CS234968B1 - A method of preparing a drip concentrate - Google Patents

Abstract

The invention relates to a method for preparing a liquid concentrate containing zinc in the form of an organo-metallic complex with a chelate character, which can be prepared by reacting 100 parts by weight of zinc oxide and/or zinc carbonate and/or zinc hydroxide and/or metallic zinc with 5 to 200 parts by weight of sulfuric acid and/or nitric acid) and/or hydrochloric acid, with 80 to 810 parts by weight of citric acid) being added at any time before or during the reaction and the pH of the reaction mixture being adjusted to a value of 6.5 to 8.0 with hydroxides and/or alkali metal carbonates and/or ammonia and/or hydroxides and/or carbonate and/or ammonium carbamate.

Description

234968

The invention relates to a process for preparing a zinc-containing liquid concentrate by reacting zinc oxide and / or carbonate and / or zinc and / or zinc metal with mineral acids and citric acid, followed by adjusting the pH of the reaction mixture. One hundred elements form an important part of plant nutrition and their harmonic growth. The relative significant trace elements include zinc, which, among other things, has an effect on the regulation of uptake by phosphorurines. Plants sensitive to lack of zinc can include 'maize, hops', potatoes, beans, l'an, peaches and others.

Zinc deficiency symptoms may be caused by various factors. Stage factors include, for example, pH of the pod, its structure, the ratio of total and resorbable zinc in the pod; high level mamangan and iron in it and p'od. Other agents are the plants themselves, mainly from the point of view of the need for zinc according to the type and the production differences. Not less important factors include climatic conditions such as temperature and humidity. For example, zinc deficiency is more severe in the spring months in cold and damp bases containing the lower level of resorbable zinc. Also, excessive fertilization of phosphorus causes deficiency symptoms. Currently, zinc sources are used to remove the zinc deficiency or symptoms of its deficiency. We do not include inorganic ionic and complex compounds, zinc oxide, Zn-frits, natural organic complexes, as well as synthetic chelates and organometallic complexes (Mortvedt J. J .: Fertilizer Solutions 23, 3. 64 [19791].

The relatively hungry source of zinc is sulfate zinc and zinc oxide, sometimes zinc chloride is also used. It is advisable to use these formyzines in combination with physiologically acid-reactive fertilizers! ammonium nitrate, which increases the resorption of zinc.

The application of sulfate and zinc oxide in combination with nitrogen, phosphoric fertilizers [e.g., amophos, ammoniacalised superphosphate and the like] often results in the formation of sparingly soluble zinc compounds that are difficult to access by plants. it is limited solely to acidic and sandy spots. It is generally valid that the efficiency of the source, the zinc is higher on neutral and acidic bases than on the alkaline bases.

One of the most progressive forms of removing zinc deficiency, as well as other micronutrients, is the use of their compounds in a quaternary form that provides rapid efficacy and uniformity, especially for foliar (non-root) application. From the aspect of the miscibility of liquid zinc films and other trace elements with liquid nitrogen-phosphorous fertilizers, the carriers of these trace elements, and condensed phosphates, are believed to be [e.g. pat. 80 03386 (1980)], naturally occurring chelating agents such as lignosulfonates are polyflavonoids, and the like. (DTPAJ, hydroxyethylenediaminetetraacetic acid (HEDTA1 and nitrilotriacetic acid (NTA)).

As reported by Mortvedt [Fsrt. Solutions 23, 64, (1979)], an experimental use has begun. "Zinc-citric acid" prepared by reaction of zinc chloride with citric acid (pH of the liquid concentrate of 0.7) and zinc glucoheptanate.

For the synthesis of the chelates or organometallic complexes with the character of chelates, it is necessary to use a chelating agent of any of the water-soluble zinc salts of ionic character.

It has now been found that zinc-containing liquid zinc concentrate in the form of organometallic complexes with chelating properties can be prepared from the water-soluble zinc compounds according to the invention.

The invention is based on the fact that each 100 parts by weight of zinc oxide and / or zinc carbonate and / or zinc hydroxide and / or zinc metal is reacted with 5 to 200 parts by weight, preferably with 55 to 195 parts by weight of sulfuric acid and / or. or nitric acid and / or hydrochloric acid], wherein 80 to 810 each, preferably 170 to 350 parts by weight of citric acid, are added each time during the course of the reaction, and the pH of the reaction mixture is adjusted to 5.5. to 9.0, preferably 6.5 to 8.0 alkali metal hydroxides and / or carbonates and / or ammonium and / or ammonium hydroxide, ammonium and / or ammonium carbamates. Furthermore, it has been found that, in view of achieving the maximum degree of degradation of said zinc sources (zinc extract in solution), it is not necessary to add mineral acids in excess of the stoichiometric amount.

It has also been found that from the aspect of the extract in the solution it is preferred that the concentration of mineral acids reaches a concentration of 20 to 45% by weight.

Simultaneously releasing dilution heat, (mineral acid reactions, zinc sources are pronounced exothermic) accelerate the reaction. An advantage of the process according to the invention is that it makes it possible to produce liquid zinc concentrate containing zinc or zinc in the form of organometallic compounds from less valuable zinc-containing secondary raw materials in the form of carbonate and / or hydroxide and / or zinc oxide and / or metal. citrate-based chelate properties, it also makes it possible to process less valuable mineral acids, which are rarely usable and due to the low insoluble residue content that moves due to lower concentrations and / or contaminant content. from 0.35 to 1.25% by weight, this is a practically waste-free technology.

Another advantage of the liquid concentrate produced by the process of the present invention is its miscibility not only with liquid nitrogen fertilizers, but also with liquid nitrogen-phosphorous fertilizers which contain phosphorus in the form of trihydrogen phosphate salts and / or salts thereof. -dated phosphoric acids. The zinc citrate form is particularly advantageous from its biodegradable base due to the action of microorganisms, as well as metabolic processes in plant organisms. Finally, a preferred method of the invention is that liquid concentrates, with a relatively high zinc content of 5 to 8% by weight, can be prepared. The following examples illustrate, but do not limit, the invention. Example 1

In a glass or enamelled stainless steel clad boiler equipped with a stirrer, a poor condenser and a cooling shell (361.55 parts by weight of water, 102.42 parts by weight of zinc technical oxide (content of 78.44% Zn) were put in duplicate and 123.11 parts by weight of H 2 SO 4 at a concentration of 97.9% were added to the suspension so formed, and the temperature of the reaction mixture rose to 88 ° C, while 260.83 parts by weight of 99% crystalline crystals were fed to the reaction mixture. The reaction mixture was cooled to about 20 ° C and 367.69 parts by weight of NH 4 OH at a concentration of 28.46% NH 3 to cool the reaction mixture while cooling the reaction mixture. the mixture did not exceed 60 ° C. The product obtained had the following specification: expected Zn content: 6.61% actual Zn content: 6.32% yield mesh: 95.60% insoluble residue content: 0.65% pH: 8.1 Example 2

In the device, as in Example 1, it was presented. 361.55 parts by weight of water and 102.42 parts by weight of technical ZnO containing 78.44% of Zn and 260.83 parts by weight of 92% crystalline citric acid were added with stirring, while the temperature of the reaction mixture decreased to +10 to + by the negative dissolution heat of citric acid Noc: 6 ° C. 123.11 parts by weight of H 2 SO 4 at a concentration of 97.9% were charged into the resulting suspension and the temperature of the reaction mixture was stepped to 71 ° C.

After addition of sulfuric acid, the reaction mixture was stirred for 60 minutes. The reaction mixture was cooled to about 20 ° C and 325.1 wt.% NHIOH of 28.46% NH 3 was charged in the cold while maintaining the temperature in the range of 50-55 CIC. The liquid concentrate obtained had the following specification: expected Zn content: 6.85% actual Zn content: 6.76% insoluble residue: 0.35% yield: 98.70% pH: 7.8 Example 3

The procedure was similar to that of. in example2. To. The reaction mixture consisted of 265 parts by weight of water: 102.42 parts by weight of technical ZnO containing 78.44% Zn and 260.83 parts by weight of 99% crystalline citric acid (temperature dropped to + 6 ° C) with stirring 234 parts by weight of HNO 3, with the temperature of the reaction mixture at 48 ° C. After the addition of HNO 3, the reaction mixture was stirred for 60 minutes while the temperature of the reaction mixture reached 35 ° C. 340.1 parts by weight of NH 4 OH with a concentration of 28.48% of NH 3 and cooling maintained the temperature in the range of 30 to 45 ° C. The obtained product had the following specification: expected Zn content: 6.68% actual Z content: n: 5, 90% yield: 88.30% insoluble residue: 1.25% pH: 7.6 Example 4

The procedure was similar to that of. in Example 2. To the reaction mixture consisted of 102.42 parts by weight of ZnO (78.44% Zn), 320 parts by weight of H2O and 260.83 parts by weight of 99% citric acid soot, continuously stirring the 145.32 parts by weight of the mixture sulfuric acid] containing 98.47 wt H2SO4 97.9% and 46.85 wt HNO3 66.17%, the temperature rising to about 70 ° C. The reaction mixture was allowed to cool

Claims (1)

the acid addition was stirred for 60 minutes, then 323.44 parts by weight NH 4 OH of 28.46% NH 3 were metered in while cooling. The liquid concentrate obtained had the following specification: 8 Zn content expected: 6.97% actual Zn content: 6.80% yield: 19.60% insoluble residue: 0.60% ipH: 7.6 PRCDMET EXCEPTION Preparation of liquid concentrate containing or zinc chelated organometallic complex, characterized in that each 100 parts by weight of zinc oxide and / or zinc carbonate and / or zinc hydroxide and / or zinc metal is not reacted with 5 to 200 parts by weight of sulfuric acid and / or zinc. or nitric acid] and / or hydrochloric acid], each time 80 to 810 parts by weight of citric acid are added during the reaction and the pH of the reaction mixture is adjusted to 5.5 to 9.0 with hydroxides and / or carbonates alkali metals and / or ammonia and / or ammonium hydroxide and / or ammonium carbonate. Severografia, n. P., Závod 7, Most Gena 2,40 Kcs