WO1998034877A2

WO1998034877A2 - Two-component agent for water-treatment in aquariums for tropical fish

Info

Publication number: WO1998034877A2
Application number: PCT/EP1998/000490
Authority: WO
Inventors: Günter Ritter; Uwe Erfeling
Original assignee: Tetra Werke Dr. Rer. Nat. Ulrich Baensch Gmbh
Priority date: 1997-02-10
Filing date: 1998-01-30
Publication date: 1998-08-13
Also published as: EP0958246A2; WO1998034877A3; JP2001511064A

Abstract

The invention relates to a two-component agent comprising a biotolerant flocculant containing polymeric aluminium salts and polybasic organic acids, and an active ingredient mixture as a co-flocculant, containing one or several carbonate hardness or alkalinity carriers, a magnesium ion carrier and hydrocolloids. Said agent is used for water treatment and the elimination of bacteria, algae, viruses, pathogens, parasites and heavy metals by flocculation in aquariums for tropical fish, particular in the presence of soft water. The invention also relates to the use of the two-component agent and methods for treating water by flocculation.

Description

Two-component agent for the water clarification of tropical

Ornamental fish aquariums

description

The invention relates to a two-component agent for water purification and removal of bacteria, algae, viruses, pathogens, parasites and heavy metals by flocculation treatment of tropical ornamental fish aquariums, especially in soft water, its use and methods for water purification by flocculation treatment.

When holding tropical freshwater fish in aquariums of the types: - Complete or show aquarium,

- bare, not furnished aquarium for quarantine, treatment, sales purposes,

- Keeping aquariums in trade fairs and exhibitions sometimes lead to undesirable water cloudiness.

A distinction can be made between the following causes of water turbidity:

- Planktonic algae, which lead to cloudy green water, are rarely observed in aquariums. - Finely distributed to colloidal mineral particles, e.g. B. as abrasion from aquarium gravel when it is newly introduced, churning or washing; Tones from substrate fertilizers, which are brought in or brought into the Soil to be washed out. The result is a whitish, milky cloud of water.

- Mass development of planktonic unicellular organisms that occur after bacterial mass developments, e.g. B. in freshly furnished aquariums. The result is an opaque milky water cloud.

The last-mentioned biological turbidity can be expected more frequently in the following aquariums:

- Very small vessels, aquariums and / or bowls without filtration or filter systems, especially with dense stocking.

- Average aquariums with heavy overfeeding and / or insufficient filter performance.

- Freshly set up and furnished show aquariums, e.g. B. at trade fairs, congresses and conferences, exhibitions,

Trade fairs etc. with a biologically not yet activated filter system.

Common to all of the opacities described is that they are undesirable for aesthetic and biological reasons and cannot be eliminated at short notice by conventional filtering methods.

The natural disappearance of such cloudiness, e.g. B. by sedimentation, adsorption, death or biodegradation usually takes days to weeks.

Analogous occurrences of cloudiness in garden ponds are very effectively removed or reduced by adding flocculants based on monomeric and polymeric aluminum salts according to the prior art.

Flocculants like these have proven to be particularly biologically compatible, even with relatively soft water are described in WO 9626905. The special biological compatibility was achieved by combining polymeric aluminum salts, e.g. B. polymeric aluminum chloride (Al ₂ (OH) ₅ C1), achieved with polybasic organic carboxylic acids, especially tartaric acid.

It was therefore initially obvious to use these biotolerant non-toxic flocculants for garden ponds also to clarify the described cloudiness in aquariums, populated with tropical fish.

Surprisingly, however, it was found that tropical ornamental fish, which are kept in hot water aquariums, are very sensitive to any flocculation treatment with aluminum salts.

Even with the addition of biotolerant flocculants

(containing polymeric aluminum chloride and polybasic carboxylic acids) tropical ornamental fish show acute stress reactions, especially in softer water.

When the carbonate hardness was above 4 ° dH, breathing was greatly accelerated and the fish looked very restless.

The fish recovered within a few hours, but such water treatment, especially with repeated repetition, which triggers such pronounced stress reactions in ornamental fish, can lead to a severe weakening of the condition and resistance of the fish. In addition, the user would not accept a product with the clear side effects described.

With carbonate hardness below 4 ° dH, the stress-related behavioral reactions of the ornamental fish became even more intense Time to fully recover the fish even longer (8-24 hours).

With carbonate hardness of 2 ° dH and below, an increasing mortality of the fish was observed.

Because tropical ornamental fish very often from extremely soft

Waters originate and therefore are often kept in soft water (carbonate hardness <4 ° dH) in the aquarium, the sole use of the described biotolerant flocculants for clarifying cloudy aquarium water was not advisable for the reasons described.

Other aluminum-free flocculants, e.g. B. based on quaternized acrylamides, led to unsatisfactory clarification results or had a toxic effect on ornamental fish.

The invention was therefore based on the object of developing clarifying agents and processes for eliminating the cloudiness described at the outset in aquariums, which are also distinguished by a very good fish tolerance in soft water.

In our investigations to minimize fish toxicity and possible harmful effects in the flocculation treatment of cloudy aquarium water with polymer aluminum hydroxychloride alone or in combination with polybasic organic carboxylic acids, it was surprisingly found that after a previous water treatment with a mixture of active substances acting as coflockulans, significant improvements in flocculation behavior and fish toxicity were found Effects are achieved. The invention therefore relates to a two-component agent for clarifying and purifying the water in ornamental fish aquariums, consisting of a flockulan and the active ingredient combination of a coflockulan, and to a method for clarifying and purifying by defined use of the two-component agent.

Another object of the invention is a combination of active substances suitable as coflockulans.

The lower limit of carbonate hardness, at which flocculation treatment is still possible without acute toxic side effects, is reduced from KH 2 - 4 ° dH or alkalinity 0.71 - 1.41 mVal / 1 (with biotolerant flocculants alone) to below KH 0. 5 ° dH or alkalinity 0.18 mVal / 1 reduced.

Since tropical aquarium fish are generally kept in water with carbonate hardness> 0.5 ° dH, the combination of biotolerant flocculant (polymeric Al-hydroxychloride + polybasic carboxylic acid) and special coflockulans according to the invention can be used in aquariums without restrictions.

In the case of carbonate hardness above 4 ° dH or with an alkalinity above 1.43 mVal / 1, even unchanged polymeric aluminum chloride (without polybasic carboxylic acid) is moderated by the coflockulan according to the invention to such an extent that toxic effects on ornamental fish no longer occur and therefore this combined treatment is avoided the limitation - carbonate hardness above 4 ° dH - can also be used. The stress effect on ornamental fish is, however, to be classified higher than with the combination of biotolerant flockulans and coflockulans according to the invention described first. In addition, the Limit for carbonate hardness too high.

The use of the first-mentioned combination is therefore preferred in any case.

The treatment of cloudy aquarium water according to the invention uses the combination of a biotolerant flocculant and a mixture of active substances as coflockulans. The composition of the two components is described as follows:

1. Biotolerant flocculant:

Solution of polymeric aluminum salt, e.g. B. polymeric

Aluminum chloride, Al ₂ (OH) ₅ Cl, and one (or more) polybasic organic acids in the molar ratio AI: organic acid between 0.5: 1 and 50: 1, preferably between 2: 1 and 10: 1.

The following polybasic organic acids have proven to be suitable:

Citric acid, glycolic acid, tartaric acid, maleic acid, hydroxymaleic acids, hydroxy tartaric acids, malonic acid, malic acid, lactic acid, tartronic acid, - hydroxypropionic acid, sugar acids, such as. As gluconic acid, sugar acid, glucuronic acid, mucic acid or mannosugaric acid.

Of all the acids mentioned, L-f-tartaric acid in combination with polymeric aluminum hydroxychloride has achieved the best results.

2. Active ingredient mixture of coflockulans:

The mixture of active ingredients consists of several functional components: a) Carbonate hardness carriers, alkalinity carriers, preferably alkali hydrogen carbonates in an amount of 25-40% by weight, based on the total weight of the coflockulan. NaHC0 ₃ and / or KHCO3 are preferred, particularly preferably a mixture of NaHC02 in an amount of 15-25% by weight and KHCO3 in an amount of 10-15% by weight. Introducing carbonate hardness before adding * the flocculant increases the initial carbonate hardness and, after adding the flocculant, compensates for the carbonate hardness that occurs during the formation of AI (OH) 3 flakes.

b) Magnesium ion carrier in an amount of 50-60% by weight based on the total weight of the coflockulan, preferably MgSO ₄ (with 30% H ₂ O). The addition of Mg ₂ ⁺ ions increases the Mg ₂ ⁺ content in the aquarium water. Mg ₂ ⁺ - ions can facilitate 3 -Flockung floc formation in the AI (OH).

c) hydrocolloids, selected from naturally occurring biopolymers, preferably with free carboxylate groups and / or sulfate groups, such as, for example, alginic acid and its soluble salts (Na, Mg alginate), gum arabic, tragacanth gum, pectins, xanthan gum, carrageenan,

Furcelleran, Locust bean gum (Carob), Tara gum, Ghatti gum, Guar gum, Agar gum, Khaya grandifolia gum, Karaya gum, Arabian (araban), Gellan, starch, Konjac mannan, Galactomannan, Funoran, Acetan, .Welan, Rhamsan , Succinoglycan, scleroglycan, schizophyllan, tamarind gum, curdlan, pullulan, dextran and mixtures of the selected biopolymers with a total content of 2 - 20%. Carrageenan is preferred and commercially available carrageenan / furcelleran mixtures are very particularly preferred as food additives.

A mixture of active ingredients that has proven very successful in the studies has the following composition:

NaHC0 ₃ 20%

MgS0 ₄ (30% H ₂ 0) 55% carrageenan 12%

In addition to the functional components described, further constituents can be added to the solid mixture, which do not contribute to flocculation support, but which also contain other additive functions, e.g. B. table salt (NaCl), Ca salts, enzyme preparations to improve the breakdown of organic water contaminants, dyes.

The resulting mixture of active ingredients can be in the form of a powder,

Tablet, granules, extrudate, agglomerate, capsule u. a. fixed application forms are used.

In the flocculation of turbidities from aquarium water according to the invention, a liquid flocculant with high biotolerance and a solid mixture of active ingredients are used as coflockulans.

Typical examples of the two components are described below:

Example 1: Biotolerant flocculant

500 ml of a concentrated solution of Al ₂ (OH) ₅ C1 - 2 - 3 H ₂ 0 (approx. 50% solution; 23.5% Al ₂ 0 ₃ ) with 100 g L + - tartaric acid become 1 1 solution with Aqua demin. diluted with stirring. The resulting slightly viscous, clear and long-term stable solution is used to clarify cloudy aquarium water as described below.

Example 2: Active ingredient mixture, coflockulans

20% NaHC0 ₃ , 13% KHCO3, 55% MgS0 ₄ (30% water) and 12% Carrageenan are mixed and the white powder mixture is used to clear turbidity in the aquarium water as described below.

Example 3: Application example

Aquarium water, which is significantly to very cloudy due to planktonic algae, mineral particle suspensions or planktonic unicellular organisms, is treated as follows:

10 minutes to about 60 minutes before the addition of the biotolerant flocculant, 0.1 to 10 g per 10 liters, preferably 0.5 to 2 g per 10 liters, of active ingredient mixture, coflockulan, are added to the aquarium water.

After mixing and dissolving the water additive, flocculation takes place about 10 to 60 minutes later by metering in the biotolerant described in Example 1

Flocculant in an amount of 0.1 to 10 ml per 10 liters, preferably from 0.5 to 1.5 ml per 10 liters of aquarium water.

The dosage is chosen so that 1.0 to 100 mg / 1 Al ₃ ^+, preferably 5-15 mg / 1 Al ₃ ^{+, are} introduced into the treated water.

With the combination of the agents according to the invention and the type of addition mentioned above and the amount of the dosage, even with very low carbonate hardness in the starting water (≥ 0.5 ° dH), the flocculation of the opacifying agents begins within 5 to 10 minutes after the addition. After about 2 to 12 hours, the flakes - plus turbidity - have settled as agglomerates or have been bound in the filter material. The aquarium water was completely cleared without adversely affecting the ornamental fish and other aquatic animals and plants. Even in extremely soft water down to carbonate hardness of 0.5 ° dH or alkalinity of 0.18 mVal / 1, the combined treatment in all aquariums can be carried out safely and successfully without restrictions, without harming the fish, plants and other aquatic organisms recognizable damage is inflicted.

Complete flocculation of turbidities in aquarium waters, caused by floating algae, mineral particles, mass development of single cells or their combination, is achieved. The aquarium water is clear again already about 2 to 12 hours after the application of the two-component agent according to the invention.

The combination of flocculant and coflockulans leads to

- accelerated flaking,

- compensating for the Al ₃ ⁺ -bedingten loss of carbonate hardness or alkalinity,

- Possibility of repeated application without impairing the buffering capacity of the

Aquarium water and thus its pH stability.

The described combined treatment of aquarium water also eliminates high-molecular particles, pathogens, bacteria, viruses, parasites and heavy metals by flocculation and can therefore also be used for the successful cleaning of aquarium water, in which there is not necessarily a visible cloudiness of the water.

Due to the safe repeatability of using the method according to the invention, the agents according to the invention are also outstandingly suitable for one periodic use for the prophylactic purification of water from tropical ornamental fish aquariums.

Claims

claims

1. Two-component agent for clarifying and purifying the water of ornamental fish aquariums consisting of a biotolerant flocculant and the active ingredient mixture of a co-flocculant.

2. Two-component agent according to claim 1, characterized in that the biotolerant flocculant in a solution contains polymeric aluminum salts and at least one polybasic organic acid.

3. Biotolerant flocculant according to claim 2, characterized in that the polymeric aluminum salt and the polybasic organic acid are contained in the molar ratio AI: organic acid between 0.5: 1 and 50: 1.

4. Flocculant according to claim 2 or 3, characterized in that the polymeric aluminum salt and the polybasic organic acid are contained in the molar ratio AI: organic acid between 2: 1 and 10: 1.

5. Flocculant according to claims 2 to 4, characterized in that the polymeric aluminum salt is polymeric aluminum hydroxychloride.

6. flocculant according to claims 2 to 5, characterized in that the polybasic organic acid or a mixture thereof is selected from the group citric acid, glycolic acid, tartaric acid, maleic acid, hydroxymaleic acids, hydroxy tartaric acids, Malonic acid, malic acid, lactic acid, tartronic acid, α-- hydroxypropionic acid, gluconic acid, sugar acid, glucuronic acid, mucic acid and / or mannosugaric acid.

7. Flocculant according to claims 2 to 6, characterized in that the polybasic organic acid is L + tartaric acid.

8. Two-component agent according to claim 1, characterized in that the co-flocculant is composed of carbonate hardness carriers, magnesium ion carriers and hydrocolloids.

9. Co-flocculant, characterized in that 25-40% by weight carbonate hardness carrier, 50-60% by weight magnesium ion carrier and 2-20% by weight hydrocolloids.

10. Co-flocculant according to claim 9, characterized in that the carbonate hardness carrier is an alkali hydrogen carbonate or a mixture of alkali hydrogen carbonates.

11. Co-flocculant according to claims 9 or 10, characterized in that the carbonate hardness consists of 15-25% by weight NaHC0 ₃ and 10-15% by weight KHCO3 based on the total weight of the co-flocculant.

12. Co-flocculant according to claim 9, characterized in that the magnesium ion carrier is MgSO ^ (with 30% H ₂ 0).

13. Co-flocculant according to claim 9, characterized in that the hydrocolloid is selected from the group of alginic acid and its soluble salts

(Na, Mg alginate), gum arabic, tragacanth gum, pectins, xanthan gum, carrageenan, furcelleran,

Locust bean gum (Carob), Tara gum, Ghatti gum, Guar gum, Agar gum, Khaya grandifolia gum, Karaya gum, Arabian (araban), Gellan, starch, Konjac mannan, Galactomannan, Funoran, Acetan, Welan, Rhamsan, Succinoglycan, Scleroglycan, Schizophyllan, Tamarind gum, Curdlan, Pullulan, Dextran and their mixtures.

14. Co-flocculant according to claim 13, characterized in that the hydrocolloid is carrageenan or a carrageenan / furcelleran mixture.

15. Co-flocculant according to claim 9, characterized in that it contains 20% NaHC0 ₃ , 13% KHC0 ₃ , 55% MgS0 ₄ (30% H ₂ 0) and 12% carrageenan / furcelleran mixture.

16. Use of a two-component agent according to claim 1 for removing turbidity, algae, high molecular weight particles, pathogens, bacteria, viruses, parasites and heavy metals from the water of aquariums.

17. Processes for removing turbidity, algae, high-molecular particles, pathogens,

Bacteria, viruses, parasites and heavy metals from the water of aquariums, characterized in that first a co-flocculant according to claims 9 to 15 and then a biotolerant flocculant according to claims 3 to 7 is evenly distributed in the aquarium water.

18. The method according to claim 17, characterized in that the biotolerant flocculant is added to the aquarium water 10 to 60 minutes after the co-flocculant.

19. The method according to claim 17 or 18, characterized in that the co-flocculant in an amount of 0.1 to 10 g per 10 1 aquarium water and the biotolerant flocculant in an amount of 1.0 to 100 mg / 1 Al ₃ ⁺ be introduced into the aquarium water.

20. The method according to claim 17 or 18, characterized in that the co-flocculant in an amount of 0.5 to 2 g per 10 1 aquarium water and the biotolerant flocculant in an amount of 5 - 15 mg / 1 Al ₃ ⁺ in the Aquarium water can be introduced.