Concentrated phosphorus fertilizers are disclosed that comprise a buffered composition of an organic acid and salts thereof and a phosphorous-containing acid and salts thereof. The concentrated phosphorus fertilizers can be diluted with water of ph ranging from about 6.5 to about 8.5 at ratios of concentrate to water at about 1:40 to about 1:600 to result in a fertilizer having a ph in the range acceptable for foliar uptake of phosphorus.
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44. A multiple buffered phosphite fertilizer comprising:
(i) a first buffer system comprising a phosphite; and
(ii) a second buffer system comprising an organic acid and a salt of an organic acid.
1. A multiple buffered phosphorus fertilizer comprising:
(i) a first buffer system comprising a phosphorous acid and a salt of a phosphorous acid; and
(ii) a second buffer system comprising an organic acid and a salt of an organic acid.
91. A method of making a substantially fully solubilized use-dilution fertilizer, said method comprising:
mixing water with a ph as low as about 6.5 and a concentrate comprising a first buffer system comprising a phosphorous acid and a salt of a phosphorous acid, thus forming said use-dilution fertilizer, wherein said use-dilution fertilizer concentrate has phosphorus in an amount equivalent to at least about 0.30 kg/L P2O5, and said use-dilution fertilizer has a ratio of concentrate to water of as high as about 1 part concentrate to about 40 parts water, and has a foliage acceptable ph for phosphorus uptake.
106. A substantially fully solubilized use-dilution fertilizer having a foliage acceptable ph for phosphorus uptake, produced by a process comprising:
mixing water with a ph as low as about 6.5 and a concentrate comprising a first buffer system comprising phosphite, thus forming said use-dilution fertilizer, wherein said use-dilution fertilizer concentrate has phosphorus in an amount equivalent to at least about 0.30 kg/L P2O5, and said use-dilution fertilizer has a ratio of concentrate to water of as high as about 1 part concentrate to about 40 parts water, and has a foliage acceptable ph for phosphorus uptake.
87. A substantially fully solubilized use-dilution fertilizer comprising a concentrate comprising a first buffer system, wherein said first buffer system is derived from a phosphorous acid and salt of a phosphorous acid, wherein phosphorus is present in said first buffer system in an amount equivalent to at least about 0.30 kg/L P2O5, such that when said concentrate is diluted with water having a ph as low as about 6.5 at a ratio as high as about 1 part concentrate to about 40 parts water, there is formed a substantially fully solubilized use-dilution fertilizer having a foliage acceptable ph for phosphorus uptake.
101. A substantially fully solubilized use-dilution fertilizer having a foliage acceptable ph for phosphorus uptake, produced by a process comprising:
mixing water with a ph as low as about 6.5 and a concentrate comprising a first buffer system consisting of a phosphorous-containing acid and salt thereof, thus forming said use-dilution fertilizer, wherein said use-dilution fertilizer concentrate has phosphorus in an amount equivalent to at least about 0.30 kg/L P2O5, and said use-dilution fertilizer has a ratio of concentrate to water of as high as about 1 part concentrate to about 40 parts water, and has a foliage acceptable ph for phosphorus uptake.
96. A method of applying phosphorus to a plant, said method comprising:
(a) mixing water with a ph as low as about 6.5 and a concentrate comprising a first buffer system comprising a phosphorous acid and a salt of a phosphorous acid, thus forming a substantially fully solubilized use-dilution fertilizer, wherein said use-dilution fertilizer concentrate has phosphorus in an amount equivalent to at least about 0.30 kg/L P2O5, and said use-dilution fertilizer has a ratio of concentrate to water of as high as about 1 part concentrate to about 40 parts water, and has a foliage acceptable ph for phosphorus uptake; and
(b) applying said substantially fully solubilized use-dilution fertilizer to the foliage of said plant, thus applying said phosphorus to said plant.
2. The multiple buffered phosphorus fertilizer according to
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9. A substantially fully solubilized use-dilution fertilizer having a ph acceptable for foliage uptake of phosphorus, said use-dilution fertilizer comprising:
(i) the multiple buffered phosphorus fertilizer according to
(ii) water.
10. The use-dilution fertilizer according to
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23. A substantially fully solubilized use-dilution fertilizer having a ph acceptable for foliage uptake of phosphorus, said use-dilution fertilizer comprising:
(i) the multiple buffered phosphorus fertilizer according to
(ii) water.
24. The use-dilution fertilizer according to
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0. 37. A substantially fully solubilized use-dilution fertilizer having a ph acceptable for foliage uptake of phosphorus, said use-dilution fertilizer comprising:
(i) the multiple buffered phosphorus fertilizer according to
(ii) water.
0. 38. The use-dilution fertilizer according to
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0. 40. The multiple buffered phosphorus fertilizer according to
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45. The multiple buffered phosphite fertilizer according to
46. The multiple buffered phosphite fertilizer according to
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50. The multiple buffered phosphite fertilizer according to
51. The multiple buffered phosphite fertilizer according to
52. A substantially fully solubilized use-dilution fertilizer having a ph acceptable for foliage uptake of phosphorus, said use-dilution fertilizer comprising:
(i) the multiple buffered phosphite fertilizer according to
(ii) water.
53. The use-dilution fertilizer according to
54. The use-dilution fertilizer according to
55. The multiple buffered phosphite fertilizer according to
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64. The multiple buffered phosphite fertilizer according to
65. The multiple buffered phosphite fertilizer according to
66. A substantially fully solubilized use-dilution fertilizer having a ph acceptable for foliage uptake of phosphorus, said use-dilution fertilizer comprising:
(i) the multiple buffered phosphite fertilizer according to
(ii) water.
67. The use-dilution fertilizer according to
68. The use-dilution fertilizer according to
69. The multiple buffered phosphite fertilizer according to
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0. 80. A substantially fully solubilized use-dilution fertilizer having a ph acceptable for foliage uptake of phosphorus, said use-dilution fertilizer comprising:
(i) the multiple buffered phosphite fertilizer according to
(ii) water.
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This is a continuation of U.S. application Ser. No. 10/686,411, filed Oct. 14, 2003, now U.S. Pat. No. 6,896,714, which issued May 25, 2005, which is a continuation of U.S. Application No. 10/341,966, filed Jan. 13, 2003, now U.S. Pat. No. 6,645,268 B2, which is a continuation of U.S. application Ser. No. 09/637,621, filed Aug. 11, 2000, now U.S. Pat. No. 6,929,673, which issued Aug. 16, 2005, which is a continuation of U.S. application Ser. No. 09/126,233, filed Jul. 30, 1998, now U.S. Pat. No. 6,113,665, which is a continuation of U.S. application Ser. No. 08/642,574, filed May 3, 1996, now U.S. Pat. No. 5,830,255, which issued Nov. 3, 1998, which application was re-examined as B1 5,830,255 (certificate issued Jul. 11, 2000), which is a continuation of U.S. application Ser. No. 08/192,508, filed Feb. 7, 1994, now U.S. Pat. No. 5,514,200, which issued May 7, 1996
Fertilizers are added to the soil of crops or in some cases they can be applied directly to crop foliage to supply elements needed for plant nutrition. Seventeen elements are known to be essential to the health and growth of plants. Typically, nitrogen, phosphorus, and potassium are provided in the greatest quantity. With increasing knowledge of the role of each of the nutrients essential to plants, there is a better understanding of the importance of providing a given nutrient at the appropriate stage of phenology. To accomplish this, rapid changes in fertilizer formulations and methods of application have been necessary.
Another factor changing fertilization formulations and methods is a phosphorous-containing acids and their salts. The formulation stabilizes the phosphorous against oxidation to phosphate. Suitable phosphorous-containing acids are phosphorous acid and polyphosphorous acid, based generally on the formula H3PO3, and hypophosphorous acid and polyhypophosphorous acid, based generally on the formula H3PO2. Phosphite, the salt of phosphorous acid, has properties that are known to be beneficial to crop production. It is taken up through the foliage of avocado and citrus, two species which classically do not take up phosphate through their foliage. Phosphite has fungicidal properties with regard to some species of pathogenic fungi: Rhizoctonia solani, Botrytis cinerea, Piricularia oryzae, Plasmopora viticola, Phytophthora cinnamomi, and Phytophthora parasitica. Recently, it has been demonstrated that phosphite also serves as a source of metabolically active phosphorus in plants. The properties of phosphite that make it desirable as a fertilizer are enhanced when it is formulated according to the present invention as a double or multiple buffer with phosphorous acid, hypophosphorous acid, polyphosphorous acid and/or polyhypophosphorous acid and their respective salts and organic acids and their salts per this invention.
Suitable organic acids have the formula R—COOH or R—COO− where R is hydrogen or a carbon-containing molecule or group of molecules. Suitable organic acids are those that maintain the phosphite ion in a substantially fully solubilized form upon dilution with water at pH varying from about 6.5 to about 8.5 and that result in a use dilution fertilizer having a foliage acceptable pH for phosphorus uptake. Preferred organic acids are dicarboxylic and tricarboxylic acids.
By the term “substantially fully solubilized” it is meant that upon dilution, the phosphite does not precipitate, or at least not appreciably, so as to affect administration of the liquid product to the plant foliage, and thus is in a form available to the plant. With present phosphite fertilizers, there is a tendency for phosphite to precipitate if diluted with alkaline water, thereby rendering the phosphite in a form that is unavailable to the plant for uptake.
By the term “foliage-acceptable pH for phosphorus uptake”, it is meant a pH that allows phosphorus to be absorbed by the plant without causing damage to the foliage. A foliage-acceptable pH for phosphorus uptake usually ranges between about 5.0 to about 7.0, and preferably between about 5.5 to about 6.5. Phosphorus is most readily taken up by foliage at pH 6.0. Depending on the plant species, a pH below 5.0 can cause damage to leaves and/or the flowers and/or fruit. At higher pH, between about 7.0 to about 7.5, there is reduced uptake of nutrients, although generally there is no plant damage. A pH between about 7.5 and 8.0, depending on the plant species, plant damage may result. A pH greater than 8.0, generally causes damage to the plant in addition to reducing uptake of the nutrients. Accordingly, suitable organic acids are those that help provide a “buffered composition” having the desired pH range. This means that a “use-dilution fertilizer” having an acidic to neutral pH (pH 5.0 to 7.0) can be achieved upon high dilutions (up to about 1/600) of the concentrated fertilizer with highly alkaline water (up to a pH of about 8.5).
Organic acids that meet this these criteria include but are not limited to intermediates in the Kreb's Tricarboxylic Acid Cycle, amino acids such as glutamic acid and aspartic acid, vitamin acids such as ascorbic acid and folic acid, and their respective salts. Particularly preferred organic acids are dicarboxylic and tricarboxylic acids selected from the group consisting of citrate, pyruvate, succinate, fumarate, malate, formate, oxaloacetate, citrate, cis-aconitate, isocitrate, and α-ketoglutarate. Citrate is a particularly preferred organic acid because of it is relatively inexpensive and readily available.
These formulations allow the maintenance of continued solubility, and thus availability for uptake by plants, of phosphorus, with or without other nutrients, over a significantly wide range of concentrations and pHs. The increased solubility of these formulation formulations over that of phosphate or phosphite fertilizers makes it possible to prepare fertilizers with a greater concentration of phosphorus per unit volume than traditional phosphate or polyphosphate fertilizers or the simple unbuffered salts of phosphorous acid recently being marketed as fertilizers for foliar application which are available as super saturated solutions with only about 16% phosphite, and which are diluted approximately 1:100 to about 1:300. The resulting pH of these fertilizers varies significantly depending upon the pH of the water used, thus affecting the availability of the nutrients for foliar uptake. In contrast, the highly concentrated fertilizers of the present invention, which can be diluted with water at a ratio of about 1:600, allow for more cost effective shipping, handling, and application. They result in greater uptake of phosphorus by the canopy of plants than traditional phosphate or recent phosphite fertilizers not formulated in this manner.
The formulations provided herein also make it possible to formulate various combinations of other essential plant nutrients or other inorganic or organic compounds as desired and maintain their solubility when used over a wide range of concentrations and pHs, which is not possible for present phosphate or phosphite fertilizers. For example, boron, manganese, calcium; iron and other elements can be provided at relatively high concentrations in these formulations. Thus, these phosphorus fertilizers also enhance the canopy uptake of other mineral nutrients essential to plants. They can be used as a canopy application to improve pre- and post-harvest crop quality.
Formulations can also be prepared with copper. However, when high concentrations of copper are used; the copper used, the copper is not-fully not fully solubilized. In this situation, the insoluble copper is desirable as it prevents rapid uptake of the copper and thus minimizes the potential for copper toxicity. As the insoluble copper is rewetted over night overnight by dew, dissolution occurs so that additional copper is taken up. The buffering capacity of the formulation maintains the pH at a foliage-acceptable pH when the insoluble copper is rewetted so that conditions are optimal for uptake and are benign to the plant tissues. While copper is an element essential to plants, it is required in only small amounts. In relation to nitrogen, plants require, in general, 10,000- to 75,000-fold less copper. Provided to the foliage of the plant at the rate provided by this formulation, copper is a very effective fungicide, in addition to being a plant nutrient and fertilizer.
In addition to the above-mentioned advantages, the formulations disclosed have a direct benefit to the environment. Because the formulations allow successful foliar feeding of phosphorus to a number of plants that do not effectively take up phosphorus when supplied in phosphate or polyphosphate forms, and because these formulations enhance the uptake of other nutrients, they are cost-effective and can replace less efficient, traditional soil-feeding methods. This results in reducing phosphate pollution of the groundwater and eutrophication of freshwater ponds, lakes and streams.
The phosphorus fertilizers disclosed herein can also be advantageously applied through the soil or by irrigation systems as solid (granular) or liquid formulations. These formulations can be used at pHs sufficiently low to clean irrigation lines and alter the pH of the soil to solve alkalinity problems while supplying essential nutrients to plants. Example 2, below discloses a suitable formulation for irrigation application. With irrigation application, the fertilizer flowing through the irrigation system will typically have a pH lower than about 2.5, usually less than about pH 1.5. The low pH is designed to supply phosphorus while killing bacteria and algae (slime) which plug irrigation lines, thus cleaning the lines. The low pH also dissolves calcium carbonate deposits at and around the emitters, and solubilizes the calcium carbonate so Ca2+ is available to the plant. Once delivered to the soil near the plant, sufficient water is applied to achieve a pH suitable for phosphorus uptake by the plant. The form in which the phosphorus is supplied in these formulations is more mobile than phosphate fertilizers or than the simple salts of phosphorous acid recently being sold as fertilizers, and thus more available and more readily taken up by the roots of plants. An advantage of these formulations is that the form in which phosphorus is supplied does not inhibit the development of mycorrhizal fungi to the same degree that traditional phosphate fertilizers do. The present compositions can also be formulated with certain nutrients in addition to phosphorus that are readily absorbed through soil applications at pH of about 5.5 to about 7.0. Such nutrients include nitrogen, calcium, magnesium, potassium, molybdenum, boron, and sulfur.
Another advantage with the phosphorus fertilizers disclosed herein is that they do not support the growth of green algae to the same degree that traditional phosphate fertilizers do. This is of significant importance to agriculture, commercial nurseries, the ornamental and cut flower industry, and the home and garden industry, as it will prevent the growth of green algae which typically proliferate and plug irrigation emitters, foul pots and benches, and provide a niche for the growth of pathogenic bacteria and fungi. These formulations also endow the phosphorus fertilizer with anti-viral, anti-bacterial and anti-fungal activity. This bacterialcidal bactericidal activity in a phosphorus fertilizer makes it possible to use this fertilizer to inhibit ice-nucleating bacteria to thus protect plants from frost damage.
Methods of Preparation
The phosphorus fertilizers are prepared by first forming solutions of the phosphorous and organic acids. Other desired nutrients can then be added with constant stirring. The amount of phosphorous relative to organic acid is not critical, as long as appropriate buffering and solubility are achieved. Generally the amount of organic acid that is added will depend upon the form in which the nutrient elements are added. For example, if calcium is to be added in the form of calcium hydroxide (a base), then the acid form of the organic acid, for example citric acid, would be used rather than its salt, citrate. In addition to the desired nutrients, other additives, that are known in the fertilizer industry, can be added. These include, for example, wetting-agents, surfactants, spreaders, stickers etc., and are described in The Farm Chemical Handbook, supra (incorporated herein by reference). The fertilizer compositions can also be prepared as solid formulations, identical to the liquid ones by simply leaving out all of the water. The properties are the same as the liquid formulations but have the additional advantage of weighing less for the same amount of nutrient.
Methods of Application
The fertilizer is applied according to crop-specific recommendations which will depend upon the application method (foliar, soil, irrigation, etc.), time of application, rate of application, and product formulation. Crops that will benefit from the fertilizer include, but are not limited to, avocado, citrus, mango, coffee, deciduous tree crops, grapes and other berry crops, soybean and other commercial beans, corn, tomato, cucurbits and cucumis species, lettuce, potato, sugar beets, peppers, sugarcane, hops, tobacco, pineapple, coconut palm and other commercial and ornamental palms, hevea rubber, and ornamental plants.
In addition to the foliar, soil, and irrigation application methods mentioned above, the present fertilizer may prove beneficial to certain crops through other application methods. For example, trunk paints or other methodologies may provide for a continuous low supply of fertilizers, such as, for example, “intravenous” feeding as practiced in the boron nutrition of soybeans.
In order that the invention described herein may be more fully understood, the following examples are set forth. All chemicals used were of analytical reagent quality and approximately 100% by weight unless otherwise specified. All formulations are expressed in terms of weight to volume. It should be understood that these examples are for illustrative purposes only and are not to be construed as limiting the scope of the invention in any manner.
A formulation was prepared of 1 gallon of 0-40-0 fertilizer with 3.86 lbs H3PO3, 1.34 lbs tripotassium citrate, 1.34 lbs of trisodium citrate, and 4.0 lbs of 58% ammonium hydroxide. The components were dissolved in water with constant stirring. This single formulation can be used at a rate of 2 quarts in as little as 20 gallons of water of pH 6.5 to 8.5 up to 300 gallons of water of pH 6.5 to 8.5 and maintain a pH between 5.5 to 6.5 without the formation of any precipitate.
A formulation was prepared of 1 gallon of 0-40-0 fertilizer with 3.86 lbs H3PO3 and 0.5 lbs citric acid. This formulation is stable at pH 1.0 or less and is designed for application through the irrigation system. It is stable against oxidation and precipitation when supplied through the irrigation water.
A formulation was prepared of 1 gallon of 0-30-0 fertilizer with 74.89% elemental boron with 2.89 lbs H3PO3, 28.67 lbs borax (Na2B4O7.10 H2O), 17.16 lbs boric acid (H3BO3), 1.54 lbs H2SO4 and 2.67 lbs citric acid. A solution of the phosphorous and citric acid was first prepared, then the other elements were added with constant stirring. This formulation can be used at the rate of 2 quarts in as little as 20 gallons of water of pH between 6.5 to 8.5 up to 300 gallons of water of pH 6.5 to 8.5 and maintain a pH between 5.5 to 6.5 without the formation of any precipitate.
A formulation was prepared of 1 gallon of 0-30-0 fertilizer with 21.57% Zn zinc and 23.22% Mn manganese with 2.89 lbs of H3PO3, 7.92 lbs ZnSO4, 7.16 lbs Mn(H2PO2)2.H2O, 0.61 lbs citric acid and 0.87 lbs 58% NH4OH. This formulation can be used at the rate of two quarts in as little as 20 gallons of water of pH between 6.5 to 8.5 up to 300 gallons of water of pH between 6.5 to 8.5 and maintain a pH between 5.5 to 6.5 without the formation of any precipitate.
A formulation was prepared of 1 gallon of 0-30-0 fertilizer with 5.4% Ca calcium. It was packaged in a two-container system where 1 gallon of solution A contained 2.89 lbs H3PO3, 0.68 lbs Ca(OH)2, and 0.28 lbs citric acid, and 1 gallon of solution B contained 0.16 lbs Ca(OH)2, 0.60 lbs KOH, 3.34 lbs 58% NH4OH, 0.28 lbs citric acid, and 0.67 lbs EDTA (ethylenediaminetetraacetic acid). Two quarts of solution A can be added to as little as 20 gallons of water of pH between 6.5 to 8.5 up to 300 gallons of water of pH between 6.5 to 8.5 followed by the addition of two quarts of solution B. The final solution is between pH 5.5 to 6.5 and without precipitation.
A formulation of 1 gallon of 0-30-0 fertilizer with 4.32% Ca calcium can be made without requiring EDTA. This formulation is also packaged in a two-container system where 1 gallon of solution A contains 2.89 lbs H3PO3, 0.67 lbs Ca(OH)2 and 0.28 lbs of citric acid, while 1 gallon of solution B contains 2.67 lbs of 58% NH4OH, 0.6 lbs KOH. Two quarts of solution A can be added to as little as 20 gallons of water of pH between 6.5 to 8.5 up to 300 gallons of water of pH between 6.5 and 8.5 followed by the addition of two quarts of solution B. The final pH of the solution is between 5.5 and 6.5 and without precipitation.
A formulation was prepared of 1 gallon of 0-30-30 fertilizer with 2.89 lbs H3PO3, 2.99 lbs KOH, and 0.84 lbs citric acid. Two quarts can be added to as little as 20 gallons of water of pH between 6.5 to 8.5 and up to 300 gallons of water of pH between 6.5 and 8.5. The pH of the final solution is between 5.5 and 6.5 without precipitation.
A formulation was prepared of 1 gallon of 0-30-0 fertilizer having 4.8% iron with 2.89 H3PO3, 1.75 lbs iron-citrate, 0.74 lbs KOH, 0.62 lbs NaOH, and 2.00 lbs of 58% NH4OH. Two quarts of the formulation can be added to as little as 20 gallons of water pH 6.5 to 8.5 and up to 300 gallons of water of pH 6.5 to 8.5. The pH of the final solution is between 5.5 to 6.7 without precipitation.
A formulation was prepared of 1 gallon of 0-30-0 fertilizer having 23.22% manganese with 2.89 H3PO3, 7.16 lbs. Mn(H2PO2)2, and 0.133 lbs. sodium citrate. Two quarts of the formulation can be added to as little as 20 gallons of water pH 6.5 to 8.5 and up to 300 gallons of water of pH 6.5 to 8.5. The pH of the final solution is between 5.5 to 6.5 without precipitation.
A formulation was prepared of 1 gallon of 0-30-0 fertilizer having 57% copper with 2.89 H3PO3, 7.3 lbs Cu(OH)2 (57% Cu), and 1.34 lbs of 58% NH4OH. Two quarts can be added to as little as 20 gallons of water of pH 6.5 to 8.5 up to 300 gallons of water of pH 6.5 to 8.5. The pH of the final solution is between 5.5 to 6.5. The copper is not fully soluble, however this is desirable in that it prevents the rapid uptake of copper when applied to plant foliage.
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