WO1994008896A1 - Fertilisant a liberation lente et sol synthetique actif - Google Patents

Fertilisant a liberation lente et sol synthetique actif Download PDF

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Publication number
WO1994008896A1
WO1994008896A1 PCT/US1993/009906 US9309906W WO9408896A1 WO 1994008896 A1 WO1994008896 A1 WO 1994008896A1 US 9309906 W US9309906 W US 9309906W WO 9408896 A1 WO9408896 A1 WO 9408896A1
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Prior art keywords
parts
fertilizer
calcium
ammonium
potassium
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PCT/US1993/009906
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English (en)
Inventor
Douglas W. MING
D. C. Golden
Earl R. Allen
Donald L. Henninger
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LUNDEEN DANIEL N
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LUNDEEN DANIEL N
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Priority to AU53623/94A priority Critical patent/AU675257B2/en
Priority to CA002146359A priority patent/CA2146359C/fr
Priority to KR1019950701514A priority patent/KR950704190A/ko
Priority to GB9507918A priority patent/GB2288172B/en
Publication of WO1994008896A1 publication Critical patent/WO1994008896A1/fr
Anticipated expiration legal-status Critical
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    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05B—PHOSPHATIC FERTILISERS
    • C05B7/00—Fertilisers based essentially on alkali or ammonium orthophosphates
    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05B—PHOSPHATIC FERTILISERS
    • C05B17/00—Other phosphatic fertilisers, e.g. soft rock phosphates, bone meal
    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05D—INORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C; FERTILISERS PRODUCING CARBON DIOXIDE
    • C05D9/00—Other inorganic fertilisers

Definitions

  • the present invention relates to an active synthetic soil for horticulture. More particularly the present invention relates to an active synthetic soil made from synthetic apatite and natural zeolite having a complete spectrum of agronutrients necessary for plant growth.
  • Synthetic soils for horticulture include two general categories-inert and active.
  • Inert substrates are commonly used in nutriculture (e. g., hydroponics) and are designed to provide mechanical support, proper root aeration and drainage. Quartz sand is a good example of an inert soil.
  • Plant nutrients are added separately as, for example, liquid fertilizers such as Hoagland's solution.
  • Soils which are defined as "active” have the ability to provide nutrient retention and release (i. e., incorporate fertilizing capability) in addition to the other primary soil functions of the above mentioned inert soils.
  • Mineral zeolites have been found to be a class of very useful ion exchange media. Many natural species are prevalent and numerous synthetic species have been made in the laboratory. Zeolites are hydrated aluminosilicates of alkali and alkaline-earth cations that possess infinite, three-dimensional crystal structures (i.e., tektosilicates). The primary building units of the zeolite crystal structure are (AI,Si) ⁇ 4 tetrahedra. When Al 3+ and sometimes Fe 3+ substitute for Si 4+ in the central cation position of the tetrahedron, a net-negative charge is generated.
  • Agronomists and botanists have long recognized the vital function of sixteen nutrients needed by growing plants including the trace elements or micronutrients - zinc, chlorine, iron, manganese, copper, molybdenum and boron. It is also known that the optimal spectrum and concentration of micronutrients in a particular soil can vary depending on the plants being grown, soil properties, climate, and the stage of the plant growth cycle.
  • micronutrients While most natural soils contain micronutrients at least to some extent and the overall need is small, depletion can occur with intensive agricultural activity. Even when the soil concentration is putatively adequate, other factors can prevent micronutrient uptake by the plant. Since micronutrients must be available as soluble ions, such ions can be immobilized in low solubility alkaline soils and/or can be trapped on clays or organic materials as insoluble complexes. It has been common practice to supplement phosphorus- impoverished soil by using a mineral fertilizers such as rock phosphate or natural apatite Such minerals, however, do not supply the required micronutrients and can contain toxic elements such as fluorine and cadmium. Rock phosphate as mined is relatively insoluble in water.
  • the raw product is generally pretreated to enhance phosphate solubility prior to use.
  • Such processes are considered too expensive for farmers in underdeveloped countries. Yet, fertilizer use is necessary to promote economic development.
  • the present invention provides a synthetic soil and fertilizer composition for horticulture which contains an entire spectrum of nutrients essential for plant growth.
  • the soil combines a cation exchange medium charged with ammonium and potassium exchange cations and a synthetic apatite composition comprising magnesium, sulfur and plant micronutrients.
  • the synthetic apatite unlike natural varieties is essentially free of toxic elements.
  • the presence of moisture mobilizes the plant nutrients at a slow, steady rate.
  • the nutrient release rate can be closely tailored to the horticultural requirements.
  • the fertilizer is made from a synthetic apatite comprising matrix of calcium phosphate having a dispersion of one or more agronutrients and a cationic exchange medium having a charge of one or more agronutrients.
  • the apatite and cationic exchange medium are preferably essentially free of agrotoxins, such as, for example, fluorine, cadmium and sodium, in amounts detrimental to the growth of most plants.
  • Agronutrients include, for example, potassium, ammonium- nitrogen, magnesium, sulfur, zinc, chlorine, iron, manganese, copper, molybdenum and/or boron.
  • the fertilizer can further include a pH buffer to maintain a pH balance of from about 5.5 to about 7.
  • the cationic exchange medium can comprise natural or synthetic zeolite, phyllosilicate or a combination thereof including clinoptilolite, chabazite, mordenite, phillipsite, Linde type A, Linde type X, vermiculite, smectite or a combination thereof.
  • the cation exchange medium has a cation exchange capacity (CEC) of at least 50 cmol c /kg, preferably at least 100 cmol c /kg, and more preferably at least 150 cmol c /kg.
  • the cation exchange medium preferably has a charge of ammonium and potassium ions at a weight ratio of from about 1 to about 5:1 of ammoniumrpotassium.
  • the fertilizer preferably comprises from about 5 to about 100 parts by weight of the synthetic apatite per 100 parts by weight of the cationic exchange medium.
  • the present invention provides a horticultural method. In one step, a botanical species is planted in a sufficient amount of the fertilizer composition described above. In another step, the fertilizer is contacted with moisture to mobilize the agronutrients.
  • the present invention provides a method of making an active synthetic fertilizer.
  • a synthetic apatite is prepared by admixing in an aqueous medium from about 1.0 to about 1.6 moles per liter of a soluble ionic calcium compound and a solution mixture comprising from about 0.5 to about 0.8 moles per liter of a soluble ionic phosphate compound and an agronomic amount of, one or more soluble agronutrients selected from magnesium, zinc, sulfur, chlorine, iron, manganese, copper, molybdenum and boron to form a crystalline calcium phosphate precipitate having agronutrients dispersed therein.
  • the precipitate is recovered, dried and suitably granulated.
  • individual zeolite portions are charged with ammonium and potassium cations to displace native cations.
  • the precipitate is blended with the charged zeolites at a proportion of from about 5 to about 100 part by weight of the precipitate per 100 parts by weight of the ammonium and potassium charged zeolites.
  • the weight ratio of ammonium charged zeolite to potassium charged zeolite is from about 1 to about 5:1.
  • the zeolite is preferably clinoptilotite.
  • the fertilizer blend preferably includes from 0 to about 10 parts by weight of a pH buffer per 100 parts by weight of the ammonium and potassium charged zeolites.
  • the Figure shows diffractographs with peak spacing for three different synthetic apatite compositions of the present invention.
  • the diffractographs indicate that the present synthetic apatite has a crystalline structure similar to naturally occurring hydroxyapatite and carbonate hydroxyapatite.
  • the major component of the synthetic soil composition is a synthetic apatite fertilizer.
  • the apatite has a calcium phosphate matrix which is at least slightly soluble in water. Water solubility is necessary to give mobility to nutrient elements contained in the apatite matrix.
  • suitable calcium phosphates include dicalcium orthophosphate (CaHPO j), monocalcium orthophosphate (Ca(H2P ⁇ 4)2), tricalcium orthophosphate (Ca3(P ⁇ 4)2), hydrates thereof and calcium pyrophosphate pentahydrate (Ca2P2 ⁇ 7-5H2 ⁇ ).
  • CaHPO j dicalcium orthophosphate
  • Ca(H2P ⁇ 4)2 monocalcium orthophosphate
  • Ca3(P ⁇ 4)2 tricalcium orthophosphate
  • hydrates thereof calcium pyrophosphate pentahydrate
  • Ca2P2 ⁇ 7-5H2 ⁇ calcium pyrophosphate pentahydrate
  • from about 30 to about 50 parts by weight phosphorus are used per 100
  • Essential agronomic nutrients in addition to calcium and phosphorus, include potassium, nitrogen, magnesium, suifur, zinc, chlorine, iron, manganese, copper, molybdenum and boron.
  • the latter seven elements are generally referred to as micronutrients and are needed by plants in lower amounts than the other essential agronutrients.
  • Agronutrients are provided in the present composition as water soluble inorganic (ionic) compounds.
  • the inorganic compounds should not have acute toxicity (e. g. cyanide salts), or other undesirable properties and should be free of excessive amounts of agrotoxins including unwanted elements and organic toxins.
  • Undesirable elements typically include most heavy metals such as lead, cadmium, mercury, and the like, and other elements such as fluorine, sodium, arsenic, antimony, selenium, tin, and the like.
  • the synthetic apatite can, however, contain a relatively small amount of any of these toxins below a toxic level for plants and, where appropriate, grazing animals.
  • natural apatite contains about 6 percent fluorine and has only limited potential as a soil supplement because of the fluorine toxicity, particularly to grazing animals such as sheep which can ingest the fluorine, e.g. by licking the soil containing the supplement.
  • Prior art phosphatic fertilizers in contrast, can contain about 3000 ppm fluorine, whereas natural soils average about 300 ppm and plants typically contain about 3 ppm fluorine.
  • the present synthetic apatite composition should generally contain no more than 10 parts fluorine per 100 parts calcium, by weight, but preferably contains no more than 3000 ppm fluorine, more preferably no more than 300 ppm, and especially no more than 3 ppm.
  • Tolerance levels of specific plants and animals for other agrotoxins can be found in the literature or determined empirically.
  • the amount of agrotoxins in the synthetic apatite should be less than an amount which would result in release into the environment of the agrotoxins in excess of a given tolerance level.
  • Suitable water soluble compounds of agronutrients used in the preparation of the synthetic apatite include potassium compounds such as potassium chloride, potassium nitrate, potassium nitrite, potassium sulfate, and potassium phosphate; magnesium compounds such as magnesium nitrate, magnesium chloride, magnesium nitrite, magnesium chlorate, magnesium perchlorate and hydrates thereof; sulfur compounds such as sodium sulfate, ammonium sulfate, potassium sulfate, and hydrates thereof; zinc compounds such as zinc chloride, zinc nitrate, zinc nitrite, zinc sulfate and hydrates thereof; chlorine compounds such as sodium chloride, potassium chloride, ammonium chloride; iron compounds such as ferric nitrate, ferrous nitrate, ferrous nitrite, ferric nitrite, ferric chloride, ferrous chloride, ferric sulfate, ferrous sulfate and hydrates thereof; manganese compounds such as manganese(ll) n
  • the synthetic apatite composition can also comprise a silicon and/or carbonate solubility control agent dispersed in the apatite matrix.
  • the solubility control agent increases or decreases the water solubility and permits enhanced control over the rate at which nutrient elements are released.
  • the effect of carbonate content on natural apatites is described in several publications including Caro, J., Journal of Agricultural Food Chemistry. 4:684-687, 1956; McClellan, G., American Mineralogist. 54:1374-1391, 1969; and Lehr R., National Fertilizer Development Center Bulletin. Y-43, Vol. 8 published by the Tennessee Valley Authority, Muscle Shoals, Alabama which are hereby incorporated herein by reference.
  • the solubility control agent is provided in the synthetic apatite composition as a water soluble inorganic or organic compound.
  • suitable water soluble carbonate compounds include sodium carbonate, sodium bicarbonate, ammonium carbonate, ammonium bicarbonate, potassium carbonate and potassium bicarbonate.
  • water soluble silicon compounds include inorganic silicates such as sodium silicate, sodium disilicate, sodium metasilicate, sodium orthosilicate, potassium disilicate, potassium metasilicate, potassium hydrogen disilicate, ammonium silicate, and hydrates thereof, and organic silicates such as ethyl orthosilicate and propyl orthosilicate.
  • a solubility control agent can comprise from 0 to about 15 parts by weight per 100 parts calcium.
  • a carbonate agent is preferably used in an amount of 0 to about 15 parts by weight per 100 parts calcium, more preferably from about 2 to about 10 parts by weight and optimally from about 4 to about 6 parts by weight.
  • a silicon agent is preferably used in an amount of 0 to about 10 parts by weight per 100 parts calcium, more preferably from about 2 to about 6 parts by weight and optimally from about 3 to about 5 parts by weight.
  • the present synthetic apatite composition can optionally include a binder agent to assist processing of the calcium phosphate into pellet form.
  • processing aid binders include calcium- lignosulfonate, cellulose, and the like.
  • the binder comprises from 0 to about 10 percent by weight or more of the synthetic apatite.
  • the present synthetic apatite composition is the precipitated product of a water soluble calcium compound and a water soluble phosphate mixture comprising a water soluble phosphate compound and one or more water soluble agronutrients.
  • the resulting product has nutrient elements incorporated into the structure of the calcium phosphate matrix.
  • the second component of the present synthetic soil is a cationic exchange medium saturated with a charge of exchange cations of one or more agronutrients.
  • Suitable cationic exchange media have a cation exchange capacity (CEC) greater than about 50 cmol c /kg.
  • CEC cation exchange capacity
  • Cationic exchange media preferably have a CEC of at least about 100 cmol c /kg, but more preferably at least about 150 cmol c /kg.
  • suitable cationic exchange media are substantially chemically inert, have low solubility in water and are essentially free of elements toxic to plant growth.
  • a most preferred class of suitable cationic exchange media are mineral zeolites.
  • Zeolites as mentioned previously are hydrated aluminosiiicates of alkali and alkaline-earth cations that possess infinite, three-dimensional crystal tetrahedral structures.
  • Natural zeolites are a common mineral matter widely found in a relatively pure state.
  • Synthetic zeolites have also been manufactured. Zeolites generally have a theoretical CEC of from about 200 cmol c /kg to about 600 cmol c /kg or more for some synthetically produced varieties.
  • zeolites include clinoptilolite (Na3,K3) ⁇ Al6Si3 ⁇ 72 ⁇ -24H2 ⁇ , chabazite
  • a most preferred natural zeolite is clinoptilolite which is widely found in a relatively pure state.
  • Clinoptilolite has been found to have good drainage and water holding characteristics, and a high theoretical cation exchange capacity of about 200 cmol c /kg.
  • Clinoptilolite also has a high affinity for NH4 + and the ability to hold the ion internally away from nitrifying bacteria. Hence nitrification rates are slow and the amount of leached N is low.
  • Clinoptilolite is commercially available as sand-sized particles.
  • zeolites are preferred cationic exchange media, other types can be used. Examples of other natural mineral exchange media are phyllosilicate clays such as vermiculite and smectite. Ion exchange resins can also be used though more expensive.
  • the cationic exchange medium will be referred to hereinbelow as the preferred but non-limiting zeolite embodiment.
  • the zeolite in the present synthetic soil is wholly or partially saturated with a charge of exchange cations of one or more agronomic nutrients so that existing native cations such as Na + are replaced with the desired agronutrient cations.
  • Applicable agronutrients which can be charged on the zeolite generally include potassium, ammonium, manganese(ll), zinc, iron(ll), copper(ll), calcium and magnesium.
  • the zeolite is preferably saturated with ammonium and potassium cations (totally replacing native cations) at a weight ratio of from about 1 to about 5:1 of ammonium:potassium.
  • ammonium and potassium cations totally replacing native cations
  • agronomic nutrients saturated on the zeolite will be referred to by the preferred but non-limiting potassium and ammonium embodiment.
  • the present soil comprises from about 5 to about 100 parts of the synthetic apatite per 100 parts by weight of the K + , NH4 + saturated zeolite.
  • a third optional but preferred component of the present soil composition is a pH buffer to maintain a soil pH in the range of from about 5.5 to about 7.
  • suitable pH buffers include weak acids (e. g., humic acid).
  • the pH buffer is used at from about 0 to about 10 parts per 100 parts by weight of the K + , NH4 + saturated zeolite.
  • the synthetic apatite is conveniently made, for example, by preparing two or more aqueous stock solutions containing the appropriate compounds and mixing the stock solutions together. An inorganic replacement reaction occurs in the solution mixture to produce a precipitate. The precipitate can be recovered, e. g. by filtration, and dried.
  • a first stock solution is made by dissolving a suitable quantity of the water soluble calcium compound in a neutral or basic aqueous medium.
  • suitable calcium compounds include calcium nitrate, calcium nitrite, calcium chloride, calcium chlorate, hydrates thereof, and the like.
  • Calcium nitrate tetrahydrate is a preferred compound.
  • the first solution preferably includes the calcium compound in an amount of from about 1.0 to about 1.6 moles per liter.
  • a second stock solution is prepared by dissolving a suitable quantity of the soluble phosphate compound and suitable quantities of the soluble anionic nutrient compound(s) in a neutral or basic aqueous medium.
  • suitable soluble phosphate compounds include ammonium orthophosphate-mono-H, ammonium orthophosphate-di-H, ammonium orthophosphate, ammonium hypophosphate and the like.
  • the second solution preferably includes the phosphate compound in an amount of from about 0.5 to about 0.8 moles per liter.
  • the amount of anionic nutrient compound(s) in the second solution will depend on the desired concentration in the synthetic apatite end product which, in turn, will depend on the agronomic application.
  • the second stock solution can include one or more anionic nutrient compounds each in an amount of from about 0.002 to about 0.4 moles per liter.
  • a third stock solution is prepared, where appropriate, by dissolving a suitable quantity of the soluble cationic nutrient compound(s) in a neutral or basic aqueous medium.
  • the quantity of the cationic nutrient compound(s) in the third solution will again depend on the desired concentration in the synthetic apatite end product which, in turn, will depend on the agronomic application.
  • the third solution includes one or more cationic nutrient compounds, each in an amount of from about 0.05 to about 5 moles per liter.
  • the optional silicon and/or carbonate solubility control agent can be added to the second (anionic) stock solution in an amount of from about 0.002 to about 0.4 moles per liter.
  • ionic compounds having a desired component element in the anion are held in solution separately from ionic compounds having a desired component element in the cation.
  • Liquid organic compounds e. g. ethyl orthosilicate
  • a preferred basic aqueous medium comprises a solution of from about 18 to about 30 percent by weight of ammonium hydroxide in deionized water.
  • a preferred neutral aqueous medium comprises deionized water.
  • the third stock solution is mixed with the second stock solution and the combined solution is then mixed with the first stock solution.
  • the resulting mixture is then maintained at ordinary temperature and pressure for a sufficient time period for the crystalline precipitate to form.
  • the precipitate is recovered by ordinary means, such as, for example, by decanting the supernatant and filtering in a B ⁇ chner funnel.
  • the precipitate is preferably washed with deionized water.
  • the washed precipitate can be dried at room temperature.
  • the precipitate is dried at a temperature ranging from about 200°C to about 600°C for a time period of from about 2 to about 20 hours in drying equipment such as an oven, wherein the temperature is preferably boosted in steps of 200°C after 2 hour intervals.
  • the drying procedure can simultaneously dry the precipitate and dehydrate or partially dehydrate the calcium phosphate endproduct. Solubility is also partially dependent on the degree of hydration of the calcium phosphate crystals, i. e., crystal size and degree of crystallinity. Since solubility is reduced by dehydration, the drying procedure specified can be used to adjust the solubility of the final product. The actual drying procedure used is not particularly critical so long as care is exercised in obtaining the desired degree of dehydration.
  • the dried precipitate is preferably cooled in a low humidity environment.
  • the precipitate can be crushed, granulated or pelletized by conventional means to produce a suitable particle size for use in soil treatment.
  • Binding agents can be used to assist the formation of a relatively consistent granulation particle size and avoid the production of fines.
  • non-reactive binders are used.
  • the type of nutrient elements incorporated into the calcium phosphate crystal structure can vary from a single nutrient element to all seven micronutrients as well as potassium, sulfur and magnesium.
  • the quantity of each nutrient element incorporated can be specified based on the agronomic factors involved.
  • zeolite particles having a size from about 50 mm to about 1000 mm are preferably divided into individual portions for each agronutrient used. Each portion is then preferably individually charged with the desired agronutrient until saturation.
  • the agronutrient charge is conveniently provided by a sufficiently concentrated (e. g., 1 M) aqueous solution of an ionic compound such as a chloride, nitrate, sulfate, and the like of the agronutrient.
  • the zeolite and nutrient solution are contacted at a suitable weight ratio, such as, for example, from about 1 :2 to about 1 :5 zeolite:nutrient solution.
  • a suitable weight ratio such as, for example, from about 1 :2 to about 1 :5 zeolite:nutrient solution.
  • the mixture is preferably agitated in a suitable vessel for a period of time such as 24 hours, the solution is decanted, and the zeolite is washed an additional two times with the appropriate solution. Afterward, the supernatant is decanted and the zeolite is washed with deionized water to remove excess nutrient solution.
  • the wash supernatant can be tested with an indicator compound to determine the presence of excess solution in the zeolite.
  • Silver nitrate for example, is a good indicator for chloride ions.
  • the saturated zeolites are dried in an oven, for example, at a temperature on the order of 105°C for a time period on the order of 24 hours.
  • the synthetic apatite and various saturated zeolite components can be dry blended in suitable equipment at a desired ratio.
  • Desired apatite solubility and nutrient release rate are usually determined empirically based on type of plant being grown, growth cycle requirements, and the like agronomic factors.
  • the present fertilizing soil can be used in conventional agronomic applications by direct addition by conventional means to a suitably prepared field but is preferably used in horticultural applications such as zeoponics and hydroponics.
  • the present synthetic soil has potential for lunar applications since zeolite synthesis from minerals found on the moon is thought to be feasible. Furthermore, plant-essential elements occur in trace quantities in lunar rock and can be extracted.
  • a suitable greenhouse or culture environment has the present synthetic soil and fertilizer appropriately blended and spread to a sufficient depth to support the root structure of seedlings planted therein.
  • the soil is kept moist to fertilize the plants.
  • Three synthetic apatite compositions having nutrient elements incorporated into the crystalline structure were synthesized by an inorganic replacement reaction to simulate a naturally occurring hydroxyapatite mineral. Initially, three stock solutions (A, B and C) were prepared using laboratory reagent grade chemicals. Each reaction was run using 500 ml of stock solutions A and B and 20 ml of stock solution C. The composition of the solutions is shown in Table 2.
  • the three synthetic materials were characterized by powder x-ray diffraction and by electron microprobe analysis.
  • the Figure shows diffractographs of the compositions.
  • the peaks (d-spacing) correspond to peaks for natural hydroxyapatites. Peak width was narrow suggesting that individual crystals have a width of from about 200-500 angstroms.
  • the chemical analysis of the composition is shown in Table 3.
  • the apatite compositions prepared in Examples 1-3 were contacted with an aqueous medium wherein the pH was varied between 5 and 7 to determine the equilibrium ion concentration after dissolution.
  • the procedure was similar to Examples 4-12 except that a 0.5 M sodium acetate solutions buffered with acetic acid to the desired pH were used instead of deionized water. Results are given in Table 5.
  • the synthetic apatite dissolved to a greater extent in a more acidic medium. Table 5

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  • Fertilizers (AREA)

Abstract

Un fertilisant/sol synthétique destiné à l'horticulture contient tous les agro-nutriments essentiels pour la croissance des plantes. Ce sol comprend un fertilisant de synthèse à base d'apatite doté de soufre, de magnésium et de micro-nutriments dispersés dans une matrice de phosphate de calcium, un milieu d'échange de cations de zéolithe saturé avec une charge de cations potassium et azote, et un tampon pH à titre facultatif. L'humidité dissout l'apatite et mobilise les nutriments provenant de la matrice d'apatite et de la charge de zéolithe.
PCT/US1993/009906 1992-10-16 1993-10-15 Fertilisant a liberation lente et sol synthetique actif Ceased WO1994008896A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
AU53623/94A AU675257B2 (en) 1992-10-16 1993-10-15 Slow release fertilizer and active synthetic soil
CA002146359A CA2146359C (fr) 1992-10-16 1993-10-15 Sol/engrais synthetiques a liberation lente
KR1019950701514A KR950704190A (ko) 1992-10-16 1993-10-15 서방성 비료 및 활성 합성토양의 제조방법(slow release fertilizer and active synthetic soil)
GB9507918A GB2288172B (en) 1992-10-16 1993-10-15 Slow release fertilizer and active synthetic soil

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Application Number Priority Date Filing Date Title
US96334892A 1992-10-16 1992-10-16
US96334992A 1992-10-16 1992-10-16
US07/963,349 1992-10-16
US07/963,348 1992-10-16

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Cited By (7)

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WO1999004617A1 (fr) * 1997-07-28 1999-02-04 Allor Foundation Procede et substrat ameliorant la croissance vegetale
DE10240938A1 (de) * 2002-09-02 2004-03-11 Rheinische Friedrich-Wilhelms-Universität Bonn Gedeckeltes Düngermitteldepot
US7818916B2 (en) 2004-12-30 2010-10-26 Aerogrow International, Inc. pH buffered plant nutrient compositions and methods for growing plants
CN102645279A (zh) * 2012-04-18 2012-08-22 中国科学院遥感应用研究所 月表矿物的干涉成像光谱仪高光谱数据模拟方法
WO2014047363A1 (fr) * 2012-09-19 2014-03-27 Red Lion Chem Tech, Llc Composite pour l'élimination d'ions phosphate et ammonium
WO2015004031A1 (fr) * 2013-07-10 2015-01-15 Again Nutrient Recovery Ab Récupération de nutriments
WO2015101536A3 (fr) * 2014-01-02 2015-08-27 Chemische Fabrik Budenheim Kg Orthophosphates métalliques mixtes cristallins pour la libération contrôlée dans le temps d'oligo-éléments dans la zone du rhizoderme et de l'épiderme de plantes

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KR100353155B1 (ko) * 2001-05-31 2002-09-18 호 근 김 천연 게르마늄 광석을 함유하는 비료 조성물 및 이에의하여 재배된 곤달비를 이용하여 제조된 식품

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US4402725A (en) * 1980-08-23 1983-09-06 Bayer Aktiengesellschaft Fertilizers
US5037470A (en) * 1985-12-17 1991-08-06 Isover Saint-Gobain Nutritive glasses for agriculture
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Cited By (12)

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WO1999004617A1 (fr) * 1997-07-28 1999-02-04 Allor Foundation Procede et substrat ameliorant la croissance vegetale
GB2341854A (en) * 1997-07-28 2000-03-29 Allor Found Process and substrate for improving plant growth
GB2341854B (en) * 1997-07-28 2001-07-25 Allor Found Improving plant growth using zeolite crystals and a plant extract
DE10240938A1 (de) * 2002-09-02 2004-03-11 Rheinische Friedrich-Wilhelms-Universität Bonn Gedeckeltes Düngermitteldepot
US7818916B2 (en) 2004-12-30 2010-10-26 Aerogrow International, Inc. pH buffered plant nutrient compositions and methods for growing plants
US8091275B2 (en) 2004-12-30 2012-01-10 AeroGrow International pH buffered plant nutrient compositions and methods for growing plants
CN102645279A (zh) * 2012-04-18 2012-08-22 中国科学院遥感应用研究所 月表矿物的干涉成像光谱仪高光谱数据模拟方法
WO2014047363A1 (fr) * 2012-09-19 2014-03-27 Red Lion Chem Tech, Llc Composite pour l'élimination d'ions phosphate et ammonium
US8945392B2 (en) 2012-09-19 2015-02-03 Red Lion Chem Tech, Llc Composite for phosphate and ammonium ion removal
WO2015004031A1 (fr) * 2013-07-10 2015-01-15 Again Nutrient Recovery Ab Récupération de nutriments
WO2015101536A3 (fr) * 2014-01-02 2015-08-27 Chemische Fabrik Budenheim Kg Orthophosphates métalliques mixtes cristallins pour la libération contrôlée dans le temps d'oligo-éléments dans la zone du rhizoderme et de l'épiderme de plantes
AU2014375347B2 (en) * 2014-01-02 2018-03-22 Chemische Fabrik Budenheim Kg Mixed metallic crystalline orthophosphates for the temporally controlled release of trace elements in the rhizodermal and epidermal areas of plants

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CA2146359A1 (fr) 1994-04-28
KR950704190A (ko) 1995-11-17
AU5362394A (en) 1994-05-09
AU675257B2 (en) 1997-01-30
GB9507918D0 (en) 1995-07-12
NZ257289A (en) 1996-11-26
CA2146359C (fr) 2002-01-15
GB2288172B (en) 1996-10-23
GB2288172A (en) 1995-10-11

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