CS260772B1 - The manufacture of a preservative and / or silage agent - Google Patents

Abstract

A preservative or silage agent based mainly on carboxylic acids Ci to Cs, or partly on their ammonium salts, is produced from an aqueous solution of sodium salts of carboxylic acids Cl to Ce, so-called alkaline waters, formed as a by-product in the process of catalytic oxidation of cyclohexane to cyclohexanene and cyclohexanol, under the action of mineral acids (H2SO4, H3PO4, HCl) up to the concentration of 70 to Ϊ00% of carboxylic acids. The formed organic layer and the aqueous layer are separated. The aqueous layer is either used immediately or the salts are crystallized and dried. The organic layer or a fraction of the organic layer is a silage or preservative agent. These can be additionally fortified, such as with ammonia, trihydrogenphosphoric acid or mono- to trialkylphosphates.

Description

The invention relates to a process for the production of a preservative and / or silage composition mainly based on a technically low-valued by-product from the petrochemical process.

It is known (V. A. Filipov and 1 .: Chimija i technologi i topliv i butv 1984, No. 4, p. 4) to use a mixture of formic, acetic, propionic and butyric acids as so-called. ancestral acids from the oxidation of higher paraffins to higher fatty acids, as well as mixtures of formic and acetic acids, aldehydes and ketones (V. Macho et al., Czech Author's Certificate 210 250) for silage grass, sugar shavings and silage maize. U.S. Pat. No. 3,732,112 inhibits the growth of bacteria, yeasts and fungi in feed and food compositions containing 20-60 ° / o water by the addition of 0.05-50 °. (o) linear aliphatic diols having 4 to 1.5 carbon atoms per molecule or esters of such diols with acids having 2 to 20 carbon atoms per molecule, their production is technically 1 raw material demanding and costly (US Pat. 3,958,009) is also known (US Pat. of ammonium and potassium isobutyrate as pathogenic growth inhibitors, with 0.7 to 1.5% same as with 2% calcium propionate, the activity of which is further enhanced by citric acid. The production of admixtures of butyric acid and isobutyric acid itself, as well as their salts, usually requires special production.

On the other hand, the process for the production of a preservative and / or silage agent based on predominantly C 1 -C 6 carboxylic acids, possibly with part of their ammonium salts, is carried out by the so-called aqueous solution of predominantly sodium salts of carboxylic acids C1 to C6. alkaline waters, formed as a by-product in the process of catalytic oxidation of cyclohexane to cyclohexanone and / or cycloliexanol, are treated with a mineral acid such as sulfuric acid or trihydrogen phosphoric acid until displacement. of carboxylic acids from their sodium salts by 70 to 100 percent. The predominantly organic layer and the aqueous layer formed are separated, the aqueous layer is applied or crystallized, and / or phosphoric acid, and the organic layer, optionally after partial ammonialkalization, is a preservative and / or silage agent or is separated into fractions, the front fraction containing predominantly C 1 -C 6 carboxylic acids (and water being a silage and / or preservative, and another fraction, predominantly containing valeric acid, caproic acid and hydroxycaproic acid, is a preservative.

The method according to the invention has the advantage of being technical. simplicity, ensuring even higher technical appreciation of the so-called. alkaline waters as a by-product from the process of oxidation of cyclohexane to cyclohexanone and cyclohexanol, technical evaluation of not only known but also other difficult to determine components, so-called alkaline waters. Finally, the advantage is in fact the simultaneous production of either sodium salts of phosphoric acid as a feed component, especially feed salts, as well as a component of a nutrient solution for the production of petroproteins, both from n-alkanes and alcohols (methanol or ethanol) or sodium sulfate for the glass industry. detergents and other uses.

Called. Alkaline (fallen) waters or alkaline waste "lyes" isolated in considerable quantities as a by-product, technically low-value product from the process of catalytic oxidation of cyclohexane to cyclohexanone and cyclohexanol are mainly aqueous solutions of sodium salts of carboxylic acids C1 to Cs, but also dissolved other oxygen organic compounds and, as a rule, parts of free sodium hydroxide, possibly also mechanical impurities or also higher molecular weight insoluble substances, which should be removed, whether by harvesting, in particular with the aid of hydrophobic collection equipment or devices, filtration, centrifugation and the like. Inorganic acid is best applied to alkaline waters free of solid, gooey and other insoluble matter. Suitable mineral acids are hydrochloric acid, in particular sulfuric acid and phosphoric acid.

The organic layer as such or additionally with the addition of other known ingredients such as nontoxic biocides, anticorrosive additives, ammonia or ammonium hydroxide as an odor reducing agent of said acids is a preservative or silage agent or composition.

However, the organic layer of the present invention may be separated into two or more fractions, under normal, but most often under reduced pressure. Differential distillation can be used for separation, but in particular rectification, in particular with the assistance of compounds which preferably form an azeotrope with water or a black azeotrope with carboxylic acids. Such suitable reagents or compounds are mainly C2-C8 aliphatic alcohols, in particular ethanol and butanol.

As in the case of the initial organic layer, some of the ammonium hydroxide or ammonia, or other known anti-corrosion additives and biocides, may also be added to the individual fractions to reduce the odor intensity of the C1-C6 acids.

Distillation residue from the organic layer, i. j. a mixture of unidentified oxygen-containing organic substances may be a component of the fractions mentioned, or it may be added as a component to other oxygen-containing by-products of the so-called. MEK from the degree of hydrolysis, or so-called. hydrolysis in a hydrolysis column of the cyclohexanone plant. In the region, it can be used as a high calorific fuel.

The fraction containing mainly valeric acid, caproic acid, optionally hydroxycaproic acid and hydroxyvaleric acid, is a suitable preservative or preservative component for feed grain.

The production process of the present invention can be carried out continuously, semi-continuously or continuously. The preservative and / or silage agent produced by him may also be a component of other already known silage and preservatives.

Further details of the method of the invention as well as other advantages are apparent from the examples.

Example 1

From the production of cyclohexanone and / or cyclohexanol by catalytic oxidation of cyclohexane, the resulting by-product, so-called " alkaline waste liquors, respectively. Alkaline water drain (the expander water treating PK-107 in the production PS-103], composed essentially of an aqueous solution of sodium salts of carboxylic acids, a C to C. The density of such alkali wastewater at 20 ^C C = 1165 kg. ^m3, pour point = ~ - 27 ° C; ash - 21.6% w / w; pH = = 13.6; total sodium content - 8.4% w / w; sodium formate - 0.7%; sodium acetate - = 4 17% w / w sodium propionate - 2.91% w / w sodium n-butyrate = 5.71% w / w sodium n-valeran - 9.72% w / w sodium n-caproate = 1.14% w / w the remainder to 100% consists of the sodium salts of dicarboxylic acid monoesters, hydroxy acids and, optionally, other unidentified higher molecular weight, mainly oxygenated organic substances, as well as excess sodium hydroxide.

To 31.6 kg of these alkaline effluents is added, with stirring and cooling, 6.4 kg of 93.1% by weight sulfuric acid.

Reaction with free sodium hydroxide and sodium carboxylic acid salts leads to stratification. After stirring was discontinued, 10.6 kg of the upper organic layer and 27.4 kg of the lower aqueous layer were separated.

The aqueous layer is passed through a heat exchanger to a spray drier at a temperature of 320 to 350 ° C, in which not only free but also crystalline water of sodium sulfate and organic impurities are dried to give 8.7 kg of practically anhydrous sodium sulfate powder.

In the second variant, at 20 + 1 degree Celsius, predominantly sodium sulfate decahydrate is crystallized, from which it is dried in a stream of air at 28 + +1 ° C to obtain 13.5 kg and the filtrate is fed to a jet dryer as · in the first variant. For the purpose of producing pure Na2SO4. . 10 H2O is recrystallized again from water and water. NasSOí. 7 H2O from cold water (below 12 ° C). Both anhydrous and hydrated sodium sulphate are suitable components for the glass, paper and detergent industries.

The organic phase (organic layer) having an acid number = 266.7 mg KOH / g, saponification number - 439 mg KOH / g, pour point == = -35 ° C has the following composition (in% by weight): formic acid = 1.4%; acetic acid = 1.4%; propionic acid = 3.3%; n-butyric acid = 11.2%; n-valeric acid = 29.8%; caproic acid = 3.1%; hydroxycaproic acid = 3.7%; water = 25.9%; the remainder being unidentified oxygen species, such as dicarboxylic acid monoesters, hydroxy acids and the like.

This organic phase (organic layer) is used as a preservative (silage agent) as such (variant A), on the other hand, with an addition of 0.4% by weight. % phosphoric acid (variant B), but also with an additive of 0.4 wt. % phosphoric acid and 0.2 wt. tributylphosphate (variant Cj) The natural grass cover from the second mowing is fertilized or ensiled, fertilized with 240,0 kg. No ha ha ^1. The growth is dominated by Dactylis glomerata, Festuca pratensia and fescue The crayfish (Trifolium repens) is found in the cormorant (Poa pratensis) and the results are shown in Table 1.

Table 1

Evaluation of conserved grass matter

variant silage pH NH3 (° / w / w) Color fragrance structure The quality the class control without preservative 4.27 0,150 Brown odor undistorted IV. A in an amount of 0.50 wt. 3.47 0,044 olive green aromas. preserved I. B in an amount of 0.45% w / w. 3.52 0,042 olive green aromas. preserved I. % C in an amount of 0.45 wt. 3.50 0,038 olive green aromas. maintained I.

The results in Table 1 show that the additives of the organic layer used have a positive effect on the course and the resulting qualitative parameters of the preservation process. While in the control variant (without preservative), the finished silages are unsuccessful, characterized by an olostridial type of fermentation process accompanied by strong proteolysis (substantially higher ammonia values), with verified preservatives, respectively. silage agents A, B, C, the fermentation process is run satisfactorily.

An amount of 10 kg is taken from the organic phase (rectified layer) and rectified on a column of theoretical 4 and a refluxing ratio of 5: 1 at a pressure of 2.67 kPa. 4.042 kg of an I. fraction of m.p. in. 20 to 85 ° C / / 2.67 kPa and 3.7548 kg II. fraction o · t. in. 85-105 ° C / 2.67 kPa. The rest is 2,220 kg.

Fraction I has the following composition (in% by weight): formic acid = 2.51; acetic acid = 4.89; propionic acid - 10.58; n-butyric acid · 19.07; n-valeric acid - 17.58; caproic acid = 0.0; water - 45.26.

II. the fraction has the following composition (in wt.%): acetic acid = 0.1; propionic acid == 1.4; n-butyric acid = 14.8; n-valeric acid = 68.8; caproic acid - 13.2; water == 1.7.

The distillation residue has an average molecular weight (determined by cryptic) of 392 g. mol ^-1 ; acid number = 55.2 / mg KOH / / g; saponification number = 284 mg KOH / g; OH equals 0.9 wt.

In another variation, 1000 g is taken from the organic layer (organic phase) and rectified on a 48 packed glass packed laboratory column at a reflux ratio of 15: 1 at a pressure of 2.67 kPa. 397.5 g of a I. fraction with a boiling point of 20 to 86 ° C / 2.67 kPa and 382.5 g of a II. b.p. 94-105 ° C / 2.67 kPa. The residue is 220 g.

Fraction I has the following composition (in% by weight): formic acid - 2.76; acetic acid = 5.37; propionic acid = 11.93; n-butyric acid - 32.4; n-valeric acid = 0.6; n-caproic acid - 0.1 and water = 46.9.

II. the fraction has the following composition (in wt.%): acetic acid = 0.1; propionic acid = 0.1; n-butyric acid = 1.0%; n-valeric acid = 85.8; n-caproic acid = 12.8 and water - 0.2.

The distillation residue has an average molecular weight determined by cryoscopy of - = 417.2 g. mol ^-1 ; acid number = 23.1 mg KOH / g; saponification number = 226 mg KOH / / gS using fraction I as a silage reagent gives similar results as summarized in Table 1. The results are not impaired by the addition of ammonia up to 0.5 mol per 1 mol of organic acids.

Zasa II. fraction as well as II. a fraction together with a distillation residue, in an amount of 1.24% by weight, with an addition of 0.25% by weight; Phosphoric acid can be used for canning of wet fodder grain (barley, wheat).

Claims (3)

The results in Table 1 show that the additives of the organic layer used have a positive effect on the course and the resulting qualities of the preservation process parameters. While the control variant (without preservative) of the malfunctioning silage silage, characterized by a saolostridial type of fermentation process, accompanied by strong proteolysis (substantial higher values of ammonia), with verified preservatives, respectively. silage agents A, B, C, the course of the fermentation process is satisfactory. An amount of 10 kg was collected from the organic phase (organic layer) and rectified by the number of theoretical staples 8 and the reflux ratio of 5: 1 at 2.67 kPa. 4.042 kg of I fraction are obtained, m.p. 20-85 ° C, 2.67 kPa, and 3.7548 kg II. fractions of from 85 to 105 ° C / 2.67 kPa. The remainder is 2.220 kg. I. fraction has this composition (in% by weight): formic acid = 2.51; acetic acid = 4.89; propionic acid - 10.58; n-butyric acid · 19.07; n-valeric acid - 17.58; caproic acid = 0.0; vo-da - 45.26. II. the fraction has this composition (in% by weight): acetic acid = 0.1; propionic acid == 1.4; n-butyric acid = 14.8; n-valeric acid = 68.8; caproic acid - 13.2; water == 1.7. The distillation residue has an average molecular weight of 392 g (determined cryoprespectively). mole-1; acid number = 55.2 / mg KOH / g; saponification number = 284 mg KOH / g; OH is equal to 0.9 wt. In a further variant, 1000 g are taken from the organic layer (organic phase) and rectified on a glass packed laboratory column with a efficiency of 48 theoretical steps, reflux ratio 15: 1, at a pressure of 2.67 kPa. 397.5 g of I fraction with a temperature of 20-86 ° C / 2.67 kPa and 382.5 g of II are obtained. fraction with boiling point 94- 105 ° C / 2.67 kPa. The remainder is 220 g. I. fraction has the following composition (in% by weight): formic acid - 2.76; acetic acid = 5.37; propionic acid = 11.93; n-butyric acid - 32.4; n-valeric acid = 0.6; n-caproic acid - 0.1 and water = 46.9. II. the fraction has this composition (in% by weight): acetic acid = 0.1; propionic acid = 0.1; n-butyric acid = 1.0%; n-valeric acid = 85.8; n-caproic acid = 12.8 and water - 0.2. The distillation residue has an average molecular weight determined by cryoscopy - = 417.2 g. mole-1; acid value = 23.1 mgKOH / g; saponification number = 226 mg KOH / g- Using the 1st fraction as silage agents, similar results are obtained as summarized in Table 1. The results are not impaired by the addition of ammonia up to 0.5 moles per mole of organic acids. . Zasa II. fraction as well as II. 1.24 wt.%, with 0.25 wt. trihydrogenphosphoric acid can be used for the preservation of wet feed grain (barley, wheat). OBJECT 1. A process for preparing a preservative and / or binder based predominantly on C 6 -C 6 carboxylic acids, optionally on the basis of their ammonium salts, characterized in that the aqueous solution is predominantly sodium salt carboxylic acids C1 to Ca, the so-called alkaline water, formed as a by-product of the catalytic oxidation process of cyclohexane to cyclohexanone and / or cyclohexanol, is treated with a mineral acid such as sulfuric acid or trihydrogenphosphoric acid until displacement of the carboxylic acids from their sodium salts from > the organic layer and the aqueous layer are separated, the aqueous layer for application or crystallization and / or drying up to solid salts of sulfuric acid or phosphoric acid and the organic layer, optionally after partial ammonialization, is a preservative and / or or silage, or divided into fractions, wherein the predominant fraction is predominantly VYNA LEZ of C 1 to C 1 carboxylic acids and water is a solubilizing and / or preservative, and a further fraction, predominantly containing valeric acid, capric acid and hydroxy capro is a preservative. 2. The process of claim 1, wherein the aqueous solution of predominantly sodium salt carboxylic acids, the so-called alkaline water, is destroyed by mechanical impurities and insoluble matter prior to treatment with the mineral acid, preferably by filtration, harvesting or centrifugation. 3. A method according to items 1 and 2, characterized in that the organic layer and / or the organic layer separated by a mixture containing 60 to 100% of a mixture of valeric, caproic and hydroxycaproic acid as preservative or fodder silage in quantity 0.2 to 2% by weight, is comfortable with trihydrophosphoric acid admixtures and / or its monoalkyl to tri-alkyl phosphate. Severografia, n. P. Plant 7, Most Price 2,40 Kcs