CS213006B1 - Preparing the liquid liquid of the cheesecake with ebbase of nitrogen, nitrogen and chemically bound citric acid - Google Patents

Abstract

A method for preparing liquid and solid fertilizers by reacting individual molybdate phosphates of the 3 to 5 /nh,/2o.p2o5. 5 to 24 MaO^ or their mixtures with ammonium hydroxide and citric acid in a sterile environment. The temperature of the reaction mixture is maintained in the range of 15 to 100 *C.

Description

The invention relates to a method of preparing liquid and solid fertilizers containing molybdenum, nitrogen and chemically bound citric acid suitable for plant nutrition and treatment.

Plants absolutely need molybdenum, among other trace elements, for their harmonious development.

One of the most important physiological functions of molybdenum is its influence on the unimpeded course of biochemical processes of nitrogen fixation and on the reduction of nitrate nitrogen to amide nitrogen.

The activity and activity of beneficial microorganisms /Azotobacter, Clestridium and others/, which live in symbiosis with legumes, capable of binding atmospheric nitrogen, directly depends on the presence of assimilative molybdenum ferrites in the soil.

It is also known that molybdenum has a catalytic effect on protein synthesis and a regulatory function in the activity of enzymes such as xanthine exidase, aldehyde exidase, nitrate reductase and nitrogenase. It positively influences the ratio of organic and inorganic phosphorus and its distribution in plant leaves, as well as the formation of chlorophyll and L-ascorbic acid. Molybdenum limits the accumulation of sugars and starch in leaves, enables their transport to the correction system and has an irreplaceable function in the inactivation of phosphatases. Together with other trace elements such as boron, copper and zinc, it improves the physicochemical properties of protoplasm and regulates the water regime of plants.

Typical symptoms of molybdenum deficiency in plants are the formation of chlorotic tissue, deformation of leaves as a result of weakened nitrogen assimilation by the plant. In severe molybdenum deficiency, the chlorotic tissue withers and the leaf blade is reduced. In some plants, molybdenum deficiency is manifested by the death of the growth tip and heart, the number of nodes on the roots of legumes decreases, flowering and seed formation is slowed down or stopped /barley, corn, wheat, oats, rye and others/.

Plants that are particularly sensitive to the presence and content of molybdenum in the soil include legumes, cauliflower, beets, cabbage, lettuce, kale, spinach, flax, hops and others.

Molybdenum is applied essentially by the following methods: foliar application, i.e. leaf spraying, seed dressing and soil application. Molybdenum application mainly by the foliar method has also become widespread in viticulture in the treatment of grapevines, in which molybdenum deficiency was caused by excessive fertilization with nitrogenous fertilizers.

Mertvedt J.J., Giordane P.M., Lindsey W.L.: /Micronutrients Agriculture, «ladison, Wiscensin, USA 1972/ recommend using its water-soluble salts, e.g. ammonium molybdate, sodium molybdate, and more sparingly soluble molybdenum sources such as molybdenum oxide, molybdenum sulfides and molybdenum frits as sources of molybdenum for fertilization. Parham T.M. and Smeing Y.E.: /US Patent 3,798,020 from 1974/, with regard to good miscibility with liquid fertilizers containing phosphates, propose to use Fe, Mn, Zn and Cu in the form of citrates, while recommending to apply molybdenum exclusively in the form of water-soluble sodium and ammonium molybdates, or in the form of water-soluble ammonium paramolybdate - /NH^/^ MoyOg^MHgO.

Recommended doses of molybdenum for foliar application are 0.2 to 0.4 kg Mo.ha ^-1 , and for soil application 0.3 to 1 kg Mo.ha ^-1 .

213 η η β

In foliar application, it is advantageous to use 0.01 to 0.05% ammonium molybdenum in doses of 500 to 700 l.ha. According to the opinion of several authors /Zach: Conference on Microelements in Fertilizer Management, Turecká 1977/ there is good experience with preventive fertilization with sparingly soluble molybdenum phosphate and ammonium in doses of 1 to 2 kg of these substances per ha of treated land.

It is also known to use solutions or suspensions prepared by reacting salts of heteropolymolybdic acids, e.g. molybdatebarites, molybdatesilicates and molybdatephosphorates, with aqueous solutions of ammonia and/or alkali metals and/or certain alkaline earth metals, which are the subject of PV 1553-79.

Despite the fact that the above-mentioned soluble molybdenum compounds allow for preventive and curative intervention to eliminate molybdenum deficiency, even through foliar application in the form of sprays of their soluble solutions or their solutions in liquid fertilizers, their wider use is not without problems related to their availability and relatively high price.

Another disadvantage is the loss of molybdenum, which occurs because the amount that flows through the plant is mostly fixed to the soil complex and the molybdenum passes to a form that is difficult to absorb or not absorbable by plants.

In the case of the preparation of the Czechoslovak PV 1553-79, a certain, although not essential, drawback is the relatively high pH /approx. 8.6/, which in some mixtures, especially with liquid so-called sludge multi-element fertilizers, can cause certain difficulties. Although in these cases, when applied to the soil in comparison with molybdenum and paramolybdenate, the retragradation of molybdenum is reduced, its possibility is not excluded.

The other sources of slowly absorbable molybdenum mentioned above (MeO, MeSg, frits, ammonium molybdate phosphates) do not allow for rapid curative intervention in the form of mimecorene application.

It has now been found that the above-mentioned shortcomings and disadvantages can be largely eliminated by liquid trace fertilizers containing molybdenum, nitrogen and chemically bound citric acid, prepared by the method of the invention.

The essence of the invention consists in reacting MeO-j, NH^OH and citric acid in such a way that for every 100 parts by weight of MeO^, 34.8 to 166.3 parts by weight of NH^OH, 24.5 to 175.2 parts by weight of citric acid are added, while the temperature of the reaction mixture is maintained at a value of 20 to 80 °C, preferably 60 °C and the pH at a value of 3.5 to 7.0, preferably 3.7 to 6.5.

The method of preparing a liquid steppe fertilizer containing molybdenum, nitrogen and bound citric acid can be illustrated by a general reaction scheme.

2xMoO^ + /4x+nz/ NH^OH + /y+z/ CgHgOy.HgO + aq ..... >

-> /2x-y/ /NH ₄ / ₂ 0.Mo0 ₂ . y /NH ₄ / ₂ Oí.yCgH^ J+ ζ/Ν^/^Ηθ^ _{+ 8q>} where

2x = number of moles of MoO^ at x=1, preferably x=1 with 50 /y+z/ = 1 to 2.4 moles of CgHgO^.HgO, preferably y+z= 2 to ěx and ólev CgHgOy.HgO y = 1 to /2x-1/ η = 1 to 3, preferably n = 2

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It has further been found that it is appropriate to maintain _{the pH} ^of the product in the range of 3.5 to 7.0, preferably 3.7 to 6.5.

The liquid trace fertilizer specified and prepared according to the invention has the following advantages:

The method of preparing a liquid trace fertilizer according to the invention is relatively simple and does not require expensive technological equipment. The technological process according to the invention does not release harmful exhalations, neither liquid nor solid waste is generated, and from an environmental point of view the process is harmless, the technological process is also energy-efficient, because the reactions taking place simultaneously or sequentially are exothermic, as a result they are practically self-supporting and the temperatures during moderate cooling do not exceed 60 *C.

Liquid steppe fertilizers according to the invention can be used in agriculture and as a source of biologically active molybdenum for plant nutrition and treatment. Mixable with liquid nitrogen, nitrogen-phosphorus, nitrogen-phosphorus-potassium, phosphorus-potassium and potassium fertilizers, solution, slurry and suspension type. When appropriately diluted with water or in a mixture with the above types of liquid fertilizers, liquid trace fertilizers according to the invention can be applied foliarly /sprayed on the leaves/ or into the soil.

The liquid steppe fertilizer according to the invention is not phytotoxic and, when applied foliarly in the appropriate concentration and dose, does not damage the leaf area of the treated plants.

When applied to the soil, it shows higher efficiency compared to the commonly used ammonium paramolybdenum - /NH^/gMo^O^. 4H ₂ O. The presence of citric acid bound in the complex and in ammonium citrates increases the activity of the soil microflora. The complexing agent used - citric acid - is biologically fully edbutane and as a result helps the formation of humates.

The liquid trace fertilizer prepared by the application of the invention, and especially with the content of ammonium citrates, has the properties of buffering/sustaining solutions. The liquid trace fertilizer prepared according to the invention enables the systemic application of molybdenum.

The following examples illustrate, but do not limit, the scope of the invention.

Example 1 to 12

For the preparation of the liquid trace element fertilizer according to the invention, the following starting materials were used /their composition is expressed in % by weight/:

technical MeO^ containing 1./ 65.3%Mo 2./65.39% Me 3·/ 63.86% Mo .

/100% Mo0 ₃ contains 66.65% Mo/ NH ₄ 0H with a concentration of 25% NH^ /100% NH^OH contains 39.97% NH^Z Procedure:

The required amount of water and ammonium hydroxide was placed in a glass crucible equipped with a cooling coil, a stirrer, a thermometer, and holes for dosing liquid and solid reaction components, and the required amount of MoO^ was added with continuous stirring. The reaction mixture was maintained at a temperature of about 60 *C with moderate cooling, and after the majority of the dosed MoO^ had reacted, the dosing of crystalline citric acid CgHgOy.i^O began. The reaction mixture was cooled so that its temperature did not exceed 80 *C. After the dosing of citric acid, the reaction mixture or the final product was hemolyzed for as long as the temperature began to drop rapidly with constant cooling. The final product was then rapidly cooled to room temperature. The composition of the reaction mixtures and final products is given in the following Table 1 and for the reaction mixtures it is given both in wt.% of technical components and in wt.% of pure components.

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Table 1

Example % M· v Composition of the reaction mixture /% by weight/ MoO-j Evil Thermal clean 100 %-residues Yes MyOj amenialkalkali N NH ₄ 0H /25% NH-j/ MH4OH /39.97% NH-,/' ^C 6 ^H 8°7 ♦ H20 added H ₂ 0 1 65.39 66.65 10.0 15.29 15.00 2.92 14.20 7.31 10.95 10.95 59.56 S 2 65.39 66.65 10.0 15.29 15.00 2.94 14.30 7.36 21.9 21.9 48.51 | 3 65.39 66.65 14.0 21.41 21.00 4.09 19.89 10.23 15.33 15.33 43.37 4 65.39 66.65 10.06 15.38 15.10 6.75 32Í83 16.90 2^.04 22.04 29.75 tons 5 56.30 _ 66.65 12,.95 23.00 19.43 6.70 32.58 17.76 34.65 34.85 9.57 6 65.39 66.65 13.7 20.95 20.55 9.97 48.49 24.94 30.01 30.01 0.55 7 65.39 66.65 12.0 18.35 18.00 3.54 17.21 8.86 26.28 26.28 38.16 8 63.86 66.65 ¹ 2.0 18.80 18.00 7.79 37.89 19.49 29.96 29.96 13.35 9 63.86 66.65 12.85 20.12 19.28 6.55 31.85 16.39 30.68 30.68 17.31 10 65.39 66.65 14.00 21.41 21.00 5.11 24.85 12.78 30.66 30.66 23.08 11 65.39 66.65 14.00 21.41 21.00 6.13 29.81 15.34 30.66 30.66 18.12 12 65.39 66.65 14.00 21.41 21.00 8.14 39.59 20.37 30.66 30.66 8.34

Pekracevani tables 1

Final product sedimentation /% by weight/

Me MeOx /66.65% Me/ anenial N NH+ bonded ^C 6 ^H 8°7- ^H 2° chewing gum /H _o 0.N05 with ₄ / * ^{J saw} 20*C 10.00 15.00 2.92 3.7δ 10.95 70.29 5.68 10.00 15.00 2.94 3.79 21.9 59.30 about 4.8 14.00 21.00 4.09 5.27 15.33 58.40 5.68 10.06 15.10 6.75 8.69 22.04 54.17 6.7 12.95 19, »3 6.7 8.63 34.85 37.09 6.5 13.7 20.55 9.97 12.84 30.01 36.6 about 6.7 12.0 18.00 3.54 4.56 26.28 51.16 about 4.0 12.00 18.00 7.79 10.03 29.96 42.01 6.5 12.85 19.28 6.55 8.43 30.68 41.61 6.5. 14.00 21.00 5.11 6.58 30.66 41.76 3.76 14.00 21.00 6.13 7.89 30.66 40.45 4.66 14.00 21.00 8.14 10.48 30.66 37.86 about 5.0

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The determined solubility temperatures of some of the above products by the method of disappearance of the last crystal /so-called clearing points/ indicate sufficient stability at temperatures of -0 °C.

and

Liquid trace fertilizers with the composition given in Table 1, Example 3: solubility temperature: -1.3 C Liquid trace fertilizers with the composition given in Table 1, Example 10: solubility temperature: -5.4 *C Liquid trace fertilizers with the composition given in Table 1, Example 11: solubility temperature: -7.35 *C Example 13

Within the framework of biological /container/ experiments, the effectiveness of the liquid steppe fertilizer with the composition given in Table 1, Examples 5, 8 was compared with the effectiveness of the commonly used ammonium para-alloydate - /NH^/gMe^^.4H ₂ O - applied foliarly, by spraying on the leaves and into the soil.

The tested crop was pea ELMA, - application rates were graded from 0.2 to 2 kg Me per hectare. The main indicators of agrochemical efficiency of the liquid trace fertilizer according to the invention were the yield of dry and green matter and the plant length.

When applying the liquid steppe fertilizer prepared according to the invention to the soil at a dose of 1 kg Me per hectare, a yield increase of 8.8% was compared to the variant treated with ammonium paramolybdate. Application of ammonium paramolybdate at the same dose achieved a yield increase of 10% compared to the control variant not treated with molybdenum.

The absolute increase in yield when applying liquid steppe fertilizer to the soil, prepared according to the invention, compared to the untreated control variant is 18.7%.

When foliar application by spraying on the leaf of a liquid trace element fertilizer prepared according to the invention, at a dose of 1 kg Me per hectare, an increase in yield of 23% was observed compared to the control variant not treated with molybdenum.

In addition to this significantly higher biological effectiveness of the liquid trace fertilizer prepared according to the invention compared to ammonium paramolybdenum, an increase in the number of flower buds was observed.

Phytotoxicity tests of this liquid trace fertilizer were negative.

Claims (1)

5 213 006 Determined solubility temperatures of some of the foregoing methods by the disappearance of the last crystal (mel). woes of cleanliness / testify to sufficient dexterity at temperatures - 0 * C. a Liquid solid fertilizer · Composition given in * Table 1, Example 3: Solubility temperature: -1.3 CKlseous trace fertilizer · Composition given · * in Table 1, Annex 10d: Solubility temperature: -5.4 * CCross fertilizer The composition shown in Table 1, Example 11: solubility temperature: -7.35 * EXAMPLE 13 In the biological / container / pellet, the efficacy of the paste trace fertilizer composition was compared to that shown in Table 1, Example 5, 8 by the efficacy of the commonly used paramolybdenum ammonium- (NH4) -gOyOg4.4H2O-applied foliar, foliar spray and undercoat. The test crop was ELMA, - application rates were graded from 0.2 to 2 kgMo per hectare. The evaluators of the agrochemical efficacy of the liquid trace fertilizer according to the invention were the yield of dry and green matter and the post-mortem length of the plant. When applying the liquid trace fertilizer prepared according to the invention to the pod at a dose of 1 kg Mo per hectare, the yield increase was 8,%% compared to the ammonium treated paramolybdate. By applying ammonium paramolybdate at the same dose, the yield increased by 10% over the molybdenum-treated control variant. The absolute increase in yield when applying liquid trace fertilizer to the substrate prepared according to the invention is 18.7% over the untreated control variant. In foliar application by spraying onto a sheet of liquid trace fertilizer prepared according to the invention, an increase in yield of 23% over the control, molybdenum untreated variant was observed at a dose of 1 kg Mo per hectare. In addition to this substantial higher biological activity of the liquid trace fertilizer prepared according to the invention compared to ammonium paramolybdene, an increase in the number of petite pucks was observed. Phytotoxicity tests of this liquid trace fertilizer were negative. BACKGROUND OF THE INVENTION A process for preparing a liquid trace fertilizer, characterized in that molybdenum oxide, ammonium hydroxide and citric acid are reacted in amounts of 35 to 170, preferably 42 to 113, parts by weight of ammonium hydroxide and 25 to 175, preferably 125.1 to 170, in the environment. 5 parts by weight of citric acid, not every 100 parts by weight of molybdenum oxide, and the reaction is carried out at a temperature of 20 to 80 ° C, preferably 60 ° C, and preferably at pH 3.5 to 7.0, preferably 3.7 to 6.5%.