Patent Application
20200369537
The invention relates to a solid dosing agent and to a process for the production thereof and use thereof for dosing phosphate and/or polyphosphate in water as claimed in claims 1, 5, and 7.
For the protection of health, pipework, storage units, equipment, etc., water is generally treated before use by means of commercially available water filter cartridges. A key aspect thereof is controlling and/or preventing the formation of limescale.
This can include, firstly, the removal of hardeners from the water, for example by means of cation exchangers. In this process, calcium and magnesium ions are, for example, exchanged for sodium ions.
A second possibility is the inhibition of crystallization, i.e. the stabilization of hardness through the addition of inhibitors, for example polyphosphates. Normally, these are added to the untreated water in order to exchange them with a carbonate group, thereby disrupting limescale nucleation.
One way of achieving this is by liquid dosing with freely soluble polyphosphates or by solubility-controlled dosing through contact with poorly soluble polyphosphates.
Freely soluble polyphosphates are mostly sodium salts of polyphosphates, poorly soluble polyphosphates accordingly being calcium or magnesium polyphosphate salts.
In the case of dosing in a water tank, for example in a water tank of a household appliance, a problem up to now has been the inability of the poorly soluble salt to release sufficient polyphosphate for protection against limescale, particularly of the water tank itself, i.e. of the surfaces thereof that come into contact with the water to be stored therein. Over the course of time, this results in undesirable and unsightly deposits forming on these surfaces too.
Moreover, it is not possible for the poorly soluble polyphosphate to be stored together with a weakly acidic ion exchanger, as is the arrangement, for example, when a filter cartridge serves as a filter bed; for example, a filter cartridge for a water tank of a household appliance, since the weakly acidic ion exchanger of the filter cartridge gives rise to ambient humidity levels of over 80% relative humidity in the airtight film packaging. Airtight packaging is in turn necessary to protect the ion exchanger from drying out.
However, the stable storage of poorly soluble polyphosphate is not possible if the relative humidity is greater than 50%. If poorly soluble polyphosphate and damp ion exchanger are packed together, the consequences of this are efflorescence and free water on the surface of the polyphosphate, which disperses within the film packaging, leaving behind white spots on the product.
The use of liquid polyphosphate is likewise problematic, since not only must the dosing process employed persist for three months, overdosing must not occur. Although release can be adjusted to a certain degree by minimizing the contact surface area and diffusion, this barely addresses the problem of storage (leakage and drying out) and that of overdosing on prolonged contact.
For dosing polyphosphates within mains-fitted water-treatment devices, especially decarbonization filters, there are likewise no easy technical solutions to the problems of adequate dosage, storage in a closed container at high relative humidity, and avoidance of overdosing.
The object underlying the invention is accordingly to provide improvements both in the storage stability for antiscaling agents containing polyphosphate and in the dosing of polyphosphate from such an antiscaling agent in water.
This object is achieved by the features of claims 1, 5, and 7. The dependent claims specify advantageous and expedient developments.
The invention accordingly relates to a solid dosing agent for dosing phosphate and/or polyphosphate in water. This is characterized by the provision of a water-insoluble anion exchanger that is at least partially loaded with orthophosphate and/or polyphosphate counterions.
By using an anion exchanger having polyphosphate counterions for dosing polyphosphate in water, the ionic bonding of polyphosphate ions on an anion exchanger allows long-lasting stable storage of the polyphosphate to be achieved.
Not only that, but this bonding of polyphosphate to an anion exchanger allows polyphosphate release to be kept within an upper limit through ion-exchange equilibria reactions. Below the equilibrium, particularly with untreated water, the rate of release is however high, with the result that sufficient polyphosphate can be released over a long period.
In a preferred embodiment, a basic anion exchanger, in particular a weakly basic anion exchanger, is provided.
In another preferred embodiment, an anion exchanger based on polystyrene is provided.
An anion exchanger based on polyacrylate may alternatively or additionally be provided.
The invention also relates to a process for producing a solid dosing agent for dosing phosphate and/or polyphosphate in water. This is characterized by the use of a liquid polyphosphate solution, in particular a sodium polyphosphate solution, as starting material for loading the water-soluble anion exchanger.
The anion exchanger may preferably be loaded with polyphosphate ions by first filtering the polyphosphate solution, in particular the sodium polyphosphate solution, through an acidic cation exchanger, preferably a strongly acidic cation exchanger, and then passing it through the anion exchanger in OH−/free base form.
The invention further relates to the use of a solid dosing agent for dosing phosphate and/or polyphosphate in water. This is characterized by it being used for stabilizing water hardness.
The anion exchanger having polyphosphate counterions is preferably used in a filter device, especially in a water filter device.
In a preferred use, the water filter device may be used in a water tank, especially in a water tank of a hot-beverages machine and/or of a household appliance.
In particular, the water filter device may be used to prevent deposits from forming on surfaces in the water tank that come into contact with the water.
The water filter device may, however, also be used as a mains-fitted water filter device.
In the stabilization of water hardness through the use of an anion exchanger having polyphosphate counterions for dosing polyphosphate in water, the ionic bonding of polyphosphate ions on an anion exchanger allows long-lasting stable storage of the polyphosphate to be achieved.
Not only that, but this bonding of polyphosphate to an anion exchanger allows polyphosphate release to be kept within an upper limit through ion-exchange equilibria reactions. Below the equilibrium, particularly with untreated water, the rate of release is however high, with the result that sufficient polyphosphate can be released over a long period.
By exchanging carbonate ions, for example those present in untreated water, with the polyphosphate ions, in particular ionically bonded polyphosphate ions, loaded onto the anion exchanger, the crystallization of calcium carbonate/limescale in the water can be stopped or at least disrupted. This means that the hardness present does not precipitate and does not result in deposits forming on surfaces that come into contact with the water.
Preference is given to using a basic anion exchanger, in particular a weakly basic anion exchanger. Weakly basic ion exchangers have the advantage that they have considerably higher capacity compared to strongly basic ion exchangers. This allows considerably more polyphosphate ions to be applied to the anion exchanger and/or means that loading with the same quantity of polyphosphate ions requires a considerably smaller proportion of anion exchanger than is the case with a strongly basic anion exchanger for example.
In one particular embodiment of the invention, a weakly basic polyacrylate-based anion exchanger is used. Polyacrylate-based anion exchangers exhibit more favorable nitrosamine release compared even to suitable polystyrene-based anion exchangers.
In one use, the anion exchanger having polyphosphate counterions may be used in a filter device, especially in a water filter device.
The water filter device may preferably be used in a water tank, especially in a water tank of a hot-beverages machine and/or of a household appliance.
The water filter device may be used here, for example, to prevent deposits from forming on surfaces in the water tank that come into contact with the water.
The water filter device, however, also be used as a mains-fitted water filter device.
In such uses too, the invention described herein provides a material that is storage stable and allows uniform dosing of polyphosphate.
In a process for producing an anion exchanger having polyphosphate counterions, the starting material used for the polyphosphate anion employed may be a liquid polyphosphate solution, in particular a sodium polyphosphate solution. Sodium polyphosphate solutions are liquid at high concentrations of up to approx. 30% by weight, which makes dosing with them simple and means that the storage thereof takes up less space.
In a preferred production process, the anion exchanger may be initially loaded with polyphosphate ions using the polyphosphate solution, in particular the sodium polyphosphate solution. The solution is then advantageously passed through an acidic cation exchanger, preferably a strongly acidic cation exchanger, for example filtered and then passed through the anion exchanger in OH−/free base form. In order to transfer the polyphosphate solution to the anion exchanger in high yield, this should advantageously be diluted with water before use to a concentration of preferably 0.5% to 5% by weight.
In summary, it can be noted that, in the process for stabilizing hardness, an anion exchanger having polyphosphate counterions is used for dosing polyphosphate in water.
For production, the initially liquid polyphosphate can be bonded ionically to a preferably weakly basic anion exchanger. This is because weakly basic anion exchangers have a considerably higher loading capacity by comparison with strongly basic ones. This allows the same loading capacity to be provided with a considerably smaller amount of anion exchanger by comparison with a strongly basic anion exchanger. There is also a corresponding reduction in the space required therefor and in the volume needed.
The exchanger treated in this way may be stored almost indefinitely both in the dry and wet states. Moreover, the release of polyphosphate in contact with water is kept within an upper limit through ion-exchange equilibria reactions with substances present in the water. Below the equilibrium with untreated water, the rate of release is however high, with the result that sufficient polyphosphate can be released over a long period.
Preference is given to using a weakly basic polystyrene-based anion exchanger as the anion exchanger.
Alternatively, a preferably weakly basic polyacrylate-based anion exchanger may be used.
The envisaged starting material for the polyphosphate anion used is a liquid polyphosphate solution, in particular a liquid sodium polyphosphate solution.
The anion exchanger is loaded with polyphosphate ions by first filtering the polyphosphate solution, in particular the sodium polyphosphate solution, through a preferably strongly acidic cation exchanger in H+ form and then passing it through the anion exchanger in OH−/free base form.
The present invention is elucidated in more detail hereinbelow with reference to the included figures and the description that refers to them.
In the figures:
[H2PO4−]N: Polyphosphate ion having
chain length N and N negative charges
[H3PO4]N: Polyphosphoric acid
R−: Strongly acidic cation exchanger
R+: At least weakly basic anion exchanger
Step 1: Removal of Sodium
N.Na++[H2PO4−]N+N.[R−H+]N.[R−Na+]+[H3PO4]N
Step 2: Bonding of Polyphosphate on Anion Exchanger
N.[R+OH−]+[H3PO4]NN. R+[H2PO4−]N+N.H2O
In process step “1.)”, the anion exchanger is loaded with polyphosphate ions by first filtering the sodium polyphosphate solution 21 through a preferably strongly acidic cation exchanger 23 and then passing it through the anion exchanger 24 in accordance with process step “2.)” The latter may be present, for example, in at least weakly basic OH−/free base form.
In the assembly 20 shown by way of example, the sodium polyphosphate solution 21 held in container 21.1 is passed in the direction of arrow 21.2 onto the strongly acidic ion exchanger granules 23 in H+ form in a container 22 in order to separate the polyphosphate from the sodium, and is then fed, via the outlet 22.1, onto the support material in container 25, which is in the form of anion exchanger granules 24, in order to load the latter with polyphosphate.
Residual demineralized water 27 is run off into a container 26 through the outlet 25.1, which is provided with a means of closure 25.2.
The polyphosphate that is now ionically bonded to the anion exchanger granules 24 has almost limitless storage stability and is stable under both dry and wet conditions.
In the figure:
R+N.[H2PO4−]N+N.[HCO3−]R+N.[HCO3−]+[H2PO4−]N
The release of polyphosphate in contact with water is kept within an upper limit through ion-exchange equilibria reactions with substances present in the water. Below the equilibrium with untreated water, the rate of release is, by contrast, high. This allows sufficient release of polyphosphate over a long period.
This process for stabilizing hardness thus uses an anion exchanger having polyphosphate counterions for dosing polyphosphate in water. This is preferably a weakly basic polyacrylate-based anion exchanger. Alternatively, a weakly basic polystyrene-based anion exchanger may be used.
The starting material for the polyphosphate anion used is a liquid polyphosphate solution, in particular a sodium polyphosphate solution. Potassium polyphosphate solutions are also conceivable.
The anion exchanger is loaded with polyphosphate ions by first filtering the sodium polyphosphate solution through a preferably strongly acidic cation exchanger and then passing it through the anion exchanger in OH−/free base form.
The water filter cartridge 1 comprises a housing 2, an inlet opening 1.3 and an outlet opening 1.4 for the inflow and outflow of the water 8 held in the water tank into the filter cartridge 1 and back out again. For use in, for example, a hot-beverages machine 11 connected downstream, this water 8 is treated by passage through a filter train 4. Such a filter train may be designed in the upflow chamber 1.1 and/or the downflow chamber 1.2. The arrows 8.1 indicate the direction of flow of the water during the withdrawal thereof from the water tank 10 when the filter cartridge 1 in the fully operational state is in operation as a filter.
The water filter cartridge 1 comprises, in addition to the filter train 4 and designed separately therefrom, a reservoir 6, preferably in the form of a storage tank for an antiscaling agent 5, in particular an agent countering the formation of limescale in the water tank, with contact openings 7 provided that connect the reservoir 6 with the water 8 held in the water tank 10.
The reservoir 6 may be positioned in the housing 2 of the water filter cartridge 1; in the illustrated case in a top unit 2.1 of the housing.
The agent 5 countering the formation of limescale in the water tank may include a weakly acidic cation exchanger and/or a hardness stabilizer and/or a poorly soluble polyphosphate, in particular one that is calcium-based.
The agent 5 countering the formation of limescale in the water tank may include a freely soluble polyphosphate that is sodium-based.
In addition, the agent 5 countering the formation of limescale in the water tank may include a weakly basic anion exchanger material, in particular a weakly basic anion exchanger material having polyphosphate ions as counterions.
And the weakly basic anion exchanger material may be provided as a stabilizing agent for the polyphosphate.
The arrows 8.1 indicate the inflow of the water 8 held in the water tank 10 into the agent 5 countering the formation of limescale in the water tank. It flows through the contact openings 7 into the reservoir for the agent 5. A casing 9 or the like is optionally also provided to additionally enclose the agent 5.
The arrows 5.1 indicate the water 8 held in the water tank 10 that has already been treated with the agent 5 countering the formation of limescale in the water tank. Because the treatment substances from the agent 5 are in higher concentration in the water 8 close to the agent 5 compared to water held elsewhere in the water tank but which has not yet come into contact with the agent 5, a concentration equilibrium develops that, over the course of the storage period, also effects treatment of the remaining water stored in the water tank and thereby, in accordance with the invention, prevents the formation of limescale on the surfaces coming into contact with the water.
An agent 5 countering the formation of limescale, in the form of a hardness stabilizer, may also additionally be provided in the area through which the water undergoing treatment passes in and/or around the water filter cartridge 1. For example in and/or around the area of water inflow into the filter cartridge. A reservoir 6 therefor may also be provided, for example, in the form of a space at least partially enclosed by a fabric, for example, an insert component such as a ring filled with the agent 5, or in the form of a filling, preferably at least outwardly secured with a means of preventing the contents from escaping, for example a casing or the like. As an example thereof, a reservoir 6 filled with an agent 5 is shown above the inlet opening 1.3 in
| Number | Date | Country | Kind |
|---|---|---|---|
| 10 2018 103 004.5 | Feb 2018 | DE | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/EP2019/052686 | 2/5/2019 | WO | 00 |
