• 专利附录
  • 专利说明
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    • 专利摘要:
    Procedure for obtaining an organomineral fertilizer from sub-bituminous coal that comprises an alkaline oxidation process by treating sub-bituminous coal in KOH with air bubbling, obtaining a product rich in K and humic acids, which can be supplemented with other nutrient elements to obtain a whole family of organomineral fertilizers. The invention presented provides the main advantage of allowing maximum use of the product, not losing any product, along with a simplification in the process that results in greater economic profitability. (Machine-translation by Google Translate, not legally binding)
    公开号:ES2678421A1
    申请号:ES201730154
    申请日:2017-02-09
    公开日:2018-08-10
    发明作者:Miguel Ángel Caballero López；José Ignacio Tolosa Cortés
    申请人:Minera Catalano Aragonesa SA；
    IPC主号:
    专利说明:

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    DESCRIPTION
    Procedure for obtaining fertilizer from subbituminum coal
    The present specification refers, as its title indicates, to a procedure for obtaining fertilizer from subbituminous coal.
    Field of the Invention
    Processes to obtain organomineral fertilizers from coal subbituminosa or other types of coal. Current state of the art
    To facilitate the description of the current state of the art, we will previously carry out a series of definitions: Organomineral Fertilizer
    Fertilizers that are characterized by containing organic matter and a mineral part. The mineral part provides the nutrients that the plant needs. In general, they are minerals that provide the main nutrients (N, P and K), and can also provide secondary nutrients (Ca, Mg, S) and trace elements (Fe, Mn, Zn, etc ...). The fertilizer industry supplies all these elements in a multitude of chemical formulas and commercial presentations
    Humic substances / humic acids
    Humic acids are a major component of humic substances, which are the main organic components of the soil (humus). They are complex macromolecular clusters in which the fundamental units are aromatic compounds of phenolic character from the decomposition of organic matter and nitrogen compounds, both cyclic and aliphatic synthesized by certain microorganisms present in the biomass
    Within the humic substances, fulvic acids are also framed, characterized by being soluble in acidic medium, unlike humic acids. In general, fulvic acids are usually named within the group of humic acids, sometimes referred to as humic extracts. For clarity, in the scope of this report we will refer to humic acids including in that definition fulvic acids.
    They are useful in agriculture as organic amendments since they provide some improvements to the soil (porosity, improvement of the structure) and serve to retain and release nutrients in a controlled manner, which makes it necessary to add less nutrients to the soil with the same efficiency.
    It typically appears in soil and organic matter. In this area, particularly in compost (plant or animal waste) and in organic waste of urban origin.
    It is a component that appears in some lignites. In subbituminum coal in low level, in general. Leonardite
    Mineral that sometimes appears in the upper layers of the lignite / coal subbituminum mines and that is characterized by having a high content of humic acids (around 60-75%). Leonardite is formed from lignite layers that have suffered weathering. That is, due to the influence of environmental conditions (humidity, pressure, oxygen, CO2, NOx, etc, ..) for long periods of time, in geological terms.
    Brown coal / subbituminum coal
    Typically, coal is divided into four main types (anthracite, coal, brown coal and peat), according to its degree of mineralization or calorific value. From this general classification, attempts have been made to establish different more exhaustive and specific classifications. Most of them establish a subdivision in the field of subbituminous coals, giving three different groups (A, B and C) depending on how close (C) or far (A) that the lignite subbituminum coal is. By way of example only name the book "Vitrinite Reflectance as Maturity Parameter. Applications and Limitations. American Chemical Society, 1994 ”
    In the study “European Coal resources: a geographical database and map of EU coal basins including potential sources of coal bed methane based on a harmonized typology, European Commission, DG Energy, 2012” several classifications of coal are raised, including coal subbituminosa and lignites within a single group called "Low-rank coal".
    In any case, the data that seems to reflect the degree of carbon oxidation in a more direct way is that of the vitrinite reflectance. Thus, we can say that lignites and subbituminous hullas have vitrinite reflectance values with maximum values that vary between 0.45% and 0.60%, and minimum values of 0.25% and 0.30%, according to the various sources. There is no officially established definition, but these margins clearly mark the difference between these types of coals and the rest (mobs, bituminous coal, anthracites).
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    The vitrinite reflectance values have proven to be especially valid as a way to determine the reactivity of the different coals in liquefaction and oxidation processes. For example:
    - Vitrinite Reflectance as Maturity Parameter. Applications and Limitations. American Chemical Society, 1994.
    - Application of Coal Petrography in the Liquefaction of Subbituminous Coals and Lignites. Alberta Geological Survey, 1983.
    - Characterization and classification of Cretaceous coals from Teruel. Relationships between their characteristics and the geological environment. Carbochemical Institute-CSIC, 1993.
    In general, a low vitrinite reflectance value indicates a greater reactivity to oxidation processes. It is an important fact, since small differences in this value can vary the chances of oxidation of the lignite / subbituminous coals of the same geological origin and even within a site.
    The use of humic acids / leonardite in agriculture is well known. In scientific literature, on many occasions, the names of lignite / leonardite / coal are exchanged, or used interchangeably, leading to confusion, and the same processes described in the scientific literature, applied to different types of coal (and consequently , with different concentrations of humic acids) give necessarily different results from those originally planned, very often insufficient to the intended effects. This applies even to coals of the same type, but of different geographical origins or holdings, since they also have different concentrations of humic acids. This implies that the processes known in the scientific literature are usually not extrapolated, and should be defined and developed for each specific type of lignite, leonardite or coal in particular, specifying as much as possible the necessary characteristics of the mineral, especially at the level of concentrations of humic acids.
    It is known within the state of the art that all humic acids present in lignite / leonardite can be extracted by simple agitation of the powdered mineral in alkaline solutions. Typically NaOH, KOH in concentrations 0.1 M, 0.5 M or 1 M for a few hours at room temperature. Humic acids dissolve in that alkaline medium and can be separated from all the rest (coal, sand, minerals) by simple filtration. They are then precipitated by the addition of an acid until an adequate pH is achieved. The variations to that method (concentration of the alkaline solution, high temperature, more time, etc ...) are very numerous. These procedures only allow obtaining humic acids already present in coal (lignite, leonardite or subbituminum coal), in the form of sodium or potassium humates.
    It is also known that it is possible to obtain humic acids from lignite / subbituminic coal with low humic acid content by oxidation of the lignite. The best alternative is to act on the mineral sprayed in a stream of air or a gas, without suspension in liquids, and goes through the treatment of lignite / subbituminous coal in a stream of oxygen or air at elevated temperature. The difficulty of a good interaction makes the processes require very high reaction times (days) and high temperatures (150-170 ° C) which results in processes with high energy costs and low productions. All this means that they are not interesting from a technical / economic point of view.
    As a way to improve the interaction between coal and possible oxidants, the use of lignite / sub-luminous coal suspension treatment has been proposed. The main alternatives described are:
    - Oxidation with HNO3. Effective method, but with a high cost. In addition, HNO3 can react with some typical components of the lignite / coal subbituminosa (S, minerals) causing the generation of polluting gases such as SOx, to join the NOx formed by the reaction itself. This implies an added cost of managing these polluting gases.
    - Oxidation with H2O2. Equally very effective, but with the same problems as NHO3.
    - O2 oxidation with bubbling over a suspension in carbon heated water. Subsequent extraction of humic acids formed. Effective, but very expensive due to the use of O2. The alternative with air again implies high reaction times and high temperatures, as was the case with dry reactions.
    - O2 oxidation with bubbled over an alkaline suspension (NaOH, KOH) heated by coal. Subsequent extraction of humic acids formed. It is effective, but also of high economic cost given the use of NaOH or KOH associated with the use of O2, NaOH or KOH that are largely lost in the extraction process.
    Background of the invention
    Currently, several publications on this subject are known, among which we can highlight the patents UA57307 "Process for the preparation of complex organo-mineral fertilizer", JPH11157976 "Humus material extracted with alkali" and CN105439698 "Production method of humic acid iron compound fertilizer ", which are common extraction processes, that simply extract humic and mix it with mineral fertilizers. They do not use oxygen and do not generate new humic acids.
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    Also known are processes such as that described in patent RO127192 "Fertilizer with humic substances, process for preparing the same and method of application thereof which consists of a filtration process, which uses phosphoric acid, and in which humic acids are simply obtained that already has the lignite of departure, they are no longer generated by chemical reaction of the lignite. Keep in mind that there are lignites that have significant amounts of humic acids naturally.
    We also found processes such as those described in patents CN102070375 "Manufacturing method of active humic acid controlled-release fertilizer" and CN103274797 "Preparation method and activating reactor for granular potassium containing humic acid urea" that mix lignite, NaOH and urea. The NaOH solution dissolves humics and urea and forms a liquid compound, they add it to a solid and then granulate it, but as in the previous cases, new humic acids are not chemically generated.
    In GB1283385 "Preparation of humates from coal" it is described how to obtain humic acids by lignite reaction with oxygen, which is well known, even in dry conditions. The problem is that it requires reaction times of days and temperatures of 150 ° C , which limits the process in a limited way.Uses acids such as HNO3 or HF, more than known system to obtain humic.
    Description of the invention
    To solve the problem currently in the production of fertilizers from coal, due to an economic cost so high that it makes it unfeasible, the procedure for obtaining fertilizer from subbituminous coal object of the present invention has been devised, which basically comprises a phase of drying and grinding the ore, followed by an alkaline oxidation phase, continuing with a drying phase and ending with a forming phase.
    It starts from subbituminic coal with a low humic acid content (6-10%) and characterized by a vitrinite reflectance value of between 0.25% and 0.35%.
    The alkaline oxidation phase is carried out in a stirring reactor and comprises a first preheating step of the KOH solution, a second mixing step of the subbituminous coal with the KOH solution with a concentration between 0.5 M and 1 , 5 M, preferably between 0.75 M and 1 M, in a subbituminum coal / KOH solution ratio between 10% and 30% weight / volume, preferably between 20% and 25% weight / volume, followed by a third reaction step at a temperature between 50 ° C and 90 ° C, preferably between 60 ° C and 80 ° C, for a time between 1 and 4 hours, preferably 2 hours, during which it is bubbled Air through the mixture. From this phase a suspension product is obtained with a humic acid content between 15% and 25% by weight of the total dry sample and a K2O content between 15% and 27% by weight of the total of the dry sample.
    Optional phases of addition of complements are also planned. The first would be done between the alkaline oxidation phase and the drying phase. The second would be done by adding on the dried product and before the forming stage. In both the product obtained is mixed with other nutrient elements, obtaining various varieties of organomineral fertilizers.
    Advantages of the invention
    This procedure for obtaining organomineral fertilizer from subbituminic coal presented presents multiple advantages over the previously described oxidation and extraction processes.
    First of all, we must highlight the full use of the product, since the drying of the entire result of the reaction is carried out, not losing any product, which results in greater economic profitability.
    It is another important advantage that new humic acids are chemically generated in the reaction, significantly increasing their percentage and allowing the use of coals or subbituminous coals with low original content in humic acids.
    Another notable advantage is that we obtain in a single step a product with medium humic content and high in K, which can be marketed directly or as a base for the formulation of other organominerals.
    We must also highlight that in this process much of the possible K used in the reaction is recovered, leaving and enriching the final product, providing added value. By eliminating the common filtration in known processes, a competitively priced product is obtained since the K used has served both to increase the amount of final humic acids and to be directly valuable as a primary fertilizer. It is possible to give value to the product beyond the increase achieved in humic acids.
    It is also important to note that this process manages to largely maintain the S that the subbituminum coal has. The presence of S in subbituminous hullas is known, which causes environmental problems
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    in its use as fuel. In the classical processes of obtaining humics from lignites and subbituminous coals, oxidation of the S that was decomposing in sOx type gases occurs. This entails an additional cost derived from the environmental management of these gases. The invention described herein makes it possible to largely maintain the content of S in the subbituminum coal, avoiding the generation of SOx that must be managed and maintaining it in the product. S is a secondary nutrient that also adds interest and value to the product. It is possible to give value to the product beyond the increase achieved in humic acids.
    Another component that is usually associated with subbituminous hullas are minerals, described as ashes, the most prominent being the presence of clays. In classical oxidation and extraction processes, said clays are removed. It is well known that clays, in particular of the illite-kaolinite type, are capable of reacting with alkalis towards the formation of zeolitic type materials. Within the world of agriculture, the usefulness of zeolitic materials is well known as a way of providing porosity to soils, improving water retention and nutrient retention capacity allowing controlled release, just like humic acids. Again, an added value to the product is achieved beyond the increase achieved in the amount of humic acids.
    In summary, the described process allows obtaining an organomineral fertilizer product in a simple way from an abundant and easily accessible raw material such as subbituminous coal. Regarding the known processes, the process takes advantage of the full potential of the product and allows the recovery of all the components used in the reaction and that can be valued within the field of agricultural fertilization.
    Preferred Embodiment of the Invention
    The process for obtaining fertilizer from subbituminic coal, object of the present invention, basically comprises a phase of drying and grinding of the mineral, followed by an alkaline oxidation phase with air bubbling, continuing with a drying phase of all the the solution obtained and ending with a forming phase.
    For the performance of this procedure, subbituminic coal with a low humic acid content is included, between 6% and 10%, with a vitrinite reflectance value between 0.25% and 0.35%.
    The drying and grinding phase of the ore comprises a drying step and another grinding step of the subbituminum coal.
    The alkaline oxidation phase is carried out in a stirring reactor and comprises a first preheating step of the KOH solution, a second mixing step of the subbituminous coal with the KOH solution with a concentration between 0.5 M and 1 , 5 M, preferably between 0.75 M and 1 M, in a subbituminum coal / KOH solution ratio between 10% and 30% weight / volume, preferably between 20% and 25% weight / volume, followed by a third reaction step at a temperature between 50 ° C and 90 ° C, preferably between 60 ° C and 80 ° C, for a time between 1 and 4 hours, preferably 2 hours, during which it is bubbled Air through the mixture. From this phase a suspension product is obtained with a humic acid content between 15% and 25% by weight of the total dry sample and a K2O content between 15% and 27% by weight of the total of the dry sample.
    The drying phase is carried out until a moisture level of the suspended product obtained is obtained between 0% and 10% of the total weight of the sample if dry product is to be obtained, between 10% and 15% of the Total weight of the sample if it is to be granulated, or between 30% and 40% of the total weight of the sample if it is to be made in pellets by extrusion. The humidity values indicated are indicative, based on the state of the art known for the different types of forming, and in no case limiting.
    The forming phase comprises, if necessary, a pellet or granulate extrusion step by means of granulator plates, a final drying step, and a packaging or bagging step.
    The final product obtained is a fertilizer that is presented in the form of granules, pellets or powder.
    Obviously, although the product thus obtained can already be used directly as a fertilizer, one or more optional phases of adding complementary components are provided that allow formulating a whole family of organomineral fertilizer products.
    By way of example only, we name some possibilities of products used as complementary components
    - Organic matter: lignite, subbituminum coal, peat, leonardite, compost (of any kind), etc ...
    - Primary mineral nutrients:
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    or N: ammonium sulfate, urea, anhydrous ammonia, calcium cyanamide, lime nitrate, Chile nitrate, ammonium nitrate, calcium ammonium nitrate, ammonium nitrosulfate, nitromagnesium, nitrogen solutions or complex products with N. or P: superphosphates (single, double or triple), bicalcium phosphate, Thomas slags, crushed phosphorite or calcined phosphorite. or K: potassium chloride or potassium sulfate
    - Secondary mineral nutrients:
    or Ca: lime nitrate, calcium cyanamide, superphosphates (single or triple) Thomas slags, natural phosphates, gypsum, calcite or dolomite. or Mg: magnesium limes, dolomite or sepiolite.
    or S: ammonium sulfate, ammonium nitrosulfate, nitromagnesium, simple lime superphosphate, triple lime superphosphate, potassium sulfate.
    - Limestone amendments such as lime or dolomite.
    - Trace elements, such as Fe, Mn, B, Zn, Cu, Mb, Others (Cl, Co, I, Se, F, Si, Al, etc.)
    - Others, such as amino acids and biostimulants in general.
    - Or any combination of the above.
    Depending on the nature of said complementary components, the optional phase of adding complementary components can be performed either between the alkaline oxidation phase and the drying phase, or as incorporation into the product once dry, between the drying phase and the drying phase. forming phase, either using a combination of both possibilities.
    Thus, preferably, the non-soluble and / or complementary components that will not be affected by the temperature of the drying process, such as organic matter, gypsum, lime, dolomite, will be added between the alkaline oxidation and drying phase. sepiolite, etc ... This will lower the water content of the suspension which will result in a more economical process.
    Likewise, preferably, after drying, those complementary components that are soluble and / or are more susceptible to being affected by temperature will be added, such as salts, urea, trace elements, amino acids, biostimulants, etc. .
    The person skilled in the art will readily understand that he can combine characteristics of different embodiments with characteristics of other possible embodiments, provided that such combination is technically possible.
    As a sample of the experimental activity performed to obtain this procedure, the following examples are shown below:
    Example 1 - Reaction at 20% weight / volume ratio (subbituminum coal / 1 M KOH)
    100 g of subbituminous coal were used and placed in the reactor to then add 0.5 liters of 1 M KOH solution. The bubbling of air was started and the temperature was set at 80 ° C, maintaining this for 4 hours. At the end of the reaction, the sample was dried in a stainless steel tray with an air flow at 75 ° C. The dried product was recovered from the drying vessel and finely ground manually. 120 g of final product were obtained.
    Example 2 - Reaction at 10% weight / volume ratio (subbituminum coal / 1 M KOH)
    100 g of subbituminous coal was used and placed in the reactor to then add 1 liter of 1 M KOH solution. The bubbling of air was started and the temperature was set at 80 ° C, maintaining this for 4 hours. At the end of the reaction, the sample was dried in a stainless steel tray with an air flow at 75 ° C. The dried product was recovered from the drying vessel and finely ground manually. 145 g of final product were obtained.
    The following table reflects the analytical results that define the nature of the products obtained:
    Table. Product Analytics
     Sample  % Humic Acids% K2O
     Subbituminum coal  9.2 0.21
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     Example 1 (20% w / v)  19.8 16.66
     Example 2 (10% w / v)  25.1 26.95
    The data collected in the table clearly indicate how there has been a logical increase in the K content (expressed as% of K2O) of the product, as a result of the method used to recover much of the K used in the form of KOH in the reaction . This increase in K is reflected by the favorable mass balance expressed in both examples.
    It is also observed how the amount of humic acids present in the product has increased. This increase is more evident if we consider that:
    • In Example 1, 19.8% humic acids refers to a product that contains an amount of K that did not have the starting subbituminous coal. If we refer to the percentage of humic acids only with respect to subbituminic coal, which constitutes 83% of the new product, we see that the content of humic acids would have increased from 9% to 23%.
    • Following the same reasoning, in example 2, 25.1% humic acids refers to a product that contains an amount of K that did not have the starting subbituminous coal. If we refer to the percentage of humic acids only with respect to subbituminic coal, which constitutes 73% of the new product, we see that the content of humic acids would have increased from 9% to 34%.
    Therefore, it is observed how products rich in humic acids and K can be obtained from subbituminous hullas poor in humic acids by a simple, efficient and economically viable process. The product obtained can be used directly as an organomineral fertilizer product or serve as the basis for the formulation of organomineral fertilizers.
    All information referring to examples or embodiments is part of the description of the invention.
    权利要求:
    Claims (1)
    [1]
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    1 - Procedure for obtaining fertilizer from subbituminum coal, characterized in that it comprises
    - a phase of drying and milling of the mineral, made from a subbituminum coal with a low humic acid content, between 6% and 10%, and with a vitrinite reflectance value between 0.25% and 0 , 35%,
    - an alkaline oxidation phase with air bubbling performed in a stirring reactor,
    - a drying phase of the entire solution obtained, and
    - a forming phase.
    2 - Procedure for obtaining fertilizer from subbituminum coal, according to the previous ones
    claims, characterized in that the alkaline oxidation phase comprises a first preheating step of the KOH solution, a second mixing step of the subbituminum coal with the KOH solution with a concentration between 0.5 M and 1.5 M, in a ratio between 10% and 30% weight / volume, followed by a third reaction step at a temperature between 50 ° C and 90 ° C, for a time between 1 and 4 hours, during which time air bubbles through the mixture.
    3 - Procedure for obtaining fertilizer from subbituminum coal, according to the previous ones
    claims, characterized in that, in the alkaline oxidation phase, the concentration of KOH is between 0.75 M and 1 M.
    4 - Procedure for obtaining fertilizer from subbituminum coal, according to the previous ones
    claims, characterized in that, in the alkaline oxidation phase, the relationship between subbituminum coal
    and the KOH solution is between 20% and 25% weight / volume.
    5 - Procedure for obtaining fertilizer from subbituminum coal, according to the previous ones
    claims, characterized in that, in the reaction of the alkaline oxidation phase the temperature is between 60 ° C and 80 ° C.
    6 - Procedure to obtain fertilizer from subbituminum coal, according to the previous ones
    claims, characterized in that the reaction time of the alkaline oxidation phase is 2 hours.
    7 - Procedure for obtaining fertilizer from subbituminum coal, according to the previous ones
    claims, characterized in that from the alkaline oxidation phase a suspension product with a humic acid content between 15% and 25% by weight with respect to the total sample is obtained
    dry and a K2O content between 15% and 27% by weight with respect to the total dry sample.
    8 - Procedure for obtaining fertilizer from subbituminum coal, according to the previous ones
    claims, characterized in that the drying phase is carried out until obtaining a moisture level of the suspension product obtained comprised between
    0% and 10% of the total weight of the sample if dry product is to be obtained, 10% and 15% of the total weight of the sample if it is to be granulated, or
    30% and 40% of the total weight of the sample if it is to be made in pellets.
    9 - Procedure for obtaining fertilizer from subbituminum coal, according to the previous ones
    claims, characterized in that the forming phase comprises, if necessary, a pellet or granulate extrusion step by means of granulator plates, a final drying step, and a packaging or bagging step.
    10 - Method of obtaining fertilizer from subbituminum coal, according to the preceding claims, characterized in that it comprises a phase of addition of complementary components, carried out between the alkaline oxidation phase and the drying phase, in which the product obtained above is mix with other nutrient elements that are not soluble and / or that will not be affected by the temperature of the drying process, obtaining various varieties of organomineral fertilizers.
    11 - Procedure for obtaining fertilizer from subbituminum coal, according to the preceding claims, characterized in that it comprises a phase of addition of complementary components, performed between the drying phase and the forming phase, in which the product obtained above is mixed with other soluble nutrient elements and / or susceptible to being affected by temperature, obtaining various varieties of organomineral fertilizers.
    12 - Procedure for obtaining fertilizer from subbituminum coal, according to the preceding claims, characterized in that the complementary components are chosen from the group consisting of organic matter, primary mineral nutrients such as N, P or K, secondary mineral nutrients such as Ca, Mg
    or S, limestone amendments such as lime or dolomite, trace elements such as Fe, Mn, B, Zn, Cu, or Mb, other elements such as Cl, Co, I, Se, F, Si, or Al, amino acids, biostimulants, or any combination of the above.
    5 13 - Fertilizer obtained from subbituminic coal according to the procedure described above,
    characterized in that it is presented in the form of granules, pellets or powder.
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    同族专利:
    公开号 | 公开日
    ES2678421B1|2019-01-15|
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