CS267943B1 - Liquid Fertilizer for My Wet Nutrition ra st 11 n - Google Patents

Abstract

The solution relates to a liquid fertilizer for foliar plant nutrition containing basic, secondary and trace biogenic elements. It consists of 52 to 98 weight percent of a polyphosphate type NP solution containing at least 30% of phosphorus chemically bound in the form of unary condensed ammonium phosphates, primarily as diphosphates, so-called pyrophosphates /P^O- ~' triphosphates ÁP,P.q / and tetraphosphates /P.O., / ammonium and 2 to 48 weight percent of a liquid concentrate of secondary and trace plant biogenic elements, in which the predominant proportion of biogenic elements is chemically bound in the form of complex - non-dissociated compounds. The liquid fertilizer also contains at least one of the plant growth regulators and/or vitamins and/or adhesives and/or surfactants, with the pH of the undiluted liquid fertilizer being 5.575pH - 8.5 and its specific gravity being 1,200Sd ° - 1,450 kg.m. From the point of view of ensuring advantageous handling and storage properties of the products according to the solution, it is expedient if the liquid foliar fertilizers have the character of true aqueous solutions.

Description

The invention provides a liquid fertilizer for root nutrition of plants containing basic, secondary and trace biogenic elements, which consists of a nitrogen-phosphate solution based on linearly condensed ammonium phosphates and a liquid concentrate of secondary β trace plant biogenic elements.

The vegetation of the earth has its origin in the sea. All the factors indispensable for their development, growth and physiological development, such as: water, light, carbon dioxide, inorganic salts and several compounds of organic character, were and are therefore very well accepted by most plants. As found by HALLIDAY, D.J. /Foliar application of major nutrient* to fruit and plantation crops.” Outlock on Agriculture 3 : 111-115, 1961/, JYUNG, W.H. and WITTWER, S.H. /’’Kinetics of foliar absorption* Plant Physiol., 1963/ and WITTWER, S.H. - BUKOVAC, M.J. - TUKEY, H.B. /Advances in foliar feeding of plant nutrients” in: Fertilizer Technology and Usage, pp. 429-455, Soil Sci. Soc. of America, Madison 11, Uis., 1962/ the rate of sorption of individual biogenic plant elements by the surface /leaf area/ of plants is different:

Plant nutrient;

Time for receiving 50% of the applied plant nutrient:

nitrogen /amide from urea/ 0.5 - 2 hours phosphorus 5 - 10 day 1 potassium 10 - 24 hours calcium 10 - 24 hours magnesium 10 * 24 hours with 1 ra 5 - 10 days chlorine 1 - 4 days iron 10 - 20 days manganese 1 - 2 days zinc 1 • 2 days molybdenum 10 - 20 days

The high efficiency of plant nutrients in their foliar application has become a motive for the production of industrial fertilizers designed specifically for phosphorus application. Of the large number of preparations of this type produced abroad, the following can be mentioned in particular: solution and suspension fertilizers of the WUXAL type /by Schering AG and Philips Duphar GmBH, NSR under license from Schering, also produced by the Hemijska Industrie Zorka - Šabac, SFRJ/, solution fertilizers COMPLESAL FLUID /by Hoechst, NSR/, VITALIK-N /by Asahi Chemical Mfg.Co.Ltd., Japan/, BIOFERT 1-8 /by IHP-Prahovo, SFRJ/, FERTILIN /by Hemijska Industrie Zorka-Sabac, SFRJ/, PETRIX 1-3 /Peremartoni Vegyipari Vállalat, MLR/, FITOHORM /Bácska MGTSZ, MLR/, FERTY GREEN /by Diana, Greece/, FIKSAL A and B /SCHK-Stara Zagora, BLR/, NUTRI-FLO, NUTRI-PLEX, FOLIAR, FOLLOW-THRU /USS-Agri Chemicals, USA/, SOYBEAN MIX, CITRUS MIX, VEGETABLE MIX /Brandt Chemical, USA/ and others.

The following foliar liquid fertilizers are currently produced in the Czechoslovak Socialist Republic: HARMAVIT, HARMAVITSPECIÁL, VEGAFLOR, MKH-18, FLORAN LIQUID, HERBASOL, OBM, HUMUSOL, LAFOLAN BLUE, LAFOLAN GREEN, LAFOLAN YELLOW, FYTOVIT and experimentally produced special foliar liquid fertilizers FOLI-NICOTIANA, FOLI-BETA VULGARIS and LEGUVIT.

Although not all of the above-mentioned foliar liquid fertilizers also contain phosphorus, none of the preparations that do contain it contain a phosphorus component in a form other than monophosphate, the so-called orthophosphate form.

One of the serious problems with foliar application of phosphorus is the fact that the amount of plant nutrient that can be applied without risk of leaf damage is too small compared to the phosphorus requirements of most plants.

EN 267 943 B1

BAREL, D. and BLACK, C.A. /Extension Circular 981 g, Iowa State University, USA/ tested several phosphorus compounds in order to determine the maximum amounts of phosphorus applied to soybean and corn leaves. The various phosphorus compounds were applied in the form of their ammonium compounds at pH 7.0, and BAREL and BLACK reached the following results:

Form of phosphorus applied to plant leaves Determined average value of maximum foliar applied phosphorus /ug P/cm ² / corn ca SO) & monophosphate, so-called orthophosphate 120 80 two phosphates, also known as pyrophosphate 220 160 triphosphate, also known as tripolyphosphate 370 220 four-phospho speech nan, the so-called tetrapolyphosphate 370 220 trimetaphosphate 370 280 tetrametaphosphate 400 280 phosphoric acid triamide 340 80 hexaaminocyclotriphosphazene 190 ' 340

The beneficial effect of phosphorus applied to plant leaves in the form of condensed phosphates was also confirmed by the results of field experiments /GRAY, R.C.: Foliar fertilisation with primary nutrients during the reproductive stage of plant growth, paper presented on 14. 10. 1977 at the meeting of The Fertiliser Society of London, Proceedings No. 164, p. 9/s

Form of phosphorus applied to plant leaves: Corn ca soybean Grain yield /kg.ha ^-1 / Phosphorus content in leaves /X/ Grain yield /kg.ha“1/ Phosphorus content in leaves /X/ None - control 10,990 0.32 3,775 0.37 Monophosphate, PO^ ³ “ 11,460 0.34 3,610 0.41 Triphosphate, PjO^q 11,800 0.35 4,000 0.40 T et rafos foreč nan, P^O^ó- 11,800 0.33 3,970 0.40

Triphosphate proved to be the best source of phosphorus for both corn and soybeans, although tetraphosphate could be applied to soybeans at higher concentrations without damaging the leaves.

Based on the above-mentioned suitability of condensed phosphates for foliar application of phosphorus, in the recent period abroad, as well as in the Czechoslovak Socialist Republic, the possibility of preparing special industrial fertilizers intended for foliar plant nutrition containing condensed phosphates has been investigated.

Based on the results of laboratory tests and field trials, the American company Allied Chemical Company introduced the production of a solution NPKS - foliar fertilizer type 3-20-18-1S, intended primarily for foliar fertilization of soybeans, which the company has been supplying under the commercial name FOLIAN since 1977. This foliar liquid fertilizer contains approximately 62% phosphorus in the form of condensed potassium phosphates and consists of a concentrated aqueous solution of urea, condensed potassium phosphates and potassium sulfate.

EN 267 943 B1

Similarly, ASHMED, H.H. in U.S. Pat. No. 4,491,464 discloses a liquid fertilizer for foliar application consisting of potassium polyphosphates, ammonia, and soybean protein hydrolysates.

Already in the early seventies, a universal foliar liquid fertilizer was developed, the basis of which was an aqueous solution of urea and tetrapotassium diphosphate - K.P_0_. The method of preparing this liquid fertilizer is protected by the Czech Patent Office No. 163 523 /PV 82-73/,

The subject of Czechoslovak Agricultural Act No. 216 448 /PV 1583-81/ is liquid fertilizer concentrates of trace elements, secondary plant nutrients and phosphorus prepared on the basis of cyclic condensed phosphates, so-called metaphosphates.

Although the above preparations represented a significant contribution in the field of increasing the agrochemical and agronomic value of preparations intended for foliar plant nutrition, their common disadvantage was that they used expensive » only limitedly available linear and cyclic condensed potassium phosphates /K^P^O?, K,P,0. _nz ΙΚΡΟ,Ι , or their mixtures/ as a source of condensed phosphates. 5 3 i U on

It has now been found that liquid fertilizers intended for foliar and extra-root plant nutrition, containing basic, secondary and trace biogenic elements, with a significant proportion of the phosphorus contained in the fertilizers being bound in the form of linearly condensed phosphates, can also be prepared on the basis of nitrogen-phosphate solutions of the polyphosphate type. Foliar liquid fertilizers according to the invention consist of:

up to 98 percent by weight of a nitrogen-phosphate solution of the polyphosphate type, containing at least 30 percent of phosphorus chemically bound in the form of linearly condensed ammonium phosphates, primarily as ammonium diphosphates, primarily as diphosphates, so-called pyrophosphates, triphosphates /P^O^ ^5- / and tetraphosphates /P^O^ ⁶ / ammonium, and 2 to 48 percent by weight of a liquid concentrate of secondary and trace plant biogenic elements, in which the predominant proportion of biogenic elements is chemically bound in the form of complex-non-dissociated compounds.

The liquid fertilizer further optionally also contains at least one of the plant growth regulators and/or vitamins and/or adhesives and/or surfactants. For the pH of the undiluted fertilizer, it is 5.5 = pH 8.5 and for its mass, it is 1,200 = d ₂₀ o _c * 1,450 kg . m ³ .

It has been shown to be particularly advantageous to use one of the so-called basic NP solutions of the polyphosphate type, for example solution 10-34-0 or solution 11-37-0, in the preparation of foliar liquid fertilizers. These so-called basic NP solutions can be used in undiluted or, if necessary, diluted with water for the preparation of liquid fertilizers according to the invention.

It is preferable if the concentrate of secondary and trace biogenic plant elements contains boron and/or magnesium and/or calcium and/or iron and/or sulfur and/or zinc and/or copper and/or manganese and/or cobalt and/or molybdenum and/or titanium.

In order to ensure the necessary stability of the final preparation as well as the required biological effectiveness of trace and secondary plant nutrients, it is expedient if the liquid concentrate of secondary and trace biogenic elements contains, as the main - basic complexing substance, a salt of ethylenediaminetetraacetic acid, a salt of diethylenetriaminepentaacetic acid, or a salt of N,ν' bis-2-hydroxyethylaminoacetic acid /dihydroxyethylglycine/.

From the point of view of storage and handling, it has proven to be particularly advantageous if the final products - liquid fertilizers intended for foliar plant nutrition according to the invention

CS 267 943 B1 have the character of true aqueous solutions.

Liquid fertilizers for foliar plant nutrition have several advantages compared to currently produced and used fertilizers of this type, of which the following can be particularly emphasized: reduced risk of damage to the leaves of treated plants, higher degree of utilization of the phosphorus component, high phase stability of preparations 1 at temperatures below 0 °C and at high concentrations of biogenic elements contained in fertilizers, lower costs for providing phosphorus in condensed form, increased availability of phosphorus raw material in comparison with potassium condensed phosphates, possibility of operative correction of the content of nitrogen component in application solutions by adding arbitrary amounts of nitrogen solutions based on urea and ammonium nitrate.

The following examples illustrate, but in no way limit, the subject matter of the invention.

Example 1

Preparation of liquid concentrate of secondary and trace plant nutrients:

In a glass crucible equipped with heating by means of a glass immersion exchanger heated by steam, a stirrer, a thermometer /0 - 100 °C/ and a hopper, 78.97 kg, i.e. 62.18 dm^ of an aqueous solution of approximately 30% tetrasodium salt of ethylenediaminetetraacetic acid, commercially supplied under the name Syntron B /pH 12.84/, were introduced. With constant heating with steam to 40 - 50 °C and stirring, the following was gradually added:

6.06 kg of crystalline magnesium sulfate MgSO^ 7 í^O

1.76 kg of crystalline calcium nitrate, Ca/NOj^.AH^O

1.75 kg of crystalline manganese sulfate, MnSO^ . SH^O

2.98 kg of crystalline ferrous sulfate, FeSO^ . 7HjO

0.79 kg of crystalline zinc sulfate, ZnSO^. 7HjO

0.24 kg of crystalline cobalt sulfate, CoSO4.7H2O and 0.78 kg of crystalline copper sulfate, CuSO4.7H2O.

Individual inorganic salts were added sequentially - each subsequent one only after the previous one had dissolved. Then 2.21 kg of a liquid concentrate of complexed boron according to Czech invention A0 259 578 was added, which contained at least 4.5 wt. % XB and 3 wt. % N - NH^ ⁺ , supplied under the commercial name FOLIBOR.

After thorough homogenization of the reaction mixture, another 0.45 kg of ammonium molybdate citrate, prepared in accordance with AO No. 213 006, was added in the form of the manufactured and commercially supplied liquid Mo-concentrate MOLYCHEL. Finally, the initially alkaline chemical reaction of the reaction mixture /pH 10.2/ was adjusted to a pH of 6.41 by adding 4.01 kg of crystalline citric acid. In this way, 100.0 kg, i.e. 75.76 dm$ of liquid microelement concentrate of dark green color, in which for 10 parts by weight of MgO there were approximately 4.25 parts by weight of CaO, 4 parts by weight of Mn, 6 parts by weight of Cu, 0.5 parts by weight of Mo and 1 part by weight of B. The concentrate also contained 1.94% of total nitrogen, 1.5% of sulfur and, due to the use of green shale from the production of titanium white, also titanium.

Finalization of foliar liquid fertilizer:

87.5 kg of de-sedimented nitrogen-phosphorus fertilizer type 10-34-0 prepared by continuously conducted high-temperature neutralization of a mixture of commercial extraction trihydrogenphosphoric and superphosphoric acid from the company Boliden /Sweden/ with gaseous ammonia, according to the method according to AO 259 372, was placed in a glass kettle. The used NP-solution of bright green color contained 55% of phosphorus bound in the form of linearly condensed ammonium phosphates, of which the decisive proportion was bound in the form of di- and

CS 267 943 Bl

4- 5- · triphosphates /Ρ ₂ 0 _? ^{and P} 3°1O ^{Thin -layer} chromatography on cellulose revealed that the NP solution used contained a small amount of ammonium tetraphosphates. Next, 12.4 kg of microelement concentrate, the preparation of which was already mentioned above, and then 0.1 kg of 0.5% alcoholic solution of beta-indolylacetic acid were gradually added to the glass crucible.

Thus, 100 kg, i.e. 73.0 dm ³ of liquid foliar fertilizer of the polyphosphate type according to the invention was prepared. The product had a light green color and its pH in the undiluted state was 6.4 /pH of a 1 X solution in distilled water boto 6.81/. The liquid fertilizer in 1 dm ³ contained: 114.8 g total N; 398.0 g total P^O^; 1.6 g MgO; 0.68 g CsO; 0.64 9 Mn; 0.97 g Fe; 0.29 g Zn; 0.08 g Co; 0.32 g Cu; 0.16 g B; 0.08 g No and 2.5 g total sulfur. Furthermore, the product contained 6.8 . 10 ³ g of growth stimulator in 1 dm ³ .

Example 2

For the purpose of preparing a liquid foliar fertilizer according to the invention with a higher content of nitrogenous components, the following was gradually added to an enamel boiler equipped with a stirrer:

233.65 kg of a 10-34-0 type nitric-phosphoric acid solution of similar composition as in the previous example;

186.85 kg of nitrogenous solution containing 42.2 wt. X NH^NO-j, 32.7 wt. X CO/NHg/j and 25.1 wt. X water;

79.0 kg of liquid microelement concentrate prepared in a similar manner as in Example 1, but based on approximately 30% aqueous solution of pentasodium salt of diethylenetriaminepentaacetic acid (Na2 DTPA), in which the individual biogenic elements were represented in the following mass ratios: 1 B: 6 Mg: 3 Ca: 4 Mn: 6 Fe: 1.8 Zn: 0.5 Co: 2 Cu: 0.5 Mo, the concentrate containing 0.082% B, and 0.5 kg of 0.5% alcoholic solution of beta-indolylacetic acid.

By the above method, 500 kg of foliar fertilizer according to the invention was prepared, in which the ratio between the nitrogen and phosphorus components was balanced. The product was characterized by a weakly acidic chemical reaction /pH: 6.05: pH of 1 X aqueous solution: 6.6/ and its specific gravity was 1,330 kg m .

Example 3 3 574.05 g of NP-solution type 10-34-0 prepared by high-temperature neutralization of polyphosphoric acid from the Swedish company Boliden were placed in a 1,500 cm sulfonation flask, and 540.09 g of water and 385.05 g of granulated urea were added while stirring. In this way, 1,500 g of basic NP-solution type 1.2 - 1.0 - 0 were prepared, the pH of which in the undiluted state was 6.65 /pH^ : 6.82/ and the specific gravity was 1.215 g . cm ^-3 .

The second flask was then charged with 1,399.2 g of the prepared basic NP solution, 99.3 g of a liquid microelement concentrate of a similar type as mentioned in the previous example and 1.5 g of a 0.5% alcoholic solution of a growth stimulator (beta-indolylacetic acid). In this way, 1,500 g of a liquid foliar fertilizer of the polyphosphate type were prepared, which had a practically neutral chemical reaction (pH: 6.6; _pH : 7.02) and whose specific gravity was 1.218 g. cm.

Claims (2)

OBJECT OF THE INVENTION 1. Liquid fertilizer for off-root plant nutrition comprising basic, secondary and trace biogenic elements, which may optionally also contain at least one of plant growth regulators and / or vitamins and / or adhesives and / or surfactants, characterized in that it consists of from 52 to 98% by weight of a nitrophosphate solution of the polyphosphate type, containing at least 30% of phosphorus chemically bound in the form of linearly condensed ammonium phosphates, in particular as double phosphates, the so-called ammonium pyrophosphate (P , in which the predominant proportion of biogenic elements is chemically bound in the form of complex compounds. 2. Liquid fertilizer for off-root nutrition of plants in stage 1, characterized in that it contains, as a nitrogen-phosphorus solution, a solution of type 10-34-0 or type 11-37-0 in water-diluted or undiluted form.