FI57689C - FRAMEWORK FOR FRAMSTAELLNING AV ROEKNINGSMEDEL - Google Patents

Description

} · * £ *, · | Γβ1. ADVERTISEMENT rn / ftg «Ta l8J (11) UTLÄGGNINGSSKRIFT 3 'OÖ? ^ T ^ (51) Kv.ik.3 / Im.a.3 A 23 L 1/232 ENGLISH I - Fl N LAN D (21) PK * nttlh «lwmu« —P «tenen * eki» lm 750 ^ 33 (B) 17.02.75 (23) Alkupllvl — GIWihMfdag 17.02.75 (41) Tulkit JulklMktl - Bllvtt offwtllg 23.08.75 rekl «« - lh »riltlM (44)» M *. „Ta ** · *. r «._„ „

Patent and registration duty AmMcm utiifd oeh utUkrMtan pubikmd 30.0b. oO

_ (32) (33) (31) ** yyd «tty« tuolkuui — B «Sird priority 22.02.7 ^

Poland Pole (PL ·) + l6900l (71) Instytut PrzemyBiu M ^ snego, ul. Rakowiecka 36, 02-532 Warsaw,

Poland Polen (PL) (72) Janusz Kulesza, Warszawa, Kazimierz Miler, Warszawa, Jerzy PocLlejski, i6d £ Jozef Gora, iödz, Teresa Czajkowski, Warszawa, Zbigniew Kozlowski, Warszawa, Jadwiga Kolska, Κ0Ζ0, Jolanta Stolowska, dz, Zygmunt Rutkowski, Warszawa, Poland Pole (PL) (7 ^) Berggren Oy Ab, (5 * 0 Process for the preparation of a smoking agent - A method for the preparation of rökningsmedel

The present invention relates to a process for the preparation of a smoking agent having flavoring and preservative properties, which, when added to food protein fats, improves their taste and aroma, gives them the properties of smoked products and increases their shelf life and resists their oxidation.

It has long been generally known to provide the properties of products smoked in protein-fat products by directly applying to these products the effect of smoke obtained as a result of incomplete combustion of the cellulosic lignin material. Such a method does produce products with the taste and aroma of smoked nutrients, but at the same time they contain unnecessary and harmful ingredients, in particular nitrogenous bases and certain volatile acids, which give the products in question a foreign taste, as well as carcinogenic hydrocarbons, namely benzopyrene. benzofenatren derivatives.

2 57689

In addition, smoking by smoke on a large industrial scale is a technically cumbersome method, difficult to standardize and automate using continuous manufacturing methods that require expensive equipment and large stocks of certain types of wood necessary to produce the smoke.

The above-mentioned disadvantages and inconveniences mean that conventional smoke-based smoking has increasingly been abandoned and replaced by the so-called smokeless smoking means smoking with added substances which, when added to nutrients, give them taste and aroma characteristics which are more or less similar to those of products smoked by the said classical method, but which do not contain carcinogenic or additive additives. _

Smokers are obtained from products obtained by the decomposing distillation of wood or similar raw materials and are recovered with or without the addition of air. Initially, distillation water that separated during the distillation of wood was mainly used as a raw material, but later distillation tar and smoke formed during the dry distillation of wood were used. There are a number of methods for obtaining smoke flavorings from these raw materials by distillation, extraction, fractionation or a combination of these treatments, with the aim of removing harmful and undesirable constituents and preserving only those compounds or groups of compounds with suitable taste and aroma properties and oxidation. inhibitory and bactericidal effect.

Very high quality standards are required for smokers to meet the basic conditions set by legislation and health for nutrient additives. They must also impart to the nutrients the characteristic taste and odor of smoked products, have an antioxidant and bactericidal effect and must not contain carcinogenic compounds in excess of 1 part by weight per million parts by weight of the nutrient to be treated and must be used in quantities are from about twenty to several hundred parts by weight of said substance per million parts by weight of the product.

Only a few of the known smokers meet the mentioned 3,568689 conditions. Such are smokers obtained in accordance with Polish patent specifications Nos. 49216, 52159 and FI patent 53263. Such substances are obtained using fractional extraction with organic, water-immiscible solvents, preferably with ethyl ether, by extracting the condensed smoke condensate obtained by the decomposing distillation of cellulosic and / or lignin material to which excess air is introduced.

In the method according to FI patent 53263, three usable fractions are separated. The first basic fraction is a fraction containing mainly phenolic compounds with a molecular weight exceeding 140. This fraction can be mixed with the second terpene fraction obtained as the extraction progresses and containing compounds which do not form salt-type compounds in a medium above pH 12, 8, and as a third fraction an acid fraction is obtained which contains lower carboxylic acids and forms the final smoke. However, this method is technically very difficult and laborious and requires complex hardware.

According to the present invention, a smoke agent is prepared by distillation and extraction of distilled tar or smoke condensate obtained by decomposing distillate cellulosic and / or lignin material in an oxygen-free or oxygen-containing gas atmosphere, and the process according to the invention is characterized in that said raw material or preferably the fraction obtained by extraction with organic solvents containing phenols having a molecular weight greater than 140 is extracted with an aqueous solution of a mineral acid, preferably sulfuric acid, to remove organic nitrogen bases, or the substances are mixed with an acid which does not decompose below 250 ° C, preferably orthophosphoric acid with the intention of binding said bases, followed by a two-stage distillation under reduced pressure in an inert gas atmosphere, preferably by adding zinc, aluminum or iron flour, the pressure during the first stage being between 30 and 20 mm Hg, and recovering the first fractions of waste, said fractions containing substances with a boiling point below 110-100 ° C at said pressure, such as water, low molecular weight organic acids, hydrocarbons and 57689

B

other additional substances, while the pressure in the second distillation stage is reduced to not more than 20 mm Hg and polyhydric alcohol is preferably added, followed by recovery of a fraction containing compounds having a boiling point of up to 250 ° C at 20 mm Hg or having a correspondingly lower boiling point at a pressure lower than 20 mm Hg, the fraction of which consists of a smoke agent or a mixture of a smoke agent and a polyhydric alcohol, which mixture is subsequently partitioned by heating to 50-90 ° C to form an alcohol layer and a pure smoke agent layer, and that, if desired, said substance is further subjected to - a selective adsorption treatment by passing it, diluted or undiluted, through an adsorption mass which adsorbs any additional or harmful compounds.

The smokers obtained by the process according to the invention have bactericidal and preservative properties.

The orthophosphoric acid used in the coupling of the organic nitrogen bases simultaneously prevents the condensation-polymerization reactions, in which case these substances remain in the remainder of the distillate, which forms a residue.

The extraction uses an aqueous mineral acid solution having a concentration of 5-20%> 5 ~ 25% by weight based on the weight of the condensate formed by tar or smoke.

The extraction is preferably carried out one or more times with specified amounts of acid at room temperature, after which the upper layer containing organic nitrogen bases is separated to form a residue, while the lower tar layer is washed several times with water and aqueous sodium bicarbonate or saturated aqueous sodium chloride. On the other side of the organic nitrogen bases binding by means of orthophosphoric acid is carried out by mixing the original raw material of 0.5-5 wt -% of 85 ~ 90 $ of acid. Thus, the preliminarily purified feedstock is subjected to a two-stage distillation under reduced pressure in an inert atmosphere, e.g. a nitrogen, argon or carbon dioxide atmosphere, preferably with the addition of 1-10 wt.%, Most preferably 5 wt.%, Zinc, aluminum or iron dust. . The use of such a dust gives a smoky color which is light amber in color, since it prevents the oxidation of the hydroquinone or quinone system. Such dust may be added during the first or second distillation step.

In the first distillation step, carried out at a pressure of 30-20 mm Hg, the pre-distillates are recovered, forming a waste, i.e. a fraction, containing substances with a boiling point below 110-100 ° C. Most of these are low molecular weight organic acids, water, hydrocarbons and other unnecessary substances.

In the second stage of the distillation, the pressure is reduced to not more than 20 mm Hg and a fraction containing compounds having a boiling point of up to 25 ° C at a pressure of 20 mm Hg is recovered. At pressures below 20 mm Hg, compounds with a correspondingly lower boiling point are distilled. This fraction is the final smoke.

The remainder of the above distillation, which is mainly resin and acid, e.g. phosphoric acid, as well as bound organic nitrogen bases, is a technical waste material. It has been found that it is much easier to remove the waste forming the remainder of the distillation from the distillation apparatus if it is diluted with a polyhydric alcohol.

As a result, it is preferable to carry out the second step of the distillation process by extractive distillation at a pressure of up to 20 mm Hg using vapors of polyhydric alcohol, which alcohol also has a beneficial effect on the distillation treatment itself, in which case glycerol is preferably used.

The polyhydric alcohol is mixed with tar, separated from the fraction with a boiling point below 100 ° C at a pressure of 20 mm Hg, as well as with organic nitrogen bases, or in which the nitrogen bases are acid-bound in an amount of 1 to 10 parts by weight of alcohol per 1 part by weight of crude substance, preferably 5 parts of alcohol per 1 part of raw material. From this method a fraction is recovered which always boils at 250 ° C at a pressure of 20 mm Hg or at a corresponding lower temperature at a pressure of less than 20 mm Hg. This fraction, which is a mixture of polyhydric alcohol and smoke compounds, is then heated to 50-90 ° C to automatically separate it into two layers. The upper layer is a smoky agent while the lower layer is a polyhydric alcohol that can be reused in the distillation of the next batch of tar.

Studies have shown that positive results are obtained even if certain modifications of the method are used to obtain the smoking agent according to the invention. According to this modification, the treatment sequence is modified so that the tar and flue condensate from the crude distillation are first distilled by two-stage distillation using the method described above and maintaining the same technical parameters, and only the final distillate containing smoke is removed with organic nitrogen, preferably with sulfuric acid, preferably sulfuric acid. .

The smoking agent obtained according to the invention is a complex mixture of organic compounds containing at least 50% of phenol-type constituents, as well as higher fatty acids, terpene compounds and the like, whereby carcinogenic substances are simultaneously removed from the product.

This substance differs significantly in quality from the typical desired flavor of a smoked nutrient and, when added to protein-fat products, gives them the properties of products that have been smoked by conventional smoking methods and increases their resistance and resistance to oxidation. The yield obtained by the process according to the invention is from about 15 to 40 to 56% by weight, based on the original raw material.

The process according to the invention can also be used for the purification of fractions obtained according to FI patent 53263, in particular for the purification of a fraction containing phenols with a molecular weight greater than 140, with the aim of improving both taste and aroma properties and purity, especially with regard to harmful substances. to obtain the smallest possible amount.

Highly satisfactory quantitative and qualitative results have been obtained by subjecting the above phenol fraction to a further technical treatment consisting of distillation under reduced pressure, preferably in the presence of an undegraded acid at a temperature of up to 250 ° C, especially in the presence of orthophosphoric acid added to bind organic and organic bases. to resist polymerization and condensation events, and / or in the presence of zinc or aluminum dust to resist oxidation.

The distillation treatment is carried out at a pressure not exceeding 20 mm Hg at a temperature of always 200 ° C or correspondingly at a lower temperature of less than 20 mm Hg, in which case the acid is always added 5% by weight and the zinc or aluminum powder 1-5% by weight of the phenol fraction. . Further protection against the possibility of oxidation and improvement in the processing conditions of the process can be achieved by carrying out distillation in an oxygen-free atmosphere. A considerable improvement in the distillation conditions can be obtained by adding 3 to 6 parts by weight of polyhydric alcohol, preferably glycerol, per 1 part by weight of the phenol fraction to the phenol fraction before starting the distillation. The yield of the phenol fraction purified by the distillation method is 60-90 wt. calculated on the weight of the crude anhydrous fraction.

The distillate obtained, after separation from the alcohol, is in the form of a thick yellowish oil and is characterized by a strong taste and aroma and contains only very small amounts of substances harmful to health, in particular carcinogenic substances. Instead of using polyhydric alcohols as additives in the distillation process, it is also possible to use vegetable oils, high-boiling aliphatic hydrocarbons or silicone oils which do not accompany the distillate during distillation. When distilling in a non-acidic medium, e.g. in the presence of a polyhydric alcohol or oil, it is preferable to extract the crude or distilled phenol fraction with a mineral acid such as sulfuric acid in order to remove substances having the nature of organic bases and then wash for neutralization purposes. It has been found that, from both a technical and economic point of view, it is most efficient to carry out the distillation process as a continuous process.

By a similar purification treatment, by distillation under reduced pressure, a third fraction of the smoking agent obtained by the process of F1 patent 53263 can also be treated, which fraction contains - lower carboxylic acids.

In order to increase the removal efficiency of excess and harmful benzopyrene, dibenzoanthracene or other aromatic hydrocarbon type excess and harmful compounds from the smoke, it is treated by selective adsorption by absorption masses such as: activated carbon, high porosity silica gel, sorbents, etc. The process is carried out by first diluting the smoke agent with organic solvents such as lower aliphatic alcohols, dialkyl ethers, halogenated hydrocarbons, etc., or by heating it undiluted to 50-90 ° C and then passing it through a column filled with with a suitable ad sorbent. Per 100 parts by weight of the substance to be treated, 10 to 50 parts by weight of the absorption mass are used, depending on its quality and selective activity. After passing the liquid through an adsorption column, the solvent is removed, if necessary by evaporation under normal vacuum. This gives a purified smoke in the form of a thick, yellowish oil with the aroma of a highly smoked nutrient and a very high purity, especially with regard to carcinogenic compounds.

When preparing a smoking agent according to the invention, a product is obtained which is not only very pure, but also has excellent aromatizing and antioxidant properties. This substance is a concentrate with a very high concentration. When used in nutrients from a few parts by weight to a few hundred parts by weight per million parts by weight of the product, it is necessary to dilute said concentrate with suitable carriers. Full known carriers include, for example, ethyl alcohol, ethylene glycol, glycerol, animal or vegetable fats, table salt, starch, spices, pickle mixtures, water, etc. Depending on the nature of the carrier, said dilution is carried out either by dissolving the concentrate. a cream on a carrier or by impregnating a solid carrier with a concentrate or preparing an emulsion of a concentrate in a carrier. The preservative is diluted to a concentration of a few percent. The product diluted with the carrier is mixed with the nutrient or applied to the surface of the latter using known methods. For example, a solution or emulsion of a few percent of a smoke agent in a low viscosity carrier, with or without added dye, is sprayed onto the surface of the nutrient, preferably using an electrostatic field, after which the carrier evaporates automatically.

The method for obtaining a smoking agent according to the invention is illustrated in more detail by the following examples:

Example I

The tar obtained from the dry distillation of hardwood is subjected to extraction at room temperature using a 10 solution of 10% aqueous sulfuric acid relative to the weight of the original tar. The upper separated aqueous layer, which contains organic nitrogen bases which have a detrimental effect on the aroma of the smoke, is discarded, while the tar layer is washed four times with water and 3% sodium bicarbonate solution until neutral. The initially purified tar is then subjected to fractional distillation under a nitrogen atmosphere after first adding 5% by weight of zinc powder based on the amount of tar. The distillation is carried out under reduced pressure in two stages. First, a fraction of compounds with a boiling point below 100 ° C at a pressure of 20 mm Hg, consisting of a mixture of low molecular weight fatty acids and phenols, as well as hydrocarbons which have a negative effect on the aroma of the smoke, is recovered and discarded. Thereafter, the pressure is always reduced to 10 mm Hg and the fraction having a boiling point below 180 ° C at a pressure of 10 mm Hg and formed by the smoke agent is recovered.

The yield of the smoke thus obtained is always 30% by weight, based on the original tar.

Example II

Tar, which is the condensate of smoke obtained by the decomposing distillation of 10 57689 wood using excess air and from which nitrogen bases and compounds having a boiling point below 100 ° C at 20 mm Hg have been removed as described in Example I, is mixed with four times the amount of glycerol and subjected to extractive distillation under a nitrogen atmosphere not exceeding 20 mm Hg. In this case, a fraction with a boiling point of up to 250 ° C at a pressure of 20 mm Hg is recovered. The distilled mixture of glycerol and smoke-forming compounds is heated to 60 ° C to separate it into two layers. The lower layer is glycerol, while the upper layer is pure smoke. The yield from the treatment is 20 # based on the original raw material.

Example III

To the tar obtained from the decomposing distillation of wood is added 2% by weight of orthophosphoric acid, and this mixture is subjected to a two-stage distillation under a carbon dioxide atmosphere and under reduced pressure. Pre-distillates containing compounds with a boiling point below 110 ° C at 25 mm Hg are collected. These precursors form a mixture of low molecular weight fatty acids, phenols and hydrocarbons and are discarded as waste. After distilling off the pre-distillates, 5% by weight of aluminum powder is added to the residue and the smoke is distilled off in a carbon dioxide atmosphere with a boiling point of up to 250 ° C at 20 mm Hg. The yield of the smoke is the same as in Example I. it is passed at room temperature through a glass column filled with activated carbon. After evaporation of the solvent, the product obtained gives the product in the form of a thick yellow oil with a strong aroma of smoked nutrient. The yield of adsorption treatment is 90 #.

Example IV

The tar formed by the condensate of smoke obtained from the decomposing distillation of wood using excess air is subjected to a two-stage distillation under reduced pressure according to Example II. The distillate obtained from the second step after separation of the glycerol layer is extracted at room temperature with 10% aqueous sulfuric acid used in an amount of 7% by weight, and the upper aqueous fraction containing organic nitrogen bases is discarded as waste. The lower fraction, after washing with water and neutralization, is a pure smoke.

11 57689

Example V

To the crude phenol fraction obtained from the extraction treatment of the smoke condensate with ethyl ether is added aluminum powder in an amount of 5 parts by weight, and the fraction having a boiling point of 96-160 ° C at 10 mm Hg which forms a smoke is distilled off. The yield of the treatment is about 60%. This material is then diluted with dialkyl ether to a 10% solution, which is then passed through a column of glass filled with molecular aluminosilicate sorbent at room temperature. After separation of the filtrate, a pure smoke is obtained from the solvent in the form of a thick yellowish oil with a strong aroma of smoked nutrient. The yield of the adsorption treatment is 90%.

~ Example VI

To the crude phenol fraction obtained from the extraction of the condensate with ethyl ether is added 1 k of 85 k orthophosphoric acid, and after thorough mixing, the distillates with a boiling point of less than 110 ° C at 40 mm Hg are distilled off. 4 k of zinc dust are added to the residue and distillation is continued. The fraction with a boiling point of 100-180 ° C at 10 mm Hg is obtained in the form of a yellow oil with a strong aroma of smoked nutrient. · Treatment »

The yield is about 65%. Example VII

The crude phenol fraction obtained from Example V is extracted with 10 k sulfuric acid using 25%, then washed with aqueous sodium chloride solution until neutral, then anhydrous glycerol is added to 4 parts by weight of glycerol per 1 part by weight of phenol fraction, and distillation is carried out. . In this case - a fraction with a boiling point of 40-166 ° C at a pressure of 10 mm Hg is obtained.

The resulting distillate decomposes into two layers after heating to 60 ° C. A thick light brown oil with a strong aroma of smoked nutrient is separated as the upper layer and is a pure phenolic fraction. The yield from the whole treatment is about 68%.

Claims (8)

57689 A process for the preparation of a smoke agent by distillation and extraction from distilled tar or smoke condensate obtained by the decomposable distillation of cellulose and / or lignin material in an oxygen-free or oxygen-containing atmosphere, characterized in that said raw materials or preferably a fraction obtained by organic solvent extraction contains phenols with a molecular weight of more than 140, is extracted with an aqueous solution of a mineral acid, preferably sulfuric acid, to remove organic nitrogen bases, or the substances are mixed with an acid which does not decompose below 250 ° C, preferably with orthophosphoric acid, to bind said bases, followed by two-stage distillation under reduced pressure in an inert gas atmosphere, preferably by adding zinc, aluminum or iron flour, the pressure during the first stage being between 30 and 20 mm Hg, and recovering the first fractions of waste, said fractions containing substances with a boiling point below 110 to 100 ° C at such pressure, such as water, low-molecular-weight organic acids, hydrocarbons and other auxiliary substances, while the pressure in the second distillation step is reduced to not more than 20 mm Kg and preferably polyhydric alcohol is added, followed by recovering a fraction containing compounds having a boiling point up to 250 ° C at a pressure of 20 rm Kg or a correspondingly lower boiling point at a pressure lower than 20 mm Hg, the fraction of which consists of a smoke agent or a mixture of a smoke agent and a polyhydric alcohol, which mixture follows it is divided by heating to a temperature between 50 and 90 ° C to form an alcohol layer and a layer containing pure smoke, and that said substance is further subjected, if desired, to a selective adsorption treatment by passing it diluted or undiluted through an adsorption mass which adsorbs any excess or harmful compounds. Process according to Claim 1, characterized in that the extraction is carried out at room temperature using an aqueous mineral acid solution having a concentration of 5 to 20%, preferably 10%. 13 57689 Process according to Claim 2, characterized in that the mineral acid is added in an amount of 5 to 25% by weight, based on the amount of tar, preferably 10% by weight. Process according to Claim 1, characterized in that an acid which does not decompose at a temperature below 250 ° C, preferably orthophosphoric acid, is used up to 5% by weight of an acid of 85 to 90%. Process according to Claim 1 or 2, characterized in that zinc, aluminum or iron flour is used in an amount of 1 to 10% by weight, based on the amount of tar fraction, preferably 5% by weight, and in that said powder is added to the first or only second stage of distillation. Process according to Claim 1 or 2, characterized in that the polyhydric alcohol is used in an amount of 1 to 10 parts by weight per 1 part of tar, preferably 5 parts by weight per 1 part of tar. 1. For the purpose of obtaining a genomic extraction and a destination for the distillation of a genomic distillation of a cellulose and / or a lignin extraction with organic solvents from the fractional phenol, a fierce molecular weight of 140, extraction with water-based extraction of minerals, fatty acids, extraction of organic, quaternary or other substances, such as at a temperature of up to 250 ° C, the orthophosphorus temperature of the base gas is reduced to a minimum under reduced pressure in an inert gas atmosphere, the zinc, aluminum or lower temperature of the solid state, 30 to 30 mm Hg, and the color of the fractions obtained from the water product r uppsamlas, varvid de nämnda fractionation innehäller subs-danser med en kokpunkt below 110-100 ° C vid nämnda tryck, säsom vatten, lägmolekylära, organiska syror, kolväten och andra bal-