HU188438B - Process for production of extracts of mineral water and medicinal water and cosmetics containing thereof - Google Patents

Abstract

The present invention relates to a process for producing mineral and medicinal water extracts. The process according to the invention is characterized in that a) a flocculating agent is added at a pH of 4.9 to 5.2 for mineral and medicinal water, dissolved and dissolved in a minimal amount of dilute base solution; or b) mineral and medicinal water to bind macromolecular organic materials. the resin is eluted with a solution containing chloride or hydroxyl ions, and, if desired, an antioxidant and / or preservative and / or flavoring agent is added to the resulting extract, and / or, if desired, a humic acid pH = 1 after desalting, It is precipitated by acidification to 0 and / or precipitated from the residual solution by eluting with fulvic acid on an ion exchange resin and eluting with a hydroxyl or chloride ion eluent or by flocculation. The above extracts can also be prepared from mineral and medicinal sludge by extraction with alkali metal hydroxide, hydrogen carbonate or carbonate.

Description

The present invention relates to a medicinal water extract, a mineral water extract and to pharmaceutical and cosmetic compositions containing them.

More particularly, the present invention relates to biologically active humic substances, proteins, peptides, amino acids, polysaccharides, uronic acids, nucleic acid components, estrogenic substances, organic complexed elements and trace elements, which are characteristic of medicinal waters and mineral waters, and optionally containing the characteristic fragrances. for the production of medicinal and mineral water extracts. These extracts can be used directly for therapeutic purposes and as a pharmaceutical ingredient, as well as as a cosmetic additive. The invention also relates to cosmetics containing medicinal water extracts.

According to previous knowledge, the biological effects of medicinal and mineral waters were based entirely on the quality and quantity of inorganic components. This claim was refuted when, using ordinary water, the same concentration of inorganic components as the medicinal water was made by weighing the inorganic components and the expected therapeutic effect was not achieved. (Minerals and Medicinal Waters of Hungary. Edited by Schulhof O. Akadémiai Kiadó, Budapest, p. 923.)

Organic matter, which is present in medicinal waters and mineral waters in relatively smaller amounts than the inorganic components, is the decisive factor in biological activity and thus in the therapeutic effect. Metals and trace elements, once bound to organic matter, become complex and can be used beneficially by the human body. Recent research has shown that it is not the absolute concentration of trace elements that is decisive for biological activity, but the proportion of total concentration complexed with organic matter. The most important complexing substances in water and trace elements, water soluble humic substances are fulvic acid and humic acid. (Florence T.M .: The Specification of Trace Elements in Waters. Talanta 29, 345-363

1982. Stum W.: Aquatic Chemistry. Wiley Interschience New York, 1970, p. 282) Fumic acids and humic acids are humic substances of indeterminate composition, with lower or higher molecular weights, and more or less soluble in water.

Water-soluble humic substances exert their therapeutic effects not only by complexed trace elements but also by their very active biologically active organic components which bind to the peripheral part of their molecules. Among the hydrolysis products of the peripheral region, peptides, uronic acids, polysaccharides, oestrogenic agents, nucleic acid components, glycosides and most naturally occurring amino acids, including the physiologically .: Z. Pflanzenerváhr Düng. Bedenk 96, 11-34 1962).

Water-soluble humic substances have been found to be effective in the physiological examination of therapeutic mud.

G. Csajághy and E. Reisz produced press liquids from various medicinal mud. According to their tests, their healing effect was dependent on the dissolved organic matter content (water soluble humic matter content) of the juice. (Csajághy G. Reisz, E. et al., Military Medical Review 6, 8 (1954). Austrian and German researchers have established in medical procedures that brown, high humic water with a high organic content can be used more effectively for therapeutic purposes than medical mud). In the same indications as medicinal waters, no suitable method for the direct extraction of humic substances from medicinal or mineral waters is known. The barium-containing concentrated humic substances, according to the researchers, can be used in hospitals, sanatoriums, The vaginal irrigations performed with these have also been shown to be very effective and have been used successfully for chronic musculoskeletal disorders, chronic genital disorders in women, certain neurological disorders and traumatic events. for the treatment of gingivitis and in all medical conditions where medicinal water is indicated as drinking cure for eg: cataract and ulcerative processes of the intestinal mucosa, colitis, gallbladder liver disease, kidney stone, chronic pyelitis, bronchitis, chronic pruritus, J). J.: Spinger Verlag. Wien 1957, Kowarschik J .: Die österreichische Moorforschung 1956 8, Stöber O: Die Neydhaertiger Moor-Trink Kur Wels 1957)

Their successful gynecological application is due to their oestrogenic substance content. The presence of oestrogenic substances in medicinal waters containing "peaty" or humic substances has been confirmed by several researchers. (Gierhake E., Weherfritz E.: Dtsch. Med. Wschr. 62, 350 (1936). Ascheim-Hohlweg: Dtsch. Med. Wschr. 59, 12-14. (1933). Munteau N .: Dtsch. Med. Wscht. 96, 110 (1957). Straub, J., Hidr. Journal 3-4, 156 (1954).

The therapeutic effect of the two major components of water-soluble humic substances, fulvic acids and humic acids, has been widely observed and reported in numerous papers. T. Béres and King I. of SOTE Medicine. Institute researchers have found that fulvic acids have a detoxifying and liver-protecting effect. Fulvic acids have been found to be able to protect against the toxic effects of killer cane and carbon tetrachloride. This was confirmed by the histological picture of the liver.

Oral doses of fulvic acid used in human medicine are 0.20 g in pro-gastric, gastrointestinal, bile and liver diseases. At the above doses, fulvic acids increase appetite, and after 8 to 10 daily doses relieve stomach cramps and pains. In acute gastroenteritis, diarrhea is eliminated within hours. They regulate dyspepsic stools and normalize the production of stomach acid: they reduce the production of increased acid in the case of hyperacidity, and increase the production of reduced acid in the case of hypoacidity. In chronic hepatitis, cirrhosis with water retention, diuresis is initiated. SOTE and

188 438

Fulvic acid is a completely atoxic substance, according to research conducted at the SZOTE Institute of Pharmacy and the National Veterinary Institute. For test animals (mouse, rat, rabbit, guinea pig, dog), in a 1% solution administered parenterally or orally at 10 mg / kg. quantity, without toxic or other symptoms. (Béres T., Kabdebo S., Kovács F., Nemeséri L. ^ Székely

A., and Vizy L .: Studies on the therapeutic use of fulvic acid with particular regard to their hepatic protective effects. Journal of Hungarian Veterinarians / 7, 351 (1957).

Fulvic acids of various origins have a fungistatic effect on pathogenic skin fungi, even at very high dilutions. Thus, among others, Epidermophyton, Kaufman - Wolf, and Candida albicans are effective at 1 in 1 dilution. (T. Béres and E. Flórián: Determination of flulic acids by their fungistatic action. Agrochemistry and Soil Science 6, 163 (1957). SOTE and National Institute of Dermatology and Genetics.

The beneficial utilization of humic acid-bound elements and trace elements in the body was reported by B. Lakatos and M. Bedő. (Administration of Tnicro and Macro Elements to Vertabrates with the Aid of Peat and Peat Humic Acids. International Peat Sympsium. Gdansk 8-12 Sep (1974)).

The virucidal action of humates in water has been described by Schultz and Thil et al. (Antiviral Properties of Humic Acids. Dt. Tierarztl. Wschr. 69, 613 (1962). Zbl. Bakt. Hyg. I Abt. Őrig. A 239, 304-321 (1977)).

Despite the many beneficial therapeutic effects, the widespread diffusion of fulvic and humic acids in human medicine has been limited by the fact that so far no suitable starting material has been found which allows the production of water-soluble humic substances of the same quality and guaranteed for a long time. The terms humic acid and fulvic acid do not refer to a series of specific compounds of similar structure, but to a macromolecular substance association in which a large number and variety of organic molecule units are linked to each other and to inorganic components by chemical and partly intermolecular forces. Therefore, the composition of humic acid and fulvic acid always depends on the quality of the raw material source and the conditions under which it is formed. A completely different composition of marine, plant and animal acid from marine, plant and animal fauna, formed by the presence of biologically active components in marine, plant and animal fauna, formed in surface water or near soil, under biosphere conditions or transformed into deep water at high pressure and temperature. . The deep-humic and fulvic acids, when dissolved in water, are saturated with trace elements and highly biologically active organic substances in the peripheral part of their molecules, when in contact with various minerals and marine substances. Plate peat has been attempted to produce humic and fulvic acid from peat soil but, due to the foregoing, is far below the physiological value of humic substances found in medicinal and mineral waters, and is difficult to extract, extract, and remove many solids. equipment requires large investments. (Tank H.: Soil. Sci. 6, 351 (1978). Banerjee S. K. and Mukkherjee S. K.: Indian J. Appl. Chem. 34, 171 (1971)).

French Patent No. 2,096,845 describes the preparation of a water-soluble powder from mineral waters, which is first partially evaporated and then spray-dried. A spray drying process is also described in U.S. Patent No. 3,817,308, wherein a water-soluble additive is added to the mineral and medicinal water prior to spray drying. A common disadvantage of these processes is that spray drying requires considerable energy.

According to US Patent No. 338,848, humic acids are prepared by binding mineral and medicinal water on a cellulose anion exchanger, eluting with 1.5 to 2.0% sodium hydroxide, and then binding the alkali content in ethanol on a cation exchanger. DEAEcellulose and / or triethylaminoethylcellulose are used as anion exchangers and KB4 and KV23 resins are used as cation exchangers. U.S. Patent No. 338,849 also discloses the recovery of humic acids by anion exchange of mineral water or medicinal water, elution with increasing concentration of sodium hydroxide followed by 50% sulfuric acid treatment and centrifugation. The humic acids are then bound again on an anion exchanger and eluted with increasing concentrations of aqueous acetone containing sulfuric acid to recover the fulvic acid. A common disadvantage of these procedures is that they do not provide a product of sufficient purity, since further reworking is required. In addition, the columns are difficult to handle.

It is an object of the present invention to provide an economical and inexpensive process for recovering high biological value organic and trace elements macronolecular polysaccharides from medicinal waters and mineral waters for use in hospitals, sanatoriums, other health care facilities and patients' homes for medical purposes. can be used as a base material and as a cosmetic.

According to the invention, the flocculating agent is added to a mineral water at a pH of 4.9-5.3, the flocculated solution is settled and dissolved in a minimal amount of dilute basic solution.

In this case, the present invention is based on the discovery that most of the thermal and mineral waters can obtain a macromolecular complex containing biologically active organic substances and trace elements having a favorable composition, the composition of which is typical of the particular thermal water or mineral water.

Preferred flocculants for use in the above process are salts containing trivalent cations, preferably aluminum and iron (III) salts. The process preferably uses aluminum sulfate, most preferably Ak (SO ₄ ) · 18 H ₂ O.

After settling, the precipitate is dissolved in a minimal amount of dilute basic solution. For this purpose, the most-31

Sodium hydroxide, preferably 0.1 to 1% by weight, preferably 0.5% by weight, is more suitable.

According to a preferred embodiment of the above process according to the invention, the pH of the medicinal or mineral water collected at the extraction temperature in a concrete basin is adjusted to 4.9-5.3 by the addition of concentrated sulfuric acid and 170 mg Al ₂ (SO ₄ ) per liter. ₃ · 18H ₂ Add O while stirring. A few hours after dosing, when coagulation, flocculation, and settling of colloid-sized organic matter has occurred, the water is drained from the precipitate. The wet precipitate is placed on trays, spread over a layer thickness of 2 cm at 50 ° C, preferably on a heat exchanger or radiator, operated with thermal water, under a stream of nitrogen until it becomes highly porous. After powdering, dissolve in 0.5% (v / v) sodium hydroxide solution corresponding to its solubility.

The faster the precipitation is, the higher the temperature of the starting material, the medicinal water and the mineral water. Precipitation at or near the extraction temperature is advantageous because, at this elevated temperature, the medicinal water and the mineral water contain only insignificant amounts of oxygen, so that the organic materials having high biological activity do not suffer from oxidative degradation and their activity remains unchanged. Degradation is observed by measuring the precipitated material E ₄ / E _e . (This quotient is the quotient of the extinctions at 465 nm and 665 nm). Its value is inversely proportional to the molecular size of the recovered material (Tank KH and Giddens JE, Geoderma, 8, 221-229 (1971)). The ratio was always higher in the case of coagulation and precipitation from chilled medicinal water and mineral water. This fact is in agreement with J. Diri, Mirgay, E. Reisz and Schulhof, Physiotherapy, Balneotherapy, Budapest, Medicina Publishing House, 1963, p. stating that the curative effect of medicinal water and mineral water and the so-called its catalytic effect decreases rapidly after cooling.

Alternatively, the present invention may be carried out by passing mineral and medicinal water through a macromolecular ion exchange resin capable of binding organic materials and then eluting the resin with a solution containing chloride ions.

A resin which binds a complex containing biologically active organic substances and trace elements may be used for the process. Examples of such resins are Amberlite IRA-958 or XAD2, as well as AT-600, AT-400 and XAD-200, which preferably have a chloride cycle. Amberlite IRA-400, 425, 904, 402, and 458 and XE-270 resins, which are preferably used in the hydroxyl cycle, are also suitable for such purposes.

After curing, the resin is eluted with as little chloride chloride solution as possible. Sodium chloride solution is preferred for elution. For example, 10% w / v sodium chloride solution is preferably used as eluent. However, dilute sodium carbonate solution may also be used.

In the above process, not only the organic material of colloidal molecular size is passed into the eluate, but also some smaller molecule organic material which is undesirable. ^'5 such as phenol or polycyclic aromatic hydrocarbons. It depends on the amount of thermal and mineral composition used, but when used in dilution with a concentration in general they will definitely smaller than the original one was ¹⁰ ye spa and mineral water. If the concentration of these undesirable organic materials is significant, it is advisable to separate the colloidal size organic material from the eluate. In such a case, it i procedure as in the above flocculation procedure, the eluate was applied ¹⁵ itself as the starting material, then adding the flocculant after the deposition and redissolve the precipitate.

The examination of the product has been found that in this way the polycyclic aromatic hydrocarbon, examples ²⁰ Daul fluoranthene, 3,4-benz-fluoranthene, 3,4-benzpyrene, etc. concentrations, the combined amount of which is limited to 0.20 pg / l by the WHO in drinking and bathing waters, is significantly lower in this extract.

²⁵ The invention relates also recovering inorganic salt content of the mineral water or mineral water.

Despite the fact that the mineral or medicinal water final desired therapeutic factor for gyógyhuminanyag, certain mineral or thermal water ²⁰ tos may be the removal of inorganic salts in the extract.

In the case of extraction of inorganic salts into the extract at the same time as the humus, proceed as follows:

After gyógyhuminokat as above ³⁵ was recovered from the thermal water or mineral water, the water is cooled, preferably cooled to 35 'when hotter. The medicinal water or mineral water still containing the mineral salts is passed to a column of cation exchange resin in Na ⁺ form. In lyatva ⁴⁰ with flow of the medicinal water or mineral water, salts bind cations, anions leave in the form of sodium salts, the cation exchange column. The brine from the cation exchange resin column is then passed onto an anion exchange column in the form of CI. Passing through the ⁴⁵ anion exchange columns, the anions of the medicinal water and the mineral water are bound, and the NaCl is removed with the effluent. Measuring the drain water from the columns ⁵⁰ Total hardness and alkalinity of flow during the thermal water or mineral cation and anion exchange column, and when it is detected on the basis thereof, the resin columns capacity is exhausted, stopping the flow. At this point, the total mineral salt content of the healing water or mineral water flowing through the resin columns is bound to the cationic and anionic columns, in the form of cations and anions.

The recovery of the medicinal and mineral water salts on the cation and anion exchange columns is carried out as follows:

The NaCl content of the humus solution obtained from the resin column prepared as described above with 10% NaCl is adjusted to 100 g / l so that the humic matter content corresponds to the amount of medicinal water or mineral65 water flowing through the cation or anion exchanger. With this solution

188 438 recover the cured and anion exchange columns of the cured and mineral water salts by pouring it on the anion exchanger, and as it flows through, the Na ⁺ cations of the humus extract are exchanged for the original cations of the curing and mineral water, used to regenerate the anion exchange column, flowing through it, Cl-ion

- instead of the anions that already existed in the medicinal water or the mineral water enter the solution of the humic acid. When draining from the anion exchange column, AgNOO solution is spiked with chloride when Cl appears in the effluent solution, so that enough of the original Cl content of the total amount of medicinal or mineral water flowing through the apparatus is preferably present in the effluent.

Alternatively, to recover the salt water and mineral water trapped on the cation exchange and anion exchange column, a 10 percent NaCl solution is passed through the cation exchange column as if regenerating the column, and the cation exchanger and Na ⁺ and then passing the solution through the anion exchange, the anions and mineral water anions also go into solution, so that the solution draining from the anion exchange contains all the mineral salts of the medicinal and mineral water. Again, the appearance of Cl · ions in the saline solution flowing from the anion exchanger is monitored, and enough Cl ions are added to the saline solution so that the original Cl content of the medicinal or mineral water flowing through the equipment is present. However, regeneration with humus solution is more advantageous since the NaCl content in the humus extract can then be used to extract the mineral salts.

The cationic and anionic exchange resins used in the extraction of inorganic salts of medicinal or mineral water must comply with the health standards for substances used in food technology.

The inorganic saline solutions of the medicinal water and the mineral water obtained as described above may be preserved together with the extracts of the humus as described for the extracts of humus.

Alternatively, the medicinal water and mineral water extracts of the present invention can be prepared from medicinal or mineral water sludges. In these, the biologically active biopolymer is an organic-inorganic material association which is present in a water-insoluble macromolecular form.

According to the process of the invention, these bioactive substances are extracted in their native form with a dilute aqueous solution of alkali metal hydroxides or alkali metal salts. Preferably, a dilute aqueous solution of sodium hydroxide, potassium hydroxide, sodium bicarbonate, sodium carbonate is used. In order to avoid peptization or degradation, the concentration of the solutions is preferably from 0.12 to 0.50 mol / liter. For example, the use of a 0.125 M sodium hydroxide solution enters native "proteohumates", whose valuable polypeptides, amino acids and proteins increase the biological effectiveness of the extract.

The extraction is conveniently carried out in a plastic or plastic-coated container. Dried or wet sludge from 10 to 20-fold amount, preferably 0.125 mol / liter concentration of alkali metal hydroxide ^5, alkali metal hydrogen carbonate, and extracted with an alkali metal carbonate solution, preferably for 4-8 hours, during some time, preferably 10- 10 minutes mixing. After extraction, the slurry was allowed to settle overnight, then the extract was separated and filtered. It is advisable to repeat the extraction with the sludge residue once more and combine the extracts.

Hereinafter, the extract thus obtained can be used directly, or it can be made into a concentrate by the methods described above.

The extract obtained in the above processes can also be used directly for therapeutic purposes or as a pharmaceutical raw material or as an ingredient in cosmetics. If also very suitable for pharmaceutical cerium lókra ²⁰ Preparation of humic acid target, the extract is desalted, for example by passage through an ion exchange resin, and the pH of the eluate is acidified to pH 1.0. Acidification causes the humic acid to precipitate and be separated. The fulvic acid remaining in the solution, which is also therapeutically advantageous, is conveniently prepared by binding to an ion exchange resin such as a resin as described above, preferably XAD-2 resin, and then eluting with, for example, sodium hydroxide solution. For therapeutic purposes, the antioxidant and / or preservative and / or flavoring agent commonly used in the preparation of medicaments is added to the extract obtained and optionally to the humic or fulvic acid obtained. Preferably, the antioxidant35 is tartaric acid and, for example, nipagin A as a preservative. If the healing water or mineral water has a characteristic strong odor, then the fragrance is flavored with its own odorant, if it is not characteristic and strong enough, ⁴⁰ other substances such as menthol or ethyl acetate, etc. employed.

According to the invention, the odorant can be produced by applying a portion of the starting medicinal water, e.g. 1/10 is distilled at 100 to 119 ° C. The first fraction distilled at this temperature contains the odor of the whole amount of the medicinal water.

The present invention also relates to cosmetics which contain medicinal water extracts and additives commonly used in the preparation of cosmetics. Cosmetics may include, for example, soap, shampoo, anti-rheumatic ointment, lotion, antifungal ointment, vaginal lotion, anti-herpes gel, toothpaste, mouthwash, lotion, chewing gum, and the like. shape.

Of course, the medicinal water extracts of the present invention may also be used for therapeutic purposes. For this purpose, the medicinal water and mineral extracts may conveniently be marketed in plastic bottles of 500, 1000 and 2000 ml. Before use, the extract should preferably be diluted with potable water, free from active chlorine-free water, at least to the original volume.

Extracts are excellent for herbal dehydration, vaginal inflammation and various fungi.

-5188 438 for the treatment of gastrointestinal infections and internally for gastric ulcer, hyperacidity and lipoacidia. Certain medicinal water extracts have liver protection in the event of intoxication and promote wound healing.

During the analysis of the products obtained by the method according to the invention, I found that a significant part of the trace elements and elements present in medicinal water and mineral water passes into the medicinal water or mineral water extract in a very favorable proportion when bound to colloidal molecular size organic substances. Organic complexation changes the effect of elements and trace elements both qualitatively and quantitatively. The biological activity of organic complexed elements and trace elements is orders of magnitude higher than that of inorganic bonds. It is known that complex-bonded Fe in the blood heme is one thousand times more potent, and complex-linked Fe in catalase is tens of billions of times more potent than simple Fe-ions. Similar data are available for J, Cu, Mn and K.

the extract obtained from various sources of medicinal water and mineral water according to the invention contains significant amounts of J, Fe, Cu, Co, Mn and K. Quantities are listed in the examples based on the analysis data. The listed elements can be detected in the precipitate washed 3 times with distilled water after destruction. It is surprising that we can detect Fe and Cu in extracts of curative water and mineral water where these cannot be detected in the original curative water or mineral water. The co-presence of Fe, Cu and Co is of great importance in promoting hematopoiesis. Iodine, which is bound to colloidal macromolecule-sized organic matter, is considered to be important in the treatment of vascular diseases such as arteriosclerosis, hypertension, female genitalia, and activation of the immune system through the adrenal glands. These effects are, of course, only complementary to the main component, the curative effects of the dissolved humic substances.

The main advantages of the process according to the invention are as follows:

a) By making better use of existing tools (baths not used in autumn, winter and spring, etc.), it will be possible to utilize the medicinal and mineral water resources more efficiently, and to produce high-therapeutic products.

(b) Due to the simplicity of the procedure, it does not require significant investment This is especially important if there is no suitable pond for obtaining natural sludge. Due to the slowness of sludge formation and the more concentrated active ingredient content of the product, the method of the present invention may also be advantageously used by spa companies having ponds. By producing the product, it is possible to employ seasonal workers throughout the year.

c) The humic substances from different locations are not of the same composition, but the composition of macromolecular organic and inorganic materials varies widely depending on the place of origin and the conditions of formation, and thus their therapeutic effect is very different depending on the place of origin. The '

The large number of qualitative and quantitative combinations of composition can result in very different therapeutic effects. Thus, the varied composition of medicinal water and mineral water extracts provides greater opportunity for users to select the most effective for each disease.

d) Medicinal waters are very suitable raw materials for the production of water-soluble humic substances for medical purposes, since they can be used for a long time to produce products of the same quality and of the same biological activity.

No special health judgment is required for the use of the medicinal water extract or the mineral water extract if the original medicinal water or mineral water has been judged to be of acceptable quality for public health. This is possible because before use the medicinal water or mineral water extract must be added to at least as much drinking water-quality active chlorine-free water as the extract obtained from the original medicinal water or mineral water. Thus, any toxic components that may be present may not be present in higher concentrations than in the original medicinal or mineral water.

(g) Extracts may be obtained from any medicinal or mineral water, preferably with a water soluble humic content of more than 10 mg / l.

The following examples illustrate the process of the invention in detail:

Example 1

In a 25m ³ concrete pool disinfected, washed and covered with Urex synthetic resin (Budalakk), 20 m ³ , 73 'C medicinal water is released. To the warm medicinal water at pH 8.5 is added 18 liters of pharma- ceutical sulfuric acid, as determined in the preliminary experiments, so that the pH is in the range of 4.9-5.3. After confirming the pH of these samples from several points in the basin, 3400 g of pharma- ceutical grade A1 ₂ (SO ₄ ) ₃ · 18 H ₂ O in freshly prepared 50 g / 1000 ml solution are added with vigorous stirring. Coagulation of colloidal-sized organic materials begins immediately and flocculation can be observed within 10 minutes. Within 4 hours, precipitation and product settling are complete. The precipitated material is drained of water and the precipitate collected is collected in plastic buckets. The aqueous precipitate is poured into aluminum trays, with a thickness of two centimeters on the trays. The precipitate was dried on 50 ° C heat exchangers or radiators or radiators heated with nitrogen to cover the trays with polyethylene foil. When the material has dried so that it can be dusted well, place it in a porcelain mortar and measure. The resulting 1400 g of powdered product is dissolved in 280 L of 5 g / 1000 ml of NaOH. The solution was filtered and dissolved in 140 g of tartaric acid as an antioxidant. Then, 1000 g of methanol and 7 liters of ethyl acetate in which are added are added

188,438 were previously dissolved in 280 g of nipagin A. When used, add 100 ml of medicinal water extract to 20 liters of 36C water free of chlorine.

Example 2

1400 g of the powdered product obtained in Example 1 are dissolved in 256.5 liters of 5 g / 1000 ml of NaOH. Meanwhile, 290 liters of original healing water yields 29 liters of distillate on a copper distillation apparatus, distilling at 117'C. The 29 liters of distillate containing the characteristic odors of 290 liters of original healing water are added to the product solution. In a product solution containing the characteristic odorants, 140 g of tartaric acid is dissolved as an antioxidant, and 2.5 liters of solutio conservans are added for preservation. (Formula II Normales V. Medicine Publishing House Budapest, 1967, p. 442)

Example 3

1400 g of the dried and powdered product obtained according to the procedure of Example 1 were dissolved in 280 L of 5 g / L NaOH in a 300 L plastic tub. After dissolution, filter through a plastic filter bag with a filter frame. Adjust the pH of the filtered solution to 1.0 by adding 5100 ml of concentrated H ₂ SO _{4 as} determined in preliminary experiments. The humic acids begin to precipitate immediately and settle within one hour. The supernatant is aspirated and the precipitated coffee-brown precipitate is filtered through a medium pore size plastic filter and dried at 50 ° C under a stream of polyethylene under nitrogen. After drying, 196 g of a dark brown powdered humic acid are obtained.

The supernatant, pH 1.0, was passed through a 15-liter hydrated Amberlite IRA XAD-2 resin (replaceable with Varion ΑΤ-400) in a DH-15 HNA column (April 4, Mechanical Engineering, Nagykanizsa). liters per minute. The bound fulvic acid is eluted with 40 liters of 10 g / l Na ₂ CO ₃ solution. The eluate was passed through a DHL-15 HNA column packed with 14 L Varion KSE resin in H ^{+ to} remove sodium, at a rate of 2 L / min, then concentrated and dried at 50 ° C. The yield was 629 g of amorphous brown fulvic acid.

EXAMPLE 4 Therapeutic water (m ³ , 73 'C) was passed from a steel buffer tank at a rate of 11 liters per minute onto 77.9 liters of Amberlite 1RA-958 chloride resin placed in a 31.5 cm diameter steel cylinder. (Can be replaced with Varion ΑΤ-400 resin).

After the indicated volume was eluted, 300 liters of 100 g / l NaCl solution were eluted at 2.5 liters / minute by dissolving the first colorless 20 liters of eluate. To 280 liters of dark brown eluate is added 140 g of tartaric acid as an antioxidant. 1000 g of menthol and 7 liters of ethyl acetate, previously dissolved in 290 g of nipagin-A, are added to the solution. In typical strong odor substance and mineral water, mineral water or the eluate is described in Example 2 to be flavored water by the original ^five recovered odor substances.

Example ⁵ The pH of 280 liters of eluate obtained as described in Example 4 was adjusted to 4.9-5.3 by the addition of 1500 ml of concentrated sulfuric acid as determined in preliminary experiments. Then, to the eluate, with vigorous stirring was added 3400 g of ¹⁵ Al2 (SO4) ₃ · 18H ₂ O as a solution with a concentration 300 g / l. Colloidal organic matter coagulation begins immediately and sedimentation is completed within 4 hours. As used herein, the precipitate as described in Example 1 to ²⁰ are processed. The amount of product recovered and dried at 50 ° C was 1519 g.

Example 6 25

To 280 liters of eluate obtained in Example 4 was added 2890 ml of concentrated sulfuric acid as determined in preliminary experiments to bring the solution to pH 1.0. It was allowed to coagulate the humic acid and ₃₀ settle. Hereinafter, humic acid and fulvic acid are isolated as described in Example 3. Yield: 119 g of humic acid

990 g fulvic acid.

Product analytical data:

Samples directly precipitated from the medicinal water or precipitated from the eluate of the medicinal water are washed with hundreds of volumes of distilled water and dried at 50 ° C to a degree of porosity. The samples were analyzed for polycyclic aromatic hydrocarbon and iodine content in the ₄₀ Water Hygiene Laboratories of the National Institute of Public Health using the currently valid standard methods. Elemental analysis is performed by Fe. Mn, Cu, Co and K determination was performed on a Perkin-Elmer atomic absorption spectrophotometer and the flame photometer Zeiss Veszprém Chemical University Department of Analytical ₄₅ sulfur.

It was washed immediately with distilled water, which was drained from the medicinal water. Dried at 50 'C The medicinal water was drained out of the cluate. washed with distilled water Dried at 50 'C product ι: ₄ i; " 4:10 6:30 C: 44.05 ,, 44.11% H: 5.75% 5.25% N 1.63% 2.50% I: 10.51 mg / 100 g (measured after digestion) 11.91 mg / 100 g (measured after digestion) Fe: 757.10 mg / 100 g (measured after digestion) 510.10 mg / 100 g (measured after digestion) Mn: 3.21 mg / 100 g (after digestion measured) 1.19 mg / 100 g (after digestion) measured) Cu: 68.52 mg / 100 g (after digestion measured) 65.72 mg / 100 g (after digestion measured)

-7188438

Direct The healing water from the medicinal water eluate precipitated, distilled precipitated, distilled washed with water. washed with water Dried at 50 'C Dried at 50 'C product product Co: 11.62 mg / 100 3.52 mg / 100 (after destruction (after destruction measured) measured) Fluoranthene: 0 pg / L o gg / i 3,4-Benzofluoranthene: 0 pg / L 0 gg / l 3,4-Benzpyrene: 0 pg / L 0 gg / l 1,12-Benzperylene: 0 pg / L 0 gg / l 1,12-Benzofluoranthene: 0 pg / L 0 gg / l Indenopyrene: 0 pg / L 0PG / l Pyrene: 0 gg / l o Bg / I Perylene: 0 pg / L 0 gg / l

The analyzed medicinal water extracts were obtained from the water of the Gyula spa water well, which has a total polycyclic aromatic hydrocarbon content of 124 gg / l, which mainly contains fluoranthene, 20 pyrene and perylene. The Kober reaction revealed the presence of oestrogenic substances. The Cober reaction is positive for products obtained from medicinal water and eluate as well. The Kober reaction is known to be specific for natural oestrogenic substances. (Sam Frankéi: Grand, Clin. Foot. Methods and Diagnosis. Vol. 1. Saint Louis The C.V. Mosby Company 1970. · p. 225)

Example 7

In Example 4, the amberlite IRA-958 resin column and thermal water, up to a temperature of 35 ° C, are cation exchanged and subsequently anion exchanged at the Nagykanizsa Precision Mechanical Company's D-7 DC complete desalination plant. The cation exchange column of the equipment is Varion KSE and the anion exchange column is Varion ADE. The resin columns are prepared with 100 g / l NaCl.

During the thermal water or mineral water to flow into the resin column of ⁴⁵ columns interest pacitásának depletion monitored drain from the columns mineral water or mineral water Total hardness and alkalinity of m measurements. The capacity of the cation exchanger is considered to be exhausted if the concentration of CaO in the effluent water and mineral water ⁵⁰ is greater than 0.4 mval / l. The capacity of the anion exchange column is considered to be exhausted when the m-alkalinity is 1 mval / l in the effluent or mineral water flowing from it. When the cation and anion exchange columns ⁵ TOWING capacity is exhausted, it is removed by the mineral water or mineral water to flow through, and bound ingest salts as follows:

The NaCl content of Example 4 humus extract containing 405 l of NaCl was added to 100 g / l at a concentration of ⁶⁰ . This solution was passed to a depleted capacity cation exchange column at 12 L / min, and then 285 L of brine from the cation exchanger was passed through an anion exchange column at 8 L / min. For the final period of flow, the presence of Cl'-ions in the test tube is monitored using 0.1 μ AgNO ₃ reagent and

after they have appeared in the effluent and mineral water, 12.91 more humus extract extract solutions are passed through the anion exchange column. The thus obtained 81, 2981 humus solution of saline is combined ';

the remaining 1 107, only current flowing through ^one R cation mineral salt solution: such as - ultimately - one 405 f _{(gyógyhuminos} mineral salt solution containing t all salts of mineral or medicinal water contain za · s. |.

The saline concentration in our example is Gyula p j

No. I extract from the water of a medicinal well; i

90.7 g / l. )

Extraction is completely 100 g / l ζ as described above.

This can also be done with a concentrated NaCl solution: in this case, the very valuable hormone is not contained in the mineral salt extract. %

Example 8

In a 2.5 m ³ plastic bath, 1700 liters of sodium hydroxide solution (0.125 mol / liter) was prepared. 150 kg of dry powdered medicinal mud are added to the solution with vigorous stirring. Stirring was continued for a further 10 minutes, followed by extraction for 6 hours with vigorous stirring of the contents of the vessel once every hour for 10 minutes. The slurry was allowed to stand overnight, then the supernatant was pumped and filtered through a pad of glass wool. The slurry was extracted once more with the same amount of sodium hydroxide solution and the two filtrates were combined. It is used in the same manner as in the extract prepared in Example 4, or the extract can be concentrated by the procedure given in Example 4.

Claims (10)

Patent claims A process for the preparation of mineral and medicinal water extracts, characterized in that: (a) adding a flocculating agent to a mineral or medicinal water at a pH of 4,9 to 5,3, settling it and dissolving it in a minimal amount of a dilute basic solution, or b) the mineral and medicinal water is passed through a macromolecular ion exchange resin capable of binding organic matter, and the resin is eluted with a solution containing chloride ions, and if desired, an antioxidant and / or preservative and / or flavor is added to the extract; In the latter case, after desalting, the humic acid is precipitated by acidification to pH 1.0 and / or from the residual solution, fulvic acid is bound to an ion exchange resin and eluted with an eluent containing hydroxy or chloride ion or flocculated. (Priority: March 22, 1983) 2. The process of claim 1 wherein the flocculant is Al ₂ (SO ₄ ) ₃ · 18 H ₂ O. (Priority: March 22, 1983) 188 438 Process according to claim 1 or 2, characterized in that the flocculation is carried out at a temperature around the production temperature of the medicinal or mineral water. (Priority: March 22, 1983) The process of claim 1, wherein the base is sodium hydroxide. (Priority: March 22, 1983) 5. The process of claim 1 wherein the resin is eluted with a sodium chloride solution. (Priority: March 22, 1983) 6. A process according to claim 1, wherein the odorant is a distillate obtained by evaporating the medicinal water as the first fraction. (Priority: March 22, 1983) 7. A process for the preparation of a pharmaceutical composition comprising the steps of claims 1-6. Mineral or medicinal water extracts prepared according to any one of claims 1 to 6 for the preparation of pharmaceutical preparations | mixed with commonly used additives such that the concentrate is present in an amount of 1-70% in the usual dosage form, preferably in the form of an ointment, cream, solution. (Priority: March 22, 1983) i 8. Cosmetics, characterized in that they are active The medicament contains as an ingredient an aqueous extract of claim 1 in an amount of from 1% to 70% with at least one additive commonly used in the manufacture of cosmetics. i (Priority: March 22, 1983) 9. A process for the preparation of mineral and medicinal water extracts, characterized in that a) from 0.12 to 0.5 moles / liter of alkali metal hydroxide, carbonate or hydrogen carbonate solution and extracted gyógyvíz- mineral slurry and, if desired, the resulting extract is able to bind ⁵ mak romolekuláris, organic materials pass through an ion exchange resin and elute the resin with a solution containing chloride ions, or b) mineral and medicinal waters macromolecules capable of binding organic substances, ^ion-0 passed through, and then the resin is eluted with a solution containing chloride ions, the effluent of the ion exchange resin in the original solution, and the extracts prepared according to process a) Na cation exchange column ⁺ -form, then transfer the Cl anion exchange column to a ⁵ column column and wash the bound ions with eluate of a solution containing chloride or hydroxyl ions, preferably containing at least 100 g / l sodium chloride, or preferably at least 100 g / l sodium chloride. i (Priority: March 5, 1985) 10. A process for the preparation of pharmaceutical compositions, characterized in that mineral water obtained according to claim 9 or medicinal extract ⁵ mixed with additives commonly used in preparing the pharmaceutical compositions, so that the composition in an amount of concentrate 1-70%, in the usual dosage form, preferably in the form of an ointment, cream, solution.