EP1220818A1

EP1220818A1 - Water treatment agent for extending water exchange intervals in tank systems

Info

Publication number: EP1220818A1
Application number: EP00956453A
Authority: EP
Inventors: Günter Ritter
Original assignee: Tetra GmbH
Current assignee: Tetra GmbH
Priority date: 1999-09-18
Filing date: 2000-08-16
Publication date: 2002-07-10
Also published as: EA006817B1; DE19944800A1; KR100747124B1; HK1049992A1; CA2382950C; CN1374930A; US6979411B1; BR0014069A; KR20020063857A; CN100457648C; DE19944800B4; CZ2002910A3; CA2382950A1; AU6838800A; PL205060B1; PL353928A1; EA200200384A1; BR0014069B1; WO2001021534A1; JP2003530824A

Abstract

A composition for long term improvement of water quality in biological tank systems is described and characterized by a content of: 1) at least one highly or poorly soluble Al?3+-, Fe3+-, TiO2+¿- or ZrO2+ salt of an organic carboxylic acid, optionally mixed with an organic carboxylic acid; 2) at least one water soluble N free biologically degradable organic compound; 3) at least one soluble alkali or earth alkali metal salt of an organic carboxylic acid; and 4) at least one Mg2+ salt of an organic carboxylic acid optionally mixed with at least one Ca2+ of an organic carboxylic acid and also 5) trace elements and vitamins, particularly water soluble vitamins of the B series. Changes in water quality determining parameters can be reduced, minimized or eliminated . by using the described agent and thus a significant reduction in partial water change frequency or a clear extension of periods without water changing can be achieved.

Description

Water treatment agent for extending the water change intervals in housing systems

The invention relates to chemically and microbiologically active preparations for extending the water change-free intervals in biological housing systems

Use of ecologically neutral, chemically and microbiologically active water additives.

In biological housing systems, e.g. B. aquariums, aquariums and garden ponds, it comes from the daily feeding of the fish and others contained therein

Aquatic animals to accumulate changes in important chemical water parameters and consequently to a constant deterioration in water quality. This results in a correspondingly reduced quality of life for the kept fish and other aquatic animals.

Has the source water, e.g. B. tap water, a sufficient quality, can be counteracted by frequent partial or complete water changes a deterioration in water quality caused by the housing. The procedure of changing the water is cumbersome and uncomfortable for the aquarist, for the kept fish and other aquatic organisms not without, e.g. T. considerable risk from undesirable properties of the fresh starting water, for example chlorine, heavy metals.

It would therefore be desirable to minimize the frequency and amount of water changes if, as described in the present invention, the deterioration of the To suppress or eliminate water quality.

Specifically, the following changes in water quality deteriorating important water parameters occur in biological housing systems:

* Increase in the phosphate content.

* Increase in nitrate content,

* Decrease in carbonate hardness and pH to the point where the carbonate hardness is completely used up. Then there is an acute risk of the so-called acid fall, i.e. H. the pH reduction goes far into the acidic range. The result is a greatly increased fish mortality.

* Consumption of important trace elements that are essential for the plant and bacterial metabolism.

* Consumption of important water-soluble vitamins from the B group, which are important for the entire ecosystem.

A regular change of partial water cannot eliminate the changes typical of the system, but only reduces them and the deterioration in water quality is only delayed. On the other hand, a regular change of partial water carries additional risks, which are derived from increased stress for fish and other aquatic organisms and caused by the fresh water used. With the very widespread use of tap water, there is a risk from chlorine, heavy metals and the absence of organic colloids, which gives the tap water a certain aggressiveness towards the mucous membrane. It is therefore desirable to develop a water treatment agent or process that reduces, minimizes or eliminates the described changes in water quality-determining parameters and thus enables a significant reduction in the frequency of partial water changes or a significant extension of the water change-free intervals.

Some of the sub-problems listed above can be countered by measures that are already known.

A) The increase in the phosphate concentration occurs mainly through constant entry with the feed. The increase in phosphate to values above 10-20 mg / 1 is disadvantageous since the undesired growth of algae is promoted by phosphate.

The following measures for reducing phosphate are known:

a) Binding of phosphate to Al ³⁺ and / or Fe ³⁺ oxides

(Granules containing hydroxide groups) which are introduced into the filter system. Their limited capacity is a disadvantage. After their exhaustion, it becomes necessary to replace the granules, which is often quite cumbersome. If the aquarist does not regularly measure the phosphate content, he will not recognize the exhaustion of the material and the PC ^ ^3- concentration in the housing water will increase again, ie the treatment success of this method is often inadequate.

b) The addition of dissolved inorganic Al ³⁺ and / or Fe ³⁺ salts also leads to a reduction in the P0 ₄ ³ concentration when used regularly. Disadvantages of this Procedure are:

- High fish toxicity of the dissolved inorganic Al and Fe, 3 + salts,

- Enrichment of the water with anions, such as. B. chloride and sulfate,

- Reduction of the carbonate hardness, the HC0 ₃ ^~ and C0 ₃ ^{2 ~} content and thus

- reduction of buffer capacity,

- lowering the pH level and risk of acid drop at KH = - 0 ° dH,

- Turbidity of the water and unsightly flocculation of AI (OH) ₃ and Fe (OH) ₃ .

Another example of the undesirable changes mentioned is the increase in the nitrate concentration due to the constant introduction of proteins and others

Nitrogen sources with the feed. All nitrogen sources from the feed, for the most part proteins, are oxidized to nitrate by ammonia and nitrite. The constant increase in nitrate is an unnatural burden on the housing water, which is undesirable for aquarists. The nitrate content of the initial water is often so high, e.g. B. at 25 - 50 mg / 1, so that the natural N0 ₃ ^~ concentration of a few mg / 1 can never be reached by water changes.

The following measures are necessary to reduce the nitrate content known :

a) Reduction of the nitrate content by anion exchangers, usually in chloride form. The disadvantage here is the replacement of the nitrate ions by the loading anions of the exchanger, usually chloride, and the replacement of

Sulphate and hydrogen carbonate ions. In addition to the undesirable reduction in carbonate hardness, the chemical water composition is completely changed.

b) Denitrification in an anaerobic environment or in anaerobic reactors. By introducing practically insoluble, biodegradable, organic, nitrogen-free material in granular form into the filter system, anaerobic areas are created by strong 0 ₂ consumption in which nitrate as an oxygen source is reduced to N ₂ . The disadvantage is:

- the unsafe dosage,

- the uncertain process control and process controllability,

- The sulfate reduction to be expected at low N (V concentrations to highly toxic

Hydrogen sulfide.

The lowering of the carbonate hardness due to nitrification is another example of the undesired water changes mentioned. The oxidation of the continuously supplied organic nitrogen takes place via the oxidation of ammonia to nitrite made possible by nitrifying bacteria. In this biological process one mole of H ⁺ ions is formed per mole of ammonia. The released H ⁺ ions react with existing bases, mostly bicarbonate as a carbonate hardness, with protonation and reduction of the carbonate hardness.

The following measures are known to compensate for the losses of carbonate hardness (or HC0 ₃ ~ losses) but also to increase the carbonate hardness:

a) addition of NaHC0 ₃ and / or Na ₂ C0 ₃ as a powder or as a solution. The method works reliably, but has the following disadvantages:

- With NaHC0 ₃ / Na ₂ C0 ₃ mixtures there are rapid pH increases in the storage water, which lead to considerable stress on the organisms.

- In waters with increased ammonium contents, a u. U. lethal amount of ammonia released.

- The water solubility of NaHC0 ₃ is relatively low, so that highly concentrated liquid products with convenient use are not possible.

b) addition of freshly prepared solutions which, in addition to dissolved calcium hydrogen carbonate, also contain a lot of free C0 ₂ . The excess CO ₂ can lead to rapid CO ₂ damage to the organisms. In addition to the HC0 ₃ concentration, the Ca ²⁺ concentration is also increased here, which is not always desirable.

It can also be chemically and biologically caused Losses of dissolved calcium bicarbonate cause undesirable water changes. C0 ₂ consumption and the associated pH increase shift the lime / carbonic acid equilibrium towards the quay separation. The disadvantageous loss of dissolved Ca (HC0 ₃ ) ₂ leads to a corresponding decrease in the calcium concentration and the HC0 ₃ ^~ concentration (carbonate hardness reduction).

The following measures are known to compensate for or increase the losses of Ca (HC0 ₃ ) ₂ :

a) Addition of solutions which, besides Ca (HC0 ₃ ) _2, still contain a lot of free C0 ₂ . This measure has the disadvantages described above. Another disadvantage lies in the complexity of the process, since the Ca (HC0 ₃ ) 2 solutions have to be prepared laboriously by dissolving CaC0 ₃ or Ca (OH) ₂ in water enriched with C0 ₂ . By adding Mg (OH) ₂ or MgC0 ₃ ^• Mg (OH) _{2 it} is also possible to prepare a solution which additionally contains Mg (HC0 ₃ ) ₂ .

b) addition of solid mixtures containing equivalent amounts of NaHC0 ₃ and soluble Ca, Mg salts (mostly chlorides). The ions Ca ²⁺ + 2C1 ^" + 2Na ⁺ + 2HC0 ₃ ^{" are} introduced by dissolving these mixtures in the holding water. In addition to the desired [Ca ²⁺ + 2HC0 ₃ ^" ], the water now also contains the equivalent amount of NaCl (or also Na ₂ S0 ₄ ), which is undesirable. The disadvantage of this process is the introduction of foreign salts, eg NaCl or Na ₂ S0 ₄ .

Finally, the consumption of dissolved carbon dioxide also changes the water quality. Algae, aquatic plants and autotrophic microorganisms constantly consume dissolved carbon dioxide. In addition to the resulting increased pH value, there is a lack of CO ₂ , which has a detrimental effect on chemical and biological processes.

The following additional C0 ₂ measures are known to compensate for the lack of C0 ₂ :

a) Supply of C0 ₂ gas from C0 ₂ pressure bottles. Problems with this method are:

- the difficult to set and control dosage,

- the price,

- Security risks associated with the compressed gas system.

b) C0 ₂ generation by anodic oxidation of a graphite electrode. The system has the following disadvantages:

- poor meterability,

- C0 ₂ peaks due to secondary chemical processes on the cathode, combined with severe decalcification,

- formation of oxyhydrogen,

- Formation of chlorine in water rich in chloride. c) Generation of C0 ₂ in external fermentation reactors. Here too there are serious, system-related disadvantages, e.g. B.

- strong temperature dependence of the fermentation / fermentation process,

- difficult to control process,

- very poor dosing options and dosing constancy.

The various problems outlined above initially appear heterogeneous and cannot be solved with one principle.

Surprisingly, it was found that the improvement in the water quality of biological housing systems can be achieved by means of which the following components are added to the housing system individually or in any combination:

a) to lower the phosphate concentration at least one easily or slightly soluble Al ³⁺ , Fe ³⁺ , Ti0 ⁺ , Zr0 ²⁺ or Ca ²⁺ salt of an organic carboxylic acid, optionally in a mixture with an organic carboxylic acid;

b) at least one water-soluble, N-free, biodegradable organic compound to reduce the nitrate concentration or limit the increase in nitrate;

c) to increase the carbonate hardness or the HCO3 ^" concentration at least one alkali or alkaline earth metal salt of an organic carboxylic acid; d) to increase the total hardness or the concentration of Ca ²⁺ and Mg ²⁺ bicarbonates, a mixture of at least one Ca ²⁺ and Mg ²⁺ salt of an organic carboxylic acid, and

e) to increase the C0 ₂ concentration at least one biodegradable compound.

Products which, in the form of water additives, reduce or solve the problems described above in a stable manner over a long period of time and without side effects, have hitherto not been known.

The invention was based on the object of developing a water additive which, from a general point of view

* the described changes in quality-determining water parameters are reduced, minimized or eliminated,

* the partial water change-free intervals of 1 to 4 weeks so far, e.g. B. extended to 6 months, and

* This makes the aquarium hobby safer, simpler and more attractive.

In particular, the water additive should reduce, minimize or eliminate the following chemical changes when used regularly:

* The increase in phosphate,

* the increase in nitrate,

* the loss of carbonate hardness and the lowering of pH, * the drop in acidity, * the consumption of essential trace elements,

* the consumption of water-soluble vitamins from the B group.

The invention thus relates to a composition for long-term improvement in the water quality of biological housing systems, characterized by a content of

1.) at least one easily or slightly soluble Al ³⁺ , Fe ³⁺ - Ti0 ²⁺ , or Zr0 ²⁺ salt of an organic carboxylic acid, optionally in a mixture with an organic carboxylic acid;

2.) at least one water-soluble N-free, biodegradable organic compound;

3.) at least one soluble alkali or

Alkaline earth metal salt of an organic carboxylic acid, and

4.) at least one Mg ²⁺ salt of an organic carboxylic acid, optionally in a mixture with at least one Ca ²⁺ salt of an organic carboxylic acid and

5.) trace elements and vitamins, especially water-soluble vitamins of the B series.

Surprisingly, it was possible to combine the above-mentioned individual components into a single combination of active ingredients for a more extensive chemical / microbiological water treatment.

The resulting composition can contain all the essential components in addition to the components necessary to eliminate the sub-problems described at the beginning Contain trace elements and water-soluble vitamins, especially those from the B group.

The use of just a single water treatment agent in the form of a combination product is considerably more convenient, easier and safer for the aquarist than different applications of individual problem-free people.

The new composition (in the form of a combination preparation) for combined problem solving contains the following individual components:

A) Components for preventing the phosphate increase or for reducing the phosphate concentration:

This function is easily or slightly soluble Al ³⁺ , Fe ³⁺ , Ti ²⁺ or Zr0 ²⁺ salts of organic carboxylic acids, eg. B. met with their acetates, formates, tartrates and in particular citrates. In addition to the strongly phosphate-binding metal ions Al ³⁺ , Fe ³⁺ , Ti0 ²⁺ or Zr0 ²⁺ , calcium salts of organic carboxylic acids can also be used in a similar way, but with a considerably smaller ability to eliminate phosphate. Mixtures of the salts of organic acids with the underlying organic acids or other organic acids can also be used with the same success, for example

Aluminum citrate plus citric acid, iron (III) citrate plus citric acid, iron (III) citrate plus tartaric acid.

The principle is shown below for Al ³⁺ and Fe ³⁺ salts, but also applies accordingly to Ti0 ²⁺ and Zr0 ²⁺ salts. If Al ³⁺ and / or Fe ³⁺ salts of carboxylic acids are added to the housing water, no flocculation and cloudiness are observed at first. Only after aerobic biodegradation in the filter system

Aluminum citrate (AI) + 3HC0 ₃ ^" aerobic degradation

Iron (III) citrate (Fe ^{i +} ) + CO 2

In the directly subsequent formation of Al (OH) ₃ or Fe (OH) ₃ according to

Fe ³⁺ (Fe (OH) ₃ )

+ 3HC0 ₃ ^" + 3C0 ₂

Al ³⁺ (Al (OH) ₃ )

phosphate is deposited and precipitated together with the hydroxides.

The precipitated metal hydroxides with co-occluded phosphate accumulate in the filter sludge and are eliminated during regular filter cleaning.

By regular addition of the organic metal salts, e.g. B. as an aqueous solution to the housing water, the phosphate increase can be completely prevented.

In contrast to phosphate precipitation with inorganic Al ³⁺ or Fe ³⁺ salts, the phosphate precipitation according to the invention has serious and surprising advantages:

- There is no clouding and flaking in the water, - the process runs largely in the biologically active filter system,

- The organic metal salts behave

toxicologically neutral, ecologically neutral, carbonate-neutral.

- No accumulating foreign ions are added.

- It is generated by aerobic degradation of the carboxylic acid anions only C0 ₂ , which has a positive influence on the C0 ₂ content or the C0 ₂ consumption z. T. compensates.

The resulting phosphate concentrations are typical for every metal:

For Fe citrate: approx. 0.0 - 0.2 mg / 1, for AI citrate: approx. 0.0 - 0.5 mg / 1, for Ca citrate: approx. 0.5 - 1.5 mg / 1.

Aluminum citrate and / or iron citrate are preferably used. The application concentration in the holding water is 0.5 - 50 mg / 1, preferably 0.5 - 10 mg / 1 at a dosage of once to three times a week.

Components to prevent or limit the increase in nitrate:

If the housing water is regularly N-free, If organic, degradable substances are added, the increase in the nitrate concentration is slowed down or limited even without the presence of anaerobic reactors and a nitrate concentration is reached which is at a medium level. Without treatment with these water additives according to the invention, the nitrate content increases monotonously and indefinitely. Since the reason for the prevented or braked increase in nitrate is a partial denitrification in anaerobic micro-areas in the filter, the nitrification-related loss of carbonate hardness (HC0 ₃ ^~ concentration) is inhibited or limited parallel to the slowing down or limitation of the nitrate increase.

In principle, all biodegradable organic compounds can be used as nitrate-reducing, water-soluble compounds, but preferably aliphatic compounds such as alcohols, e.g. As glycerin, sorbitol or ethanol, sugar, e.g. Pentoses, hexoses or sucrose, or carboxylic acids, e.g. Acetic acid, citric acid, lactic acid or tartaric acid.

Combinations of equal amounts of citric acid and sucrose or acetic acid and sucrose have also proven their worth.

Acetic acid, tartaric acid, citric acid, glycerol, glucose, sucrose are preferably used, a combination of citric acid, tartaric acid and sucrose having proven particularly useful.

The application concentrations in the cage water for citric acid are 0.5 - 100 mg / 1, preferably 1 - 20 mg / 1; for sucrose 0.5 - 50 mg / 1, preferably 1 - 20 mg / 1, and for tartaric acid 0.5 - 50 mg / 1, preferably 1 - 20 mg / 1, at a dosage of once to three times a week.

In parallel to the N0 ₃ ^" stabilization, the carbonate hardness is also stabilized at minimum values below which the carbonate hardness does not drop any further.

The added compounds are completely broken down to H ₂ 0 and C0 ₂ . The C0 _{2 formed} is used as a C source by plants, algae and nitrifying bacteria.

By introducing ventilation, the C0 ₂ ^" concentration can be corrected downwards as required.

Components to compensate for losses in carbonate hardness or hydrogen carbonate:

In the present solution according to the invention, the following microbiological / chemical principle is used, using Na ⁺ , Ca ²⁺ , Mg ⁺ and Sr ²⁺ salts of aliphatic carboxylic acids, such as, for example, acetic acid, lactic acid, citric acid, tartaric acid , Formic acid, propionic acid, malic acid and the like.

Are carboxylic acids, e.g. B. acetic acid, microbiologically degraded, only H ₂ 0 and C0 _{2 are formed} :

0 ₂ , dismantling

In contrast, if salts of the carboxylic acids are used microbiological degradation, so hydrogen carbonate is formed in addition to C0 ₂ according to the number of negative charges of the anions introduced.

0 ₂ , degradation CH3COO- C0 ₂ + 1.5 H ₂ 0 + HCO3 ^"

By introducing salts of carboxylic acids into the housing water, the bicarbonates are formed after biodegradation.

This may be the example of sodium hydrogen carbonate from organic sodium salts, e.g. B. Na acetate, Na citrate, not yet act very spectacular, since NaHC0 ₃ itself is easily accessible. But even here with liquid preparations there is the great advantage of the - in comparison to NaHC0 ₃ - mostly very high solubility, for example Na acetate, which allows high product concentrations and ranges.

Another advantage of using organic Na salts instead of NaHC0 ₃ or Na ₂ C0 ₃ is the pH-neutral application:

- The Na salt of organic carboxylic acids has a pH-neutral effect, can even be made acidic in the product with excess carboxylic acid (s). Naturally, this is not possible with NaHC0 ₃ or Na ₂ C0 ₃ .

- Biodegradation (except for formates) still produces C0 ₂ , which also counteracts a pH increase.

The advantages of the Problem solution according to the invention, if one considers the introduction of the hydrogen carbonates of the alkaline earths Mg ²⁺ , Ca ²⁺ , Sr ²⁺ , which are known not to be available as substances. By adding the soluble Mg ²⁺ , Ca ²⁺ , Sr ²⁺ salts of organic carboxylic acids, the desired concentrations of the bicarbonates can easily be built up in the holding water.

Example: (Acetate)

0 ₂ , degradation M ²⁺ (OAc) ₂ > M ²⁺ (HC0 ₃ ) ₂ + 2C0 ₂ + 3H ₂ 0

M ²⁺ = Mg ²⁺ , Ca ²⁺ , Sr ²⁺

The dosages are based on the desired setting or increase in the carbonate hardness or the HC0 ₃ ^" concentration. 1 mmol / 1 Na salt of organic carboxylic acids increases the carbonate hardness by 2.8 ° dH, 1 mmol / 1 Mg ²⁺ , Ca ^{2 +} , Sr ²⁺ salts of organic carboxylic acids increases the carbonate hardness by 5.6 ° dH.

The following are suitable as carboxylic acids:

a) For Na ⁺ salts: practically all aliphatic carboxylic acids, especially acetic acid, lactic acid, citric acid, tartaric acid and the like.

b) For Mg ²⁺ salts:

Virtually all aliphatic carboxylic acids, especially acetic acid, lactic acid, citric acid, tartaric acid and the like. c) For Ca ²⁺ salts:

All alphatic carboxylic acids that form water-soluble Ca ²⁺ salts, especially formic acid, acetic acid, propionic acid, lactic acid, malic acid and the like.

d) For Sr ²⁺ salts:

All aliphatic carboxylic acids that form water-soluble Sr ²⁺ salts, especially formic acid, acetic acid, propionic acid, lactic acid, malic acid and the like.

Na ⁺ and Mg ²⁺ salts of citric acid and tartaric acid are preferably used. Ca ²⁺ salts can be dispensed with due to the normally high Ca ²⁺ content of the initial water, but admixing is generally possible if acids are used that form soluble Ca salts.

The carbonate hardness, expediently added to the holding water once to three times a week, is 0.05-5 ° dH, preferably 0.1-1.0 ° dH. This is achieved by the appropriate addition of 0.018-1.8 mmol / 1 alkali metal salts, preferably 0.036-0.36 mmol / 1, or 0.009-0.9 mmol / 1 alkaline earth metal salts, preferably 0.018-0.18 mmol, or corresponding mixtures of alkali metal and alkaline earth metal salts.

D) Components for increasing the total hardness:

With the addition of Mg ²⁺ salts (and Ca ²⁺ salts) of organic carboxylic acids to increase the carbonate hardness as described under C), an increase in the total hardness is automatically associated. The advantages are: - Very simple and safe, defined setting and increasing the total hardness,

problem-free manufacture and use of product preparations, in particular liquid solutions,

- no introduction of unwanted foreign ions,

- Easy setting of all desired Mg: Ca ratios from ∞: 1 to 1: ∞.

- Only controlled amounts of C0 _{2 are} generated, which serve plants, algae and autotrophic microorganisms for the supply of carbon.

- In addition to the Mg ²⁺ and Ca ²⁺ bicarbonates formed from organic salts described here, other inorganic Mg ²⁺ , Ca ²⁺ salts, such as chlorides or sulfates, can also be added in combination, so that every possible or required chemical

Realization of composition of the total hardness.

Mg ²⁺ salts (if necessary also Ca ²⁺ salts) of citric acid and tartaric acid are preferably used.

The total hardness added to the housing water once or three times a week, as magnesium hardness, is 0.01

- 2 ° dH, preferably 0.01 - 1 ° dH, this corresponds to 0.0018

- 0.36 mmol / 1, preferably 0.018 - 0.18 mmol / 1 magnesium salt.

E Components for increasing the C0 ₂ concentration: When defining the above components A) to D) it has already been described that C0 is formed during the biodegradation of organic compounds in the housing system. This can be _^'2 Remove -Zufuhrsystem to an internal, microbiologically working C0. A constant and sufficient, but not yet harmful to the organism supply of C0 ₂ to the holding water fulfills various important functions:

- carbon fertilization of plant organisms,

- carbon supply of the autotrophic microorganisms, in particular the nitrifying agents,

Prevention of the pH rise caused by CO ₂ consumption,

- Setting a defined pH value by setting the HC0 ₃ ^~ / C0 ₂ acid base equilibrium,

- Intervention in the lime / C0 ₂ balance and prevention of chemical and biological lime precipitation.

It has been shown that CO ₂ concentrations between 1 and 25 mg / 1, preferably 5-15 mg / 1 are in the optimal range. Potential C0 ₂ damage to fish and other aquatic organisms does not yet occur here. Since C0 _{2 is} constantly consumed in the housing system and losses to the atmosphere occur, C0 ₂ must be added to the housing water in the correct amount.

This can be done very easily by adding biologically one to three times a week degradable organic compounds, e.g. B. of aliphatic organic carboxylic acids, alcohols and sugars. The following connections have proven particularly useful:

a) carboxylic acids: formic acid, oxalic acid, acetic acid, lactic acid, citric acid, malic acid, tartaric acid, b) alcohols: ethanol, glycerin, sorbitol, c) sugar: pentoses, hexoses, sucrose.

If the carboxylic acids are dosed alone, the equivalent amount of CO _{2 is} immediately released from the hydrogen carbonate supply in a chemical reaction:

HC0 ₃ ^" + CH3COOH C0 ₂ + H ₂ 0 + CH3COO-

During the subsequent biodegradation of the carboxylic acid anion, the consumed is slowly (within a few hours to 24 hours)

Hydrogen carbonate generated again and further C0 ₂ formed:

CH3COO ^" > HCO3 ^" + C0 ₂ + 1.5H ₂ 0

Carboxylic acids therefore generate C0 ₂ in a step process:

) In one second reaction by protonation of HC0 ₃ ^~ , b) in a reaction of a few hours to 24 hours by oxidative biodegradation.

Alcohols and sugars added to the housing system are only broken down by the relatively slow microbiological reaction to H ₂ 0 and C0 ₂ .

By choosing combinations of different C sources with different rates of C0 ₂ release, a very uniform C0 ₂ introduction can be achieved, e.g. B. by the combination of citric acid and sucrose or acetic acid and sucrose.

The maximum C0 ₂ concentration formed in the

Storage water (after the complete breakdown of the organic additives) is 1 - 100 mg / 1, preferably 5 - 50 mg / 1 at a dosage of once to three times a week.

Due to biological consumption by plant organisms and autotrophic bacteria as well as constant weak ventilation, the generated CO ₂ concentration maxima are quickly leveled.

) Components to increase the concentration or compensate for the constant loss of essential trace elements:

The general and preferred concentration ranges of the trace elements used are listed in Table 1 below.

In order to avoid accumulation of non-degradable complexing agents, all metallic complexing agents Trace elements of the water in the form of citrates, tartrates and the like. added.

Table 1

The trace elements are metered into the housing water once to three times a week with the combination agent according to the invention.

G) Components for increasing the concentration or compensating for the constant consumption of the water-soluble vitamins from the B group: 25

Table 2 below lists the general and preferred concentration ranges of the water-soluble vitamins from the B group introduced into the housing water:

Table 2

The vitamins are dosed once to three times a week with the active ingredient combination.

The following exemplary embodiment is intended to illustrate the invention in more detail.

embodiment

Fully equipped, planted, filtered and poorly ventilated hot water aquariums (70 liters content, filled with 10 - 20 medium-sized tropical fish) were added once a week with the components described above to extend the water change intervals in the form of a combination agent. With a dosage of 1 ml solution of the composition per 4 liters of aquarium water, the active substance concentrations listed in Table 3 below were achieved:

27

Table 3

The aquariums were kept for 6 months without changing the water. Evaporated water was supplemented by demineralized water in order to create a worst-case situation with regard to KH (carbonate hardness) losses and pH drop.

The following parameters of the housing water were monitored during the entire test period:

1. Phosphate concentration:

The phosphate concentration remained below 0.1 to 0.2 mg / 1 throughout the test period.

2. Nitrate concentration:

Even with the very low weekly intake of nitrate-lowering components (citric acid, sucrose, tartaric acid), the N0 ₃ content rose to approx. 100 - 140 mg / 1 and then remained constant. By doubling the nitrate-lowering component, the nitrate maximum would have been kept at 50 - 70 mg / 1 and if this amount were dosed every 2 days, the N0 ₃ content would not have increased appreciably above the initial concentration of approx. 15 - 20 mg / 1.

3. Preservation of carbonate hardness, pH values: The weekly amount of carbonate hardness (together 0.4 ° dH) was sufficient to compensate for the KH losses.

The acid drop could thus be reliably prevented, the pH values were stabilized in the pH range 7.3 - 8.0.

4. Introduction of C0 ₂ : The weekly addition of degradable organic compounds (citric acid, tartaric acid, sucrose, iron citrate, sodium citrate, magnesium citrate) ensured that Release of sufficient C0 ₂ to adequately meet the weekly C0 ₂ requirements of the aquarium.

The CO ₂ concentration remained between 2.5 and 20 mg / 1 CO ₂ .

5. Supplementation of trace elements:

The weekly addition of the trace elements listed in Table 1 (Fe to Co) steadily compensated for the losses due to trace element consumption or elimination, recognizable by very good plant growth and vital healthy fish. The fish losses were zero.

6. Supplementation of the water-soluble vitamins: The B vitamins (B1 to Biotin) listed in Table 2 were added to the aquarium water weekly in the specified application concentrations.

7. General biological assessment of the test aquariums after 7 months without water change:

The aquariums treated once a week with the composition according to the invention showed in comparison to the untreated control aquariums

* lower fish mortality (no fish died in the entire period),

* significantly improved growth and appearance of aquatic plants,

* less algae growth. The status of the aquariums was so favorable that an even longer extension of the water change-free period seems possible, for example 9 to 12 months.

Composition, preparation, dosage form of the combination product or preparation according to the invention:

The exact composition of the combination product or preparation is derived from

* the active ingredient concentrations to be introduced into the housing water (e.g. the concentrations listed in Table 3 for the weekly

Dosage and the raw materials or active ingredient precursors derived therefrom);

* the amount of water to be treated or stabilized (e.g. 1 pack for 100 - 1000 1 aquarium water);

* the dosing frequency, e.g. B.

- Every day )

- every 2 days )

- twice a week) is preferred

The combination agents according to the invention can be in the form of concentrates, aqueous solutions or solid

Preparations such as As powders, granules, extrudates, tablets, beads or in capsules can be provided. In addition to the pure active substances or active substance precursors, the preparations can contain further components corresponding to the prior art, for example preservatives, thickeners, once a week) - 1 x per 2 weeks suspension stabilizers for liquid preparations, dyes, technological aids for granulation, tableting or extrusion, flow improver for powders.

Claims

O 01/2153432 patent claims

1.) Water treatment agent for the long-term improvement of the water quality of biological housing systems, characterized by a content of

a) at least one easily or slightly soluble AI 3+ Fe ³⁺ , Ti0 ²⁺ , or Zr0 ²⁺ salt of an organic carboxylic acid, optionally in a mixture with an organic carboxylic acid;

b) at least one water-soluble N-free, biodegradable organic compound;

c) at least one soluble alkali or alkaline earth metal salt of an organic carboxylic acid, and

d) at least one Mg ²⁺ salt of an organic carboxylic acid, optionally in a mixture with at least one Ca ²⁺

Salt of an organic carboxylic acid as well

e) trace elements and vitamins, especially water-soluble vitamins of the B series.

2.) Composition according to claim 1, containing

a) an Al ³⁺ , Fe ³⁺ , Ti0 ²⁺ and / or Zr0 ²⁺ acetate, formate, tartrate and / or in particular citrate;

b) at least one carboxylic acid, an alcohol and / or a sugar; c) an alkali or alkaline earth metal salt of citric, acetic, lactic, tartaric, formic or malic acid and

d) a Ca ²⁺ or Mg ²⁺ salt or a mixture of Ca ²⁺ and Mg ²⁺ salts of organic carboxylic acids, and

3.) Composition according to claim 1 or 2, containing as component a) aluminum citrate and / or iron citrate.

4.) Composition according to claim 1 or 2, containing as component b) acetic, citric, tartaric or lactic acid, glycerol, sorbitol or ethanol or a pentose, a hexose or sucrose.

5.) Composition according to claim 4, containing as component b.) A combination of citric acid, tartaric acid and sucrose.

6.) Composition according to claim 1 or 2, containing as component d) a sodium and / or magnesium salt of citric and / or tartaric acid.

7.) Composition according to claim 1 or 2, containing as component e) magnesium citrate and / or tartrate, optionally in a mixture with calcium citrate and / or tartrate.

8.) Composition according to claim 1 or 2, containing as

Trace elements iron, boric acid, bromide, iodide, lithium, tin, manganese, zinc, nickel, copper, vanadium, molybdenum and / or cobalt. O 01/21534

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9.) Composition according to claim 1 or 2, containing as vitamins vitamin Bl, B2, B ^β , B12, nicotinamide, panthenol and / or biotin.

10.) Composition according to claims 1 to 9, containing per unit dose for 1 1 housing water, the components in the following amounts:

a) 0.5-50 mg, preferably 0.5-10 mg;

b) one or more organic compounds, preferably citric acid, sucrose and / or tartaric acid, in each case 0.5-100 mg, preferably 0.5-50 mg, particularly preferably 1-20 mg;

c) 0.018-1.8 mmol alkali metal salt, preferably 0.036-0.36 mmol, or 0.009-0.9 mmol alkaline earth metal salt, preferably 0.018-0.18 mmol, or corresponding mixtures of alkaline earth and alkali metal salts;

d) 0.0018-0.36 mmol magnesium salt, preferably 0.018-0.18 mmol;

e) 1 - 100 ug iron, preferably 2 - 20 ug; 0.5 - 50 μg boric acid, preferably 0.5 - 10 μg; 0.1-100 μg bro id, preferably 0.1-5 μg; 0.01 - 100 μg iodide, preferably 0.1 - 10 μg; 1 - 200 ng lithium, preferably 5 - 100 ng; 1 - 200 ng tin, preferably 5 - 100 ng;

0.1-100 μg manganese, preferably 0.2-20 μg;

0.1-100 μg zinc, preferably 0.1-10 μg;

0.01-20 μg nickel, preferably 0.05 - 5 μg; .01 - 20 μg copper, preferably 0.05 - 5 μ - 500 ng vanadium, preferably 5 - 100 ng; 500 ng molybdenum, preferably 5-100 nngg; , 1-50 ng cobalt, preferably 0.5-20 nngg; , 1 - 100 μg vitamin B1, preferably 0.1 - 50 μg; , 05 - 50 μg vitamin B2, preferably 0.05 - 10 μg ^; , 01-30 µg vitamin B6, preferably 0.05-10 µg ^; , 05 - 50 ng vitamin B12, preferably 0.1 - 10 ng; , 1-50 μg nicotinamide, preferably 0.1-20 μg ^; , 1 - 100 μg panthenol, preferably 0.1 - 10 μg; and, 01-10 μg biotin, preferably 0.01-1 μg;