the impregnation reaction, the polar solvent is present in a weight ratio of biochar: source nitrogen: polar solvent from 1: 1: 1 to 1: 1: 10.
    [0011]
    11. Process for the production of a controlled-release nitrogen fertilizer, according to claim 1, CHARACTERIZED by the fact that, in step b) in the impregnation reaction, the polar solvent is present in a weight ratio of biochar: source nitrogen: polar solvent from 1: 2: 10 to 1: 2: 1, or from 2: 1: 10 to 2: 1: 1.
    [0012]
    12. Process for the production of a controlled-release nitrogen fertilizer, according to claim 1, CHARACTERIZED by the fact that, in step b), the mixture is allowed to cool to room temperature and the reaction gases are released, and after the reaction gases are released, the polar solvent is separated by filtration, obtaining biochar particles impregnated with nitrogen.
    [0013]
    13. Process for the production of a controlled-release nitrogen fertilizer, according to claim 1, CHARACTERIZED by the fact that, in step c), the nitrogen-impregnated biochar particles are encapsulated or coated with a biodegradable polymer selected from alginate sodium, cellulose acetate and ethyl acetate.
    [0014]
    14. Process for the production of a controlled-release nitrogen fertilizer, according to claim 13, CHARACTERIZED by the fact that the biodegradable polymer selected from sodium alginate, cellulose acetate and ethyl acetate is dissolved in a polar solvent of 1 % by weight up to 10% by weight.
    [0015]
    15. Process for the production of a controlled-release nitrogen fertilizer, according to either of claims 13 or 14, CHARACTERIZED by the fact that the biodegradable polymer is sodium alginate and the solvent is water, and the mixture of sodium alginate / water is mixed with the nitrogen-impregnated biochar particles in a ratio of (nitrogen-impregnated biochar particles) :( sodium alginate / water) from 10: 1 (weight: volume) to 1: 1 (weight: volume) .
    [0016]
    16. Process for the production of a controlled-release nitrogen fertilizer, according to claim 15, CHARACTERIZED by the fact that the mixture of biochar particles impregnated with nitrogen and sodium alginate / water is dripped into a CaCl2 solution, allowing that the drops form gelled granules, which have a size between 1 and 5 mm.
    [0017]
    17. Process for the production of a controlled-release nitrogen fertilizer, according to claim 16, CHARACTERIZED by the fact that the gelled granules are dried at room temperature overnight.
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    同族专利:
    公开号 | 公开日
    BR112015013462A2|2017-07-11|
    BR112015013462A8|2019-10-08|
    WO2014091279A1|2014-06-19|
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    法律状态:
    2018-03-27| B06F| Objections, documents and/or translations needed after an examination request according art. 34 industrial property law|
    2019-09-03| B06U| Preliminary requirement: requests with searches performed by other patent offices: suspension of the patent application procedure|
    2020-08-18| B06A| Notification to applicant to reply to the report for non-patentability or inadequacy of the application according art. 36 industrial patent law|
    2021-01-19| B09A| Decision: intention to grant|
    2021-03-16| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 12/12/2012, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    PCT/IB2012/057245|WO2014091279A1|2012-12-12|2012-12-12|Controlled-release nitrogen fertilizer using biochar as a renewable support matrix|
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