DE19650317C2 - Cellu-Ligno carbon isolates made from natural substances containing humic substances - Google Patents

Description

The invention relates to cellu-ligno carbon isolates (CLK isolates) made of humic material containing natural substances, a process for the production of such CLK isolates as well as their use.

Applications of humic acids and huminates are from human medicine (e.g. external use for rheumatic diseases), from the veterinary arms medicine (e.g. therapy of gastrointestinal diseases), from agriculture (e.g. adjuvant for granulation fertilizers), from the petroleum industry (e.g. Emulsifier in oil drilling) and from environmental protection (e.g. treatment processing of industrial and municipal waste).

The production of humic acids and is also known Huminates from natural sources as well as the chemical synthesis of Humic acids. However, the production of such synthetic humic acids is far more complex than natural humic acid extraction Origin. In addition, synthetic humic acids have low molecular weights (<10,000 daltons). Humic acids of natural origin, however, have Molar masses from 10,000 to over 120,000 Daltons (D), which is one of the Provides the basis for their multi-layered impact profile.

Mixtures of humic acid from natural sources are usually available as water-insoluble calcium complexes and are usually by  Treatment with alkaline solutions at least partially in a water soluble form transferred. To convert the humic acid mixtures into the Water-soluble form are usually basic alkali salts, such as for example alkali metal hydroxides, or basic ammonium salts used.

The salts of humic acids or humic acid mixtures are as follows called Huminate. In this respect, both the Huminate and the humic acids or humic acid mixtures and mixtures of huminates and humic acids or mixtures of humic acids are meant used the term humic substances.

Humic substances known from the prior art are generally the by treatment with alkaline solutions in the water-soluble form transferred portions of humic substances. They usually show one in part considerable, usually even desirable physiological activity. Furthermore, such humic substances generally have adsorbing properties what they interact with many substances in adsorptive leaves. These include metal cations, such as as essential trace elements are contained in food or feed.

DD-PS 121 521 describes a method for obtaining a Sodium humate / humic acid mixture. During the manufacturing process polyvalent mucins are added in aqueous solution in order to Drying reduces dust formation during processing to reach.

DE-C 41 29 872 relates to a process for the production of humic acid Metal compounds from humic acids of natural origin and their Use. Here, an alkali-humate-humic acid mixture, obtained from natural brown coal, first extracted alkaline. The  Extraction mixture containing dissolved and insoluble constituents freed from the insoluble components by centrifugation and the Processed supernatant as an alkaline crude extract. The alkaline Crude extract is subsequently adjusted to a pH of 3.0 to 6.9 and mixed with a nucleophilic substance and a metal salt solution. The so available humic substances show adsorptive properties.

The adsorptive properties of those known from the prior art Humic substances can be disadvantageous if their use in Systems are carried out that use an at least largely chemical require inert material.

One area of application is the manufacture of pharmaceuticals Preparations. This is usually a pharmaceutical Active ingredient as formulation aid one or more carrier substances admitted. They become carriers with strong adsorptive properties Shafts used, can thereby release the pharmaceutical Active substance due to adsorption on the carrier material to undesirable Way delayed or even prevented entirely, resulting in a loss of active pharmaceutical ingredient and thus reduced Overall effectiveness of the pharmaceutical preparation can result. Therefore the humic substances known to date from the prior art are only in limited scope for use as carrier materials in pharmaceutical Suitable preparations.

When using humic substances in food it can also be of Be an advantage if the humic substances are not combined with other ingredients same food or, if necessary, additionally and largely interact with food ingested at the same time. So  remain valuable ingredients for absorption via the gastrointestinal tract receive.

Humic substances are known to have a beneficial effect on essential coli-colon flora show and covering properties Possess cell surfaces. These properties make humic substances too valuable tools, for example in the production of food, especially dietetic foods, or pharmaceutical preparations.

For example, EP-A 655 204 describes the use of synthetically produced water soluble huminate in dietetic foods. About use nothing is said of natural humic substances.

All of the methods described in the prior art have a disadvantageous effect from that usually a complex sequence of isolation steps for Extraction of pure humic substances is required. They also show off the humic substances known in the prior art are in some cases considerable Adsorption effect for active pharmaceutical ingredients (DE-C 41 29 872) or are active pharmaceutical ingredients in a biological environment (i.e. under physiological conditions) not chemically inert.

The invention is therefore based on the object of producing from natural substances Bare humic substances or mixtures containing such humic substances To make available, on the one hand, the advantageous properties of the known humic substances for the essential coli-colon flora show, for others in the biological environment, especially in the small intestine, are chemically inert and essentially no or only slight adsorptive Interactions with active substances that are present at the same time as they do are included in pharmaceutical preparations, for example.  

Surprisingly, it has now been found that those described below Isolates from natural substances containing humic substances with molecular weights of around 10,000 up to 120,000 D have covering properties for cell surfaces, in biological environment show essentially no adsorption reactions and are chemically inert. Furthermore, it was found that those in question Isolates from natural substances containing humic substances have a regulating effect on show essential coli flora. These properties are special advantageously pronounced if at least about 50 wt .-% of the isolate Molar mass of more than about 60,000, preferably more than about 80,000 D. exhibit.

The invention thus relates to a process for producing cellulose Ligno carbon isolates (CLK isolates) made from humic substances, characterized in that

• a) an alkali humate humic acid mixture, obtainable from humine substance-containing natural substances, with an alkaline, aqueous Solution is slurried
• b) a polymeric nucleophile is added to the slurry,
• c) adjusting the slurry to a pH of 5 to 7 will and
• d) the solid contained in the slurry is separated becomes.

Another object of the invention is a Cellu-Ligno carbon isolate (CLK isolate) made from natural substances containing humic acid, obtainable according to the above. Method.  

Obtain the percentages or parts used below unless otherwise stated, the weight of the substance, based on the total dry matter.

As a starting material for obtaining the CLK isolates according to the invention preferably alkali humate humic acid mixtures used as they For example, according to the information in DD 44 155, the humic substances Natural products are available in sufficient quantities. Farther should the humic substances containing natural substances be as low as possible, preferably towards zero content for humans and animals have harmful components. Such components can, for example acute or chronically toxic as well as genotoxic, teratogenic, mutagenic or be carcinogenic. Lignite is preferred as the natural substance containing humic material used, preferably lignite from layers that are only a small or does not contain any of the harmful components mentioned above. In addition, peat, bog and lake sediments can also be used become.

Preferred is that which is commercially available under the name HUMOCARB® Product, an alkali humate humic acid mixture, for the production of the CLK isolates according to the invention used. It is HUMOCARB® a black-brown and non-water-soluble solid with a Molar mass distribution from about 10,000 to 120,000 D.

The generally powdery solid becomes more aqueous, more alkaline Slurried solution (stage a)). As an aqueous, alkaline solution in the Usually a solution of an alkali hydroxide is used. For example LiOH, NaOH or KOH can be used, the use of NaOH however is preferred. In general, the alkali hydroxides are considered to be about 0.25 to 1 M aqueous solutions used.  

The slurry is then preferably about 1 to 5, preferably about 1.5 to 3 and particularly preferably about 2 h at a temperature of stirred about 10 to 30, preferably about 15 to 25 ° C. However, it is also any other form of mixing, such as shaking, is successful. If necessary, with a corresponding extension of the contact time, the Slurry can also be treated by simply standing.

The slurry is then removed without prior separation of the in the A polymeric nucleophile was added to the slurry of the solid present (Level b)). The polymeric nucleophile is preferably z. B. Poly ethyleneimine, carboxymethyl cellulose, carboxyethyl cellulose and others Cellulose derivatives, or carboxymethyl starch, carboxyethyl starch and others Starch derivatives in question. The use of carbox is preferred methyl cellulose.

The amount of polymeric nucleophile added is usually so dimensioned that a share of at least about 3% and at most one share of about 20% results. Depending on the requirement, any, between shares in these values, such as 5, 8, 10, 12, 15 or 18% can be used.

The addition of the polymeric nucleophile usually leads to the fact that the Ability of humic substances to bind metallic cations (e.g. Mn, Cu, Fe, Co) is drastically reduced. Furthermore, treated in this way Humic substances have a significantly lower solubility in water than the usual ones Alkali aluminate mixtures.

The next step (step c)) is to adjust the slurry to a pH from about 5 to 7, preferably about 5.5 to 6.8 and particularly preferably about 6 to 6.5 set. This setting can be made by adding acid in  in any form. Preferably to adjust the pH Worth, however, organic acids, preferably acetic acid, or mineral acids, such as hydrochloric acid or sulfuric acid, preferably hydrochloric acid. The Adjustment of the pH can be done in any vessel become. However, it can be beneficial if the slurry is already in a vessel during the subsequent separation operation can be used, for example a stirring nutsche.

In the next step (stage d)) solid and liquid are from the Slurry separated. This separation operation can be done by anyone Method known to the person skilled in the field of solid / liquid separation be performed. However, it has proven useful to separate by one Make a suction filter and, if necessary, create a vacuum.

Stages a) to d) are usually in the order given executed. If necessary, however, stages b) and c) in their Order can be reversed.

The remaining filter cake (CLK isolate) may be used for cleaning washed with water and then preferably dried. The Drying temperature should not exceed about 80 ° C. Especially drying is preferably carried out with a vacuum.

The dry matter thus obtainable can, if necessary, insofar as the procurement the filter cake or the further processing this requires, be ground. This is advantageously based on a grain size diameter set from about 50 to 200 microns.

So one can in the manner indicated above (stages a) to d)) so-called Cellu-Ligno carbon isolate (CLK isolate) obtained. The CLK isolate  can be processed in the form of a moist filter cake, provided that Purity and moisture content meet the processing requirements. However, as discussed above, other ver work steps, such as washing, drying or grinding, or two or more of the processing steps mentioned simultaneously or one after the other. Even the washed, the washed and dried or the washed, dried and ground product is called CLK isolate.

The CLK isolate has a humic acid content of about 70 to 90% (the 100% missing portion usually consists largely of physiologically inert ashes, water-insoluble salts and, for example, flavonoids), a specific surface area of at least about 600 m ² / g and a molecular weight of about 10,000 to 120,000 D.

There is no free humic acid in the CLK isolate, but rather theirs Alkali or alkaline earth salts.

The CLK isolate is for dermal or oral use or administration neither acute nor chronically toxic, since it is neither via the intestine nor via the outer skin is absorbable. It is not embryotoxic or mutagenic and also not teratogenic or carcinogenic.

The CLK isolate according to the invention is therefore extremely suitable as chemically inert additive to food for human consumption or animals and to pharmaceutical preparations, wherein there is a desirable regulating effect on the essential coli flora unfolded.  

In the sense of the invention, foods are understood to mean substances that of the feeding of living beings, in particular humans and of Animals. The following will refer to human Diet the term "food" when referring to animal Nutrition (unless expressly stated otherwise) is the expression "Feed" used.

The CLK isolate according to the invention is due to its regulating effect on the physiological coli flora especially for use in suitable for dietetic foods. It's about dietary foods according to the Ordinance on Dietary Food of August 25, 1988 (BGBI I, p. 1713) to "Food that is determined, a certain Serve nutritional purpose by making certain the intake Nutrients or other nutritionally effective substances in one certain quantity ratio or in a certain condition. "

The CLK isolates according to the invention are, for example, a substitute suitable for flour in the production of baked goods. You are suitable but also as an additive to feed, for example in animal rearing Area.

The present application is therefore also the use of CLK isolates according to the invention described above as an additive in Food and feed for human or animal consumption, especially in dietetic food and feed.

The invention further relates to foods, in particular dietetic foods or feed containing the invention CLK isolate.  

The foods according to the invention are generally solid or pasty foods. In the sense of the invention, pasty are considered Foodstuffs such as soft cheese, yoghurt, mustard, ketchup, curd cheese or spreads such as B. peanut butter or jam. However, it is also possible, the CLK isolates for example in dispersed or simple in slurried form as part of largely liquid food or Administer or ingest feed.

In particular, the use of CLK isolates in solid foods has become the baked goods proved to be suitable. The CLK isolate is used as Proportional replacement of flour or as an additive in the baked goods integrated. The baked goods can also contain common substances such as vegetable or animal fats, sugar and / or sugar substitutes, salt, blowing agents or Leavening agents, flavorings or mixtures of two or more thereof contain. Use in bread or permanent baking, for example, is preferred such as biscuits or crackers, the use in long-life baked goods is particularly preferred.

It is also possible to use CLK isolates in expanded Pasta extrudates, such as in so-called flips.

Furthermore, the CLK isolates according to the invention are suitable as carriers, i. H. as chemically inert substances that act as a base and framework for active substances can serve. This allows an application as a carrier in pharmaceutical preparations because of an interaction with the or respective, present in the pharmaceutical composition Active ingredients do not take place.  

The invention therefore also relates to the use of the above described CLK isolates in pharmaceutical preparations, preferably as a chemically inert carrier material.

The invention therefore also relates to pharmaceuticals Preparations containing the CLK isolate according to the invention, preferably as chemically inert carrier material.

If the CLK isolate according to the invention is used as an additive to foods, for example, baked goods, the CLK according to the invention functions Isolate is usually used as a substitute for cereal flour. The invention CLK isolate can contain up to 60% of what is usually in the recipe replace the flour used, but preferably only one less of the flour is replaced by CLK isolate. A lesser one Percentage can be, for example, about 50, 40, 30, 20 or even only 10% his.

The proportion of CLK isolate in the finished food is Usually up to about 50%, preferably up to about 30% and especially preferably up to about 25%. Of course, depending on the Requirements also include smaller amounts, such as about 15% 10% or less can be added to the food.

The CLK isolate according to the invention can also be used in a concentrated form so-called dietary or nutritional supplement are prepared. Diet- or nutritional supplements are usually added to, or partly taken as a substitute for normal food. Such diet or nutritional supplements can isolate a higher amount of CLK included as the finished foods described above. In the Use of CLK isolate as a dietary or nutritional supplement in  Food or animal feed can contain up to about 80% of CLK isolate be. However, it is preferably up to about 75% or less, for example at 60, 50, 40 or even only 30%.

When used in animal feed, the proportion of CLK isolate is usually however, far below that, for example about 10%, 5% or even less Amounts. An amount of about 0.5 to 2% is generally advantageous.

The CLK isolate according to the invention can also be used together with others Vegetable flours that are not derived from cereals are used. For this counts e.g. B. algae flour, especially the flour of Spirulina platensis. A Such a combination of CLK isolate and algae flour can be used as a biostimulator to strengthen the immune system with daily oral administration both for humans as well as for small pets and for pets Livestock rearing (especially piglets, calves, lambs, goats, foals) be used.

The CLK isolates according to the invention can be used both in Food or feed as well as when used as a carrier in pharmaceutical preparations in different dosage forms Tobe offered. These include e.g. B. powder, granules, capsule, bolus or Tablet. The different dosage forms can be produced according to the usual methods of pharmaceutical galenics.

The following examples serve to illustrate the invention in more detail.  

Examples example 1 Production of a CLK isolate according to the invention

12 kg of HUMOCARB® are slurried with 70 l of 0.25 N NaOH and 2 h stirred at room temperature in a suction filter. Thereafter, 20 parts by weight % Carboxymethylcellulose (CMC) added and stirring continued for 0.5 h. in the The pH is then adjusted by adding approximately 10 to 12 l Acetic acid (2 N) adjusted to pH 6.0. It is stirred for a further 45 min, the pH is checked again and if necessary by adding acetic acid corrected and then vacuumed. The remaining residue is in a vacuum dried at 80 ° C to a residual moisture of <10%.

Example 2 Production of long-life baked goods (crackers, biscuits)

Depending on the type of baked goods, there will be flour or broken grain or a mixture thereof with CLK isolate homogenized to a premix. Here, for example, can be used;

A: Premix

1. 55 parts of wheat flour
2. 25 parts of CLK isolate

B: basic dimensions:

3. 10 parts of fat
4. 5 parts of sugar
6. 2 parts of salt
7. 3 parts of raising agent (makes a total of 100 parts) and
8. minor amounts of flavorings.

The base and premix together make up 100 parts. 20 parts of water or milk are now worked into the base and the resulting mixture is mixed with the premix with the addition of mixed another 20 parts of water. The resulting product becomes after heat baked in the shape. The baking process is preferably as long continued until the added liquid portion at least largely is removed, preferably goes to zero. The content of CLK isolate will adjusted to about 25 parts.

Example 3 CLK isolate as an additive for rearing feed for pigs

In pig feed commercial composition based on Wheat soybean extraction meal with approx. 21% crude protein becomes CLK isolate in a quantity of 20 parts per 1,000 parts of finished feed homogeneously mixes. The intake of the feed leads to a biological stimulation of the Immune system via the intestine and to regulate the physiological Coli colon flora.  

Example 4 Manufacture of a food and feed supplement product in the combination humic substance / algae

5 parts of CLK isolate with one part of algae flour (Spirulina platensis) mixed and with fillers (cornstarch, vanilla flavoring) 10 parts filled up, mixed homogeneously and formulated.

It is used as a biostimulator to strengthen the immune system daily oral administration, both for humans and for small ones Domestic and pet animals as well as for raising livestock.

Claims (7)

1. A process for the production of cellu-ligno carbon isolates (CLK isolates) from humic-containing natural products, characterized in that

• a) an alkali-humate-humic acid mixture, obtainable from natural substances containing humine, is slurried with an alkaline, aqueous solution,
• b) a polymeric nucleophile is added to the slurry,
• c) the slurry is adjusted to a pH of 5 to 7 and
• d) the solid contained in the slurry is separated.

2. The method according to claim 1, characterized in that the alkaline, aqueous solution has a pH of less than 11. 3. The method according to any one of claims 1 or 2, characterized in that that the alkaline, aqueous solution contains NaOH. 4. The method according to any one of claims 1 to 3, characterized in that the polymeric nucleophile at least 3 wt .-% and at most 20 wt .-% (based on dry matter) is used. 5. The method according to any one of claims 1 to 4, characterized in that carboxymethyl cellulose is used as the polymeric nucleophile.   6. Cellu-Ligno carbon isolate (CLK isolate) obtainable by the process according to one of the claims 1 to 5. 7. Use of the CLK isolate according to claim 6, as an additive to life food, feed and pharmaceutical preparations.