CS214908B1 - A method of preparing a mixture suitable for fortification, preservation a) or to increase the biological value of feed - Google Patents

Abstract

The invention solves a method of preparing a mixture of urea-formaldehyde condensates and formaldehyde condensation reaction products from urea-formaldehyde condensate with different formaldehyde content. The semi-product from the production of urea-formaldehyde adhesives is used for the preparation of the mentioned mixture without further treatment a) or after its modification with the addition of urea. Free formaldehyde, which is present in the urea-formaldehyde condensate, is converted to monosaccharides with the number of carbon atoms C3 to C under the catalytic effect of oxides a) or hydroxides of alkali metals a) or earths, in the presence of catalysts of internal formaldehyde condensation, which are products of a sugary nature, preferably products of internal condensation of formaldehyde

Description

The invention provides a process for the preparation of a mixture consisting of formaldehyde formation reaction products and urea-formaldehyde condensates; suitable for orthification, preservation (a) or enhancement of the biological value of plant feed.

For the treatment of plant matter for nutritional purposes, besides the traditional method of drying, silage is used as a very important way of preserving plant matter. The process of preserving plant materials by silage makes it possible to store undried plant materials without completely destroying them, which simplifies handling, increases feed production productivity and is often the only possible way of preserving digestible nutrients in plant materials.

In the traditional way of storing the ensiled plant mixture, there is a significant quantitative and also qualitative degradation of the plant matter * mainly / by the rotting process.

However, by preserving suitable preservatives, while maintaining optimum conditions, it is possible not only to maintain but also to substantially increase the nutritional value of the ensiled feed materials.

In addition to the use of traditional preservatives, for example, mineral and organic acids themselves, such as sulfuric acid, phosphoric acid, hydrochloric acid, sulfuric acid, acetic acid and formic acid (U.S. Pat. Nos. 52,988, 53,891, 55,652, 120,464), inorganic acid salts such as calcium phosphate, sodium phosphate, sodium nitrite, potassium nitrite, calcium chloride (U.S. Pat. Nos. 52,987, 65,864, 67,249, 67,928, 72,216, U.S. Pat. No. 1009468, 1048132, US Pat. 2714057], salts of organic acids, for example, alkali metal and earth salts of acetates, formates and salicylans, in particular sodium and calcium formates, also preserve linearly C ₄ -C ₁₅ aliphatic 1,3 diols or their esters, aqueous formaldehyde solution, preferably using urea as an inhibitor of formaldehyde polymerization (French Pat. 2161099, German Pat. 2555558).

Molasses, sugar shavings, starch containing natural products are used to increase the nutritional value of the feed being shed (cf. US Pat. No. 56,722, Germany, US Pat. No. 1009,468).

Recently, mother liquors from pentaerythritol production containing mainly the formaldehyde condensation reaction products, such as aldols, unsaturated aldols, hydroxyaldehydes, hydroxyketones, glycol aldehydes, glycerolaldehydes, monosaccharide and monosaccharide condensation products, are used to fortify a) or preserve plant matter. aldehydes, respectively. ketones, pentaerythritol, calcium formate or formaldehyde.

The above chemical compounds are the main or by-products of separate production units, for example the production of phosphoric acid, acetic acid, calcium formate, or represent unwanted wastes of some chemical products, such as waste syrups in the production of pentaerythritol.

In most cases, the preparation of the preservative, energy-containing components of the fortification mixtures is simple and is carried out both by the producers of these mixtures and directly when applied to the vegetable matter or in the production of granulated feeds.

Due to the lack of beet molasses, which is used both as a tmelldlo and as an energy component, a mixture consisting of lower urea-formaldehyde condensates and products of the condensation reaction of formaldehyde is also beginning to be applied to the granulation of the compound feed.

For the preparation of a mixture of urea-formaldehyde condensates and formaldehyde condensation reaction products, urea-formaldehyde condensate containing 60-75 wt. dry matter and free formaldehyde in an amount of 1-5% by weight. Catalytic effect of calcium hydroxide at temperatures 60-75 ° C. Celsius is free formaldehyde converted to the formaldehyde condensation reaction products. The reaction is terminated at a formaldehyde concentration below 0.1% by weight.

A disadvantage of a process in which the calcium hydroxide alone catalyzes the condensation reaction of formaldehyde is the difficult to control, temperature course of the reaction, which has an adverse effect on product quality, handling loss of the reaction mixture, and a negative effect on the completion of the reaction. Indeed, the action of calcium hydroxide on the formaldehyde present in the urea-formaldehyde condensate at the selected initial temperature of the reaction mixture (60-75 ° C) forms an autocatalyst in the induction period of the formation reaction. When the critical concentration of the autocatalyst is reached, the course of the reaction is strong exothermic, manageable only at very high heat dissipation. If the temperature course of the reaction is not mastered, the reaction mixture overheats and reacts, which is accompanied by foaming and handling losses of the reaction solution. The product thus obtained is dark brown, with a caramel aroma, and is partially degraded by the dehydration and condensation reactions of the monosaccharides formed by the condensation reaction of formaldehyde. At temperatures below 55-60 ° C the reaction is not fast enough, which negatively affects the production of the device.

The present invention provides a process for the preparation of a mixture of urea-formaldehyde condensates and formaldehyde condensation reaction products from urea-formaldehyde condensate containing 60-85 weight percent. % solids, preferably 65-75 wt. % solids and 0.1-10 wt. % of formaldehyde, preferably 2-5% by weight of formaldehyde, when the condensate is used without further treatment a) or after modification with the addition of urea, respectively. from urea-formaldehyde condensate, the so-called semi-product from the production of urea-formaldehyde adhesives with a content of 30-80% by weight, preferably 40-50% by weight. % and preferably 3 - 15 wt.%, preferably 4-8 wt. formaldehyde. The free formaldehyde present in the urea-formaldehyde condensate is converted under the catalytic action of oxides a) or of earth, preferably by catalysis of oxides and / or hydroxides of calcium, barium, strontium, magnesium and sodium and potassium hydroxides in the presence of a formaldehyde internal condensation catalyst. 80 ° C, preferably at 35-45 ° C for products of a sugary nature predominantly to the monosaccharides C ₃ -C ₈ aldose and ketose, which constitute the energy component of a mixture suitable for the conservation of (a) or fortification of plant matter and granulation of feed.

Suitable catalysts for formaldehyde internal condensation are formaldehyde condensation reaction products, monosaccharides, sugar by-products, so-called " syrups from pentaerythritol production, hydroxyaldehydes, hydroxyketones etc.

An advantage of the process for preparing a mixture of urea-formaldehyde condensates and formaldehyde condensation reaction products according to the present invention is that by eliminating the induction period for the formation of the formaldehyde condensation autocatalyst, the production capacity of the device is substantially increased. suppresses the course of undesirable dehydration condensation reactions of monosaccharides, thereby avoiding significant losses in the energy component of the formulation.

The advantage of this process is also the elimination of the possibility of reacting the reaction mixture and comfortable handling of the completion of the condensation reaction of formaldehyde, thus achieving the desired formaldehyde concentration of the finished product below 0.1% by weight.

A further advantage is that the course of the reaction at lower temperatures practically eliminates the overheating of the reaction mixture above the boiling point of the mixture and thus allows the preparation of the mixture without extreme foaming and handling losses. The following examples are given for illustration: 1

Into a three-necked flask equipped with a stirrer and a thermometer, 500 g of urea-formaldehyde condensate containing:

4.5 wt. free formaldehyde and 25 g syrups from pentaerythritol production. The mixture is heated to 35 ° C, 10 g of calcium hydroxide are added and kept at this temperature for 2 hours. Then the contents of the flask are heated to 45 ° C and after stirring for 2 hours at this temperature, the reaction at zero formaldehyde concentration is complete to give a final syrup-like product with a very mild caramel aroma. Example # 2

500 g of urea-formaldehyde condensate containing 8 wt. % of formaldehyde and 50 g of formaldehyde condensation products in an alkaline medium, the reactor contents are heated to 40 ° C and 15 g of calcium hydroxide are added. After stirring the mixture at this temperature for one hour, the reactor contents were heated to 60 ° C. The end of the reaction, indicated by zero formaldehyde concentration, is reached at the indicated temperature in 10 min. The final product is obtained by concentrating the reaction product to 75% solids content.

Example # 3

A product suitable e.g. as a component for the production of granulated feeds, a similar preparation to that described in Example 1 is prepared. 1, except for the use of barium hydroxide instead of calcium hydroxide.

Example # 4

Process for the preparation of a mixture of urea-formaldehyde condensates and condensation products of formaldehyde alone similar to that of Example 1. 1 except for the use of 5 g glycol aldehyde instead of 10 g syrups from pentaerythritol production.

Claims (1)

The present invention provides a process for the preparation of a mixture of urea-formaldehyde condensates and formaldehyde condensation products from a urea-formaldehyde condensate containing 60-85% by weight. % dry matter, preferably 65-75 wt. % dry matter and 0.1-10 wt. % formaldehyde, preferably 2-5 wt. formaldehyde when the condensate is used without further treatment of a) or after modification with the addition of urea, respectively. from urea-formaldehyde condensate, the so-called semi-product from the production of urea-formaldehyde glues, containing 30-80% by weight, preferably 40-50% by weight; % dry matter and with 3-15 wt.%, preferably 4-8 wt. formaldehyde. The free formaldehyde present in the urea-formaldehyde condensate is catalysing the oxides of a] or the soils, preferably catalysing the oxides of a) or the hydroxides of calcium, barium, strontium, magnesium and sodium and potassium hydroxides in the presence of an internal catalyst. condensation of formaldehyde, converted at temperatures of 20-80 ° C, preferably at 35-45 ° C, for sugar-like products predominantly C3-C8 aldose and ketose monosaccharides, which form the energy component of the composition as appropriate preservation a) or plant fortification and granulation of feed. Suitable condensation catalysts for formaldehyde are formaldehyde condensation reaction products, monosaccharides, sugar byproducts, so-called pentaerythritol syrups, hydroxyaldehydes, hydroxyketones, etc. An advantage of the process for the preparation of a mixture of urea-formaldehyde condensates and condensation products. the formaldehyde reaction of the present invention is that the removal of the induction period for the formation of the autocatalyst condensation of formaldehyde results in a substantial increase in the production capacity of the device, which ultimately results in a considerably more efficient production, while at the same time suppressing the undesired dehydration process. monosaccharide condensation reactions, thereby avoiding significant losses on the energy component of the formulation. This process also has the advantage of avoiding the possibility of reacting the reaction mixture and the convenient control of the completion of the formaldehyde condensation reaction, thereby achieving the desired formaldehyde concentration of the finished product below 0.1% by weight. Another advantage is that the course of the reaction at higher temperatures virtually precludes overheating of the reaction mixture above the temperature of the varus and thus allows the preparation of a mixture of extremes of foaming and handling losses. The following examples are given by way of example: EXAMPLE 1 500 g is placed in a three-necked flask equipped with a thermometer stirrer. of urea-formaldehyde condensate containing 4.5 wt. free formaldehyde and 25 gsirups from pentaerythritol production. The mixture is heated to 35 ° C, 10 g of calcium hydroxide is added and kept at this temperature for 2 hours. Thereafter, the flask contents are heated to 45 ° C and after 2 hours of stirring of the mixture at zero temperature, the reaction is complete with zero formaldehyde concentration, giving a fine syrupy character with a very mild caramel flavor. Example 2 500 g of urea-formaldehyde is charged into the glass reactor. condensate containing 8 wt. of formaldehyde and 50 g of formaldehyde condensation products in an alkaline medium, the reactor contents are heated to 40 ° C and 15 g of calcium hydroxide is added. After stirring the mixture for one hour at this temperature, the reactor contents were heated to 60 ° C. The end of the reaction indicated by the zero concentration of formaldehyde is reached in 10 min at the indicated temperature. The final product is obtained by concentrating the reaction product to 75 ° / other dry matter. Example 3 A product suitable, for example, as a component for the production of granulated feed, is prepared similar to Example 1, except for using barium hydroxide instead of calcium hydroxide. Example 4 Preparation of a mixture of urea-formaldehyde condensates and condensation products of formaldehyde alone similar to Example 1 except using 5 gglycoldehyde instead of 10 g of pentaerythritol syrups. OBJECT OF THE PREFERRED EMBODIMENT A process for the preparation of a mixture consisting of formaldehyde and urea-formaldehyde condensate reaction reaction products, characterized in that the urea-formaldehyde condensate with a content of 30-80% by weight, preferably 40-75% by weight, is present. % solids, with 0.1-15 wt.%, preferably 2-8% wt. formaldehyde is treated with hydroxide (s) or with alkali metal oxides, but also with oxides, preferably oxides (a) or hydroxides of calcium, barium, strontium, magnesium, sodium hydroxide and potassium, in an amount of 0.1-30% by weight, preferably 0% by weight. 5-5% by weight, at temperatures of 20-80 ° C, preferably at 4 shots 35-45 ° C, in the presence of 0.01-50%, and waste products from pentaer manufacture, preferably 5% by weight. -20 wt. tritol products. ; the formaldehyde condensation reaction but also Ί 54 3821-84