Patent Description:
Water softening methods are well known and typically involve a pressurized water treatment wherein a water stream is passed through a filter comprising a cation exchange material (either inorganic or organic), thereby producing a softened water which is desirable for household applications like laundering, bathing and dish washing, devices like coffee machines, in particular those with steam production, as well as many industrial applications.

The main purpose of water softening is to protect devices from lime scale. This is accomplished by exchanging calcium and magnesium ions (the so-called hardness) in a water stream for example for sodium or potassium ions.

Other filters containing a weak acid cationic ion exchange resin (WAC) as cation exchange material. Such filters exchange the hardness against protons. This means that water softening is accompanied by a drop of pH of the treated water.

Each cation exchange material has a defined capacity corresponding to the amount of cations that can be exchanged against hardness. The volume of water that can be treated by the filter before the filter is exhausted and needs to be replaced depends on the composition of the treated water. For obvious reasons it is advantageous to have an indicator for the exhaustion state of the filter.

Classically the criteria used to determine the exhaustion state of a filter is the pH value of a water stream after treatment by the filter comprising the cation exchange material. Usually below a pH value of <NUM> the protection against lime scale is ensured. When the exhaustion rate of the filter has progressed to a point at which the pH exceeds a value of <NUM>, the filter needs to be replaced.

For several reasons the direct determination of the pH value of the water stream after treatment is not an optimum choice to determine the exhaustion state. The price of pH measurements is one aspect. The fact that a pH sensor would need frequent calibrations is another aspect. The optimum solution should be cost efficient and autonomous.

Another method to determine the exhaustion state of a filter can be found in the publications <CIT> and <CIT>.

In <CIT> a first sensor is placed before the filter and measures the electrical conductivity of raw water. The filter is operated in Na+-Mode. A second sensor is positioned downstream of the filter and measures the electrical conductivity of water which has passed the filter. From the measured conductivities, hardness of the raw water and the filtered water is determined. When the determined hardness of the filtered water exceeds a threshold value, a regeneration or exchange of the filter is indicated.

In analogy to <CIT> in <CIT> electrical conductivity measurements are used to determined hardness of a raw water and filtered water. Water hardness is derived from the measured electrical conductivity using a conversion factor. Exhaustion of the filter is indicated when the specific hardness of the softened water exceeds a threshold value.

The publication <CIT> discloses a water softening system with a first bed of liquid treatment medium including cation exchange resin operated in H+ mode that can also be buffered with a potassium salt or a sodium salt. This document also discloses determining electrical conductivity of the softened water with a conductivity sensor in order to determine the reduction in carbonate hardness and thus the amount of free CO2 generated.

The present invention is based on the object to provide a technical solution to the described problem of indicating the exhaustion state of a filter for a water softening process.

This object is achieved by the water softening device having the features of claim <NUM> and by the method to operate a water softening device having the features of claim <NUM>. Preferred embodiments of the device are specified in dependent Claims <NUM> to <NUM>. Preferred embodiments of the method is specified in dependent claims <NUM> to <NUM>.

The present invention is based on the understanding that the result of measurements of electrical properties of the water which is passed through a filter comprising a cation exchange material may serve as an indicator for the exhaustion state of the filter. In comparison to the direct determination of pH values measurements of the electrical conductivity are advantageous. The cost of sensors for the measurements of electrical properties, including the electronics needed to operate them, is considerably lower than for the equipment needed for pH measurements. In addition, sensors for the measurements of electrical properties usually do require only a one time calibration.

A water softening device according to the invention comprises.

The water softening device may further comprise a third sensor for detecting a water flow through the filter. However, this feature is optional.

The device comprises an electronic control unit which is connected to the first sensor, to the second sensor and optionally, if the device comprises the third sensor, to the third sensor, and which comprises an internal data memory and a data processing unit.

Further, the device is configured to determine a ratio between the measured electrical conductivity and/or of the second stream and the measured electrical conductivity and/or resistance of the first stream and use the ratio as an indicator for the exhaustion state of the filter.

In preferred embodiments the water softening device comprises at least one of the following additional features:.

Thus, it is preferred that the device has a modular design. The base unit can comprise all components which do not exhaust during operation. The filter may comprise only a cation exchange material that is subject to exhaustion during operation of the device. When exhaustion occurs, the filter can be replaced. In contrast to this, the base unit is reusable.

In further preferred embodiments the water softening device may be characterized by at least one of the following additional features:.

A screw connection can provide a very reliable and leakproof connection between the base unit and the filter. It is preferred that the filter comprises an opening part with an external thread whereas the base unit comprises a receptacle for the filter with an internal thread, wherein form and dimensions of the threads are matched to one another. The opening provides access to the filter's inlet for the first stream and the outlet for the second stream. The receptacle comprises an entry into the base unit's outlet line. In addition, the base unit's inlet line opens into the receptacle. Preferably the opening and the receptacle are interrelated and adjusted to one another such that the inlet line of the base unit is coupled to the inlet of the filter and the outlet line of the base unit is coupled to the outlet of the filter when the opening part with the external thread is screwed into the receptacle.

In order to provide leakproofness, it can be preferred that one or more sealing compounds, in particular one or more sealing rings, are arranged at the interface between the filter and the base unit.

Of course, it would be also possible to connect the base unit and the filter by other technical means, for example by means of a simple snap connection.

Generally it is preferred that the first sensor and the second sensor are configured to measure an electrical conductivity. Sensors suitable for measuring the electrical conductivity of water, in particular electrolytic cells suitable for measuring the electrical conductivity of water, are known to persons skilled in the art and need no further explanation.

In further preferred embodiments the water softening device may be characterized by the following additional feature:.

Preferably the electronic control unit and all sensors are integral parts of the base unit.

It is particularly preferred that the ion exchange resin is a buffered WAC resin, in particular a WAC resin buffered with at least one salt selected from the group of a potassium salt (K+), a sodium salt (Na+) and a lithium salt (Li+). If the WAC resin is buffered, it contains - besides H+ ions - an amount of metallic cations, in particular K+, Na+ and/or Li+.

Via the bypass line the second stream can be blended with water of the first stream. This may become useful if, for example, as a result of the treatment with the water softening device the pH of the second stream drops too far.

It is preferred that the device is characterized by a combination of all of these features. Such a device is not only capable to determine an exhaustion state of a filter. Moreover, it is capable to issue a warning signal to give information to the operator that the filter is coming to the end of its lifetime and will need to be replaced soon.

It is possible to position the base unit in a fixed, stationary position via the mount. During operation, only the filter has to be exchanged.

The method according to the invention is a method to operate a water softening device. Preferably the device operated according to this method is a device like the one described above. It comprises the steps of.

the ion exchange resin is buffered with at least one salt selected from the group of a potassium salt (K+), a sodium salt (Na+) and a lithium salt (Li+).

Preferably the measuring of the electric properties of the first and the second stream is accomplished simultaneously or in a defined delay.

In a preferred embodiment the method may be characterized by the following additional feature:.

In practice, it would also be possible to form a ratio between the electrical conductivity of the first stream and the electrical conductivity of the second stream (and not vice versa, namely between the electrical conductivity of the second stream and the electrical conductivity of the first stream). Actually in both cases a ratio is obtained which may be used as an indicator for the exhaustion state of the filter.

In further preferred embodiments the method may be characterized by the following additional features and/or steps:.

The threshold value ratio_exhaust corresponds to a pH value at which the filter needs to be replaced. As initially mentioned, usually this is the case at a pH value of <NUM>. Thus, in this case ratio_exhaust could also be named ratio_6.

In further preferred embodiments the method may be characterized by at least one of the following additional steps:.

In further preferred embodiments the method may be characterized by at least one of the following additional features and/or steps:.

More detailed description of the invention / working example.

Further features and advantages of the invention can be derived from the figures and the following detailed description of preferred embodiments. The preferred embodiments described are merely for the purposes of illustration and to give a better understanding of the invention and shall not in any way constitute a restriction.

For most natural water encountered, the total hardness TH (TH corresponds to the sum of the concentrations of Ca<NUM>+ and Mg<NUM>+ ions in the water: TH = [Ca<NUM>+] + [Mg<NUM>+]) is higher than the alkalinity Alk. (the alkalinity is proportional to the concentration of HCO<NUM>- ions: Alk. ~ [HCO<NUM>-]), so that the ratio TH / Alkalinity > <NUM>. Such water treated over a WAC resin bed operated under H+ form, would react as follow:.

<NUM> R-COO-H + Ca<NUM>+ + <NUM> HCO<NUM>- → (R-COO)<NUM>-Ca + <NUM><NUM>CO<NUM>.

The H+ ions fixed on the WAC resin are exchanged against hardness (Ca<NUM>+ and Mg<NUM>+). The H+ ions given by the resin will then react with the alkalinity (HCO<NUM>-) to be transformed into CO<NUM> (H<NUM>CO<NUM>). In other words, the hardness will be exchanged up to the alkalinity concentration.

The process, also known as de-alkalisation process, is quantitatively illustrated in <FIG>. It is governed by the ratio of TH to Alk. In order to avoid the pH of the treated water to drop to a too low value, it is possible, sometimes even advisable, to mix the treated water with a defined percentage of the raw water (for ex. <NUM> to <NUM> %). The bypass setting is usually a consequence of the raw water composition that governs the WAC resin reaction and the composition of the treated water.

The device <NUM> shown in <FIG> comprises an inlet line <NUM> for a first stream of raw water. At the junction <NUM> the first stream of raw water is split into two partial streams. One of the partial streams is led via line <NUM> to the filter <NUM>. The other partial stream flows through the bypass line <NUM>. The ratio between the two partial streams is regulated by means of the valve <NUM>.

The filter <NUM> contains a WAC resin bed operated under H+ form. When water flows through the filter <NUM>, H+ ions fixed on the WAC resin are exchanged against hardness. At junction <NUM> water which has exited from the filter <NUM> can be blended with raw water from the bypass line <NUM>. Via outlet line <NUM> the water can exit from the device <NUM>.

The device <NUM> comprises two sensors <NUM> and <NUM> for measuring electrical conductivity of the water flowing through the device. Sensor <NUM> is positioned at the inlet line <NUM>. Sensor <NUM> is positioned at the outlet line <NUM>. In addition to this, device <NUM> comprises sensor <NUM> for detecting a water flow through the filter <NUM>. The sensor <NUM> gives information about the presence of a water flow through the filter <NUM>. The sensors <NUM> to <NUM> are connected to the electronic control unit <NUM>.

With the help of the sensors <NUM> and <NUM> it is possible to determine a ratio between the electrical conductivity of softened water which has at least partially been treated in the filter <NUM> and the electrical conductivity of the raw water. After each exchange of the filter <NUM> a certain time is needed to stabilize the conductivity measurements. Then the ratio is determined. It has been found (see below) that by monitoring this ratio it is possible to identify a conductivity ratio value that corresponds to a certain pH value. Usually a filter containing a WAC resin should be replaced when the pH value of the treated water reaches <NUM>.

At the beginning of the filter's <NUM> lifetime, the conductivity ratio will decrease to reach a minimum, if the filter <NUM> contains a buffered WAC resin. After this minimum the conductivity ratio will start to increase until the end of the filter's <NUM> lifetime.

The operation principle of a WAC resin bed operated under H+ form was illustrated by <FIG>. In order to avoid the pH of the treated water to drop to a too low value especially at the beginning of the cycle, in addition to the bypass, the ion exchange resin can be buffered with an additional salt that could be any ion that would have a lower selectivity than the ions to be exchanged. Usually K+, Na+ and/or Li+ are preferred. In the present case preferably an ion exchange resin buffered with Na+ is used. The sodium quantity for this application could be located in the range from <NUM> mol to <NUM> mol of sodium per liter of ion exchange resin.

The ion exchange resin shows different selectivities for the different ions present in the solution. For a WAC resin the selectivity is usually as follows:.

K+ < Na+ < Li+ < Mg<NUM>+ < Ca<NUM>+ < H+.

This means that for a WAC resin regenerated under H+ form and buffered with any additional salt with lower selectivity than the ions to be exchanged (ex: Na+ buffer for Ca<NUM>+ and Mg<NUM>+ removal), hardness would be preferentially exchanged against the buffering ion Na+, because of the resin selectivity. When the available buffering ions Na+ are exchanged, the regular de-alkalisation process occurs. The Ca<NUM>+ and Mg<NUM>+ are exchanged against H+ that will react with the alkalinity to be transformed into CO<NUM>. The buffering ion (ex: Na+) release is leading to a smoother H+ release at the beginning of the cycle that contributes avoiding the pH to drop to a lower value.

At the beginning of the cycle, the WAC resin will exchange mostly the buffering ion (ex: Na+) against Ca<NUM>+ and Mg<NUM>+ but also H+ as described above. As far as the amount of water passed through the filter will increase, the quantity of buffering ion (ex: Na+) exchanged against Ca<NUM>+ and Mg<NUM>+ will decrease, while the amount of H+ will increase. This will lead to a decrease of the pH at the beginning of the cycle, limited by the buffer ion release. As a part of the alkalinity will be transformed into CO<NUM>, the HCO<NUM>- concentration will also decrease. At same time, the hardness leakage will start to increase accordingly.

Once all the loaded buffer ions have been released, an inflection of the curves occurs. The pH will start to increase until the complete exhaustion of the filter. It means at the beginning of the cycle, the pH will pass by a minimum value (ratio_min) and will then increase to reach the ratio corresponding to a pH of <NUM> (ratio_6. <NUM> or ratio_exchange, compare above), the criteria for filter replacement.

Experiments have been conducted with a filter containing a WAC resin buffered with Na+ from <NUM> to <NUM> mol per liter resin. A stream of raw water has been passed through the filter. The composition of the raw water at the filter inlet was analyzed:.

In the experiment the filter was brought to complete exhaustion. A water stream has been passed through the filter until the outlet water composition was similar to the inlet composition. The electrical conductivity of the water stream was continuously monitored at the inlet of the filter and at the outlet.

<FIG> illustrates the change of concentration of the ion species Ca<NUM>+, Na+ and HCO<NUM>- in the water stream passed through the filter. <FIG> illustrates the change of pH of the water passed through the filter. <FIG> illustrates the change of the ratio of the electrical conductivity of the water passed through the filter and the electrical conductivity of the raw water.

From the three curves in <FIG> it becomes evident that the HCO<NUM>- concentration, the pH and the ratio of the electrical conductivities are following the same evolution. In fact the HCO<NUM>- concentration, the pH and the ratio are linked together. In the experiment the raw water conductivity was stable. As a consequence, the ratio follows the outlet conductivity evolution. The electrical conductivity is proportional to the HCO<NUM>- concentration which is directly linked to pH and alkalinity according to the calco-carbonic equilibrium.

According to the curve in <FIG> the volume corresponding to a pH of <NUM> is about <NUM> liters. According to the curve in <FIG> the ratio corresponding to a volume of <NUM> liters is about <NUM>,<NUM>. Combining this information leads to the conclusion that a pH of <NUM> corresponds to a ratio of <NUM>,<NUM>. This is why this ratio is named ratio_6. Further, it is possible to extract from the curve in <FIG> the lowest ratio, ratio_min, which has a value of <NUM> in this case.

There is a direct link between the ratio_min and the ratio_6. To demonstrate the relation between both, a filter was tested for different water compositions (ratio TH / Alk. The filter used for the tests had a fixed given amount of WAC ion exchange resin. The resin was always conditioned in the same way, using Na+ as buffer with always the same quantity located between <NUM> and <NUM> mol of Na+ per liter of resin. The bypass was adjusted from <NUM> to <NUM> % according to the water alkalinity.

The results are illustrated in <FIG> with the values of ratio_min and ratio_6. <NUM> for the different water compositions, given as a function of the ratio TH / Alk. For the different water compositions tested, the ratio_min and the ratio_6. <NUM> were linear as a function of the ratio TH /Alk. Ratio_min and ratio_6. <NUM> depend on the WAC ion exchange resin used, its capacity and the amount of buffer loaded (here Na+), as well as on the raw water composition, especially the ratio TH / Alk.

This means that for a given WAC resin type, the same amount a buffer loaded on the resin compared to the main regenerant H+ and the same water composition, the ratio_min and ratio_6. <NUM> will always pass by the same values.

The fact the ratio_min and the ratio_6. <NUM> are both linear to the ratio TH / Alk. on the considered range leads to the conclusion that there is also a linear relation between the ratio_min and the ratio_6. This is illustrated by the curve shown in <FIG>.

Conclusion: For a given filter size, using always the same amount of WAC ion exchange resin conditioned in the same way, the ratio_6. <NUM> corresponding to the exhaustion point is linear to the ratio_min. This curve is characteristic for a defined filter type and can be used as exhaustion criteria. In the present case the exhaustion criteria is: <MAT>.

So, once the ratio_min is known, it is possible to calculate the value for the ratio_6. <NUM> from this equation, which corresponds to the point the filter will need to be replaced. The exhaustion criteria allows to make the correlation between the outlet pH the filter needs to be replaced and the conductivity ratio outlet to inlet.

Considering the described example, on the curve in <FIG> the ratio reaches its minimum at a value of <NUM>, therefore ratio_min = <NUM>. <NUM> can be determined as: <MAT>.

It means in this example that when the conductivity ratio will reach a value of <NUM>, the outlet pH will be <NUM> and the filter needs to be replaced.

Once the ratio_min and the ratio_6. <NUM> are known, a device according to the invention can be configured to determine a warning ratio (ratio_warning) to give information to a user of the device that the filter is coming to the end of its lifetime and will need to be replaced soon. The ratio_warning is calculated as follow from the Δ ratio between the ratio_6. <NUM> and ratio_min: <MAT> <MAT>.

Considering the described example above, the ratio_warning is: <MAT>.

In preferred embodiments the device according to the invention comprises three LEDs (green, orange and red) as optical signaling devices. The lightning of the LEDs is controlled as follows:.

With the LEDs it is possible to give a warning prior to the filter exhaustion in order to inform the user that the filter is at the end of its lifetime.

The relation between the ratio_min, ration_warning and the ratio_6. <NUM> is illustrated in <FIG>.

The device <NUM> shown in <FIG> comprises a base unit <NUM> and an exchangeable filter <NUM>. The base unit <NUM> and the filter <NUM> are connected via a screw connection. For this purpose the filter comprises an external thread <NUM> and the base unit comprises an internal thread <NUM>. In order to provide leakproofness, the sealing rings <NUM> and <NUM> are arranged at an interface between the filter <NUM> and the base unit <NUM>.

The base unit comprises an inlet line <NUM> for a first stream of raw water, an outlet line <NUM> for a second stream of water with decreased hardness exiting from the filter <NUM> and a bypass line <NUM>. At the junction <NUM> the first stream of raw water is split into two partial streams. One of the partial streams is led via line <NUM> to the filter <NUM>. The other partial stream flows through the bypass line <NUM>. The ratio between the two partial streams can be regulated by means of the valve <NUM>. At the junction <NUM> water which has exited from the filter <NUM> can be blended with raw water from the bypass line <NUM>. Via the outlet line <NUM> the water can exit from the device <NUM>. Arrows are used to illustrate the directions in which the water streams flow within the device.

The filter <NUM> comprises an inlet 105a for the first stream of raw water and an outlet 105b for the second stream of water with decreased hardness. The inlet line <NUM> of the base unit <NUM> is coupled to the inlet 105a of the filter <NUM> and the outlet line <NUM> of the base unit <NUM> is coupled to the outlet 105b of the filter <NUM>.

The filter <NUM> contains a WAC resin 105d operated under H+ form and buffered with Na+. The WAC resin 105d is contained in a cartridge 105c. When water flows through the filter <NUM>, Na+ ions and H+ ions fixed on the WAC resin 105d are exchanged against hardness. Initially primarily Na+ ions are exchanged. Later, the output of H+ ions increases and the output of Na+ ions decreases.

The device <NUM> comprises two sensors <NUM> and <NUM> for measuring electrical conductivity of the water flowing through the device. Sensor <NUM> is positioned at the outlet line <NUM>. Sensor <NUM> is positioned at the inlet line <NUM>. In addition to this, device <NUM> comprises sensor <NUM> for detecting a water flow through the filter <NUM>. The sensor <NUM> gives information about the presence of a water flow through the filter <NUM>. The sensors <NUM> to <NUM> are connected to an electronic control unit <NUM>, as shown in <FIG>. The electronic control unit is not visible in the cross-section showed in <FIG>.

Claim 1:
Water softening device (<NUM>), comprising
a. a filter (<NUM>) which is configured to decrease hardness of a first stream of raw water to produce a second stream of water with decreased hardness,
b. a first sensor (<NUM>) configured to measure an electrical conductivity and/or an electrical resistance of the first stream,
c. a second sensor (<NUM>) configured to measure an electrical conductivity and/or an electrical resistance of the second stream, and
d. optionally a third sensor (<NUM>) for detecting a water flow through the filter (<NUM>),
wherein
e. the filter (<NUM>) comprises an ion exchange resin (105d), which is operated in H+-mode, and which is buffered with at least one salt selected from the group of a potassium salt (K+), a sodium salt (Na+) and a lithium salt (Li+),
f. the device (<NUM>) comprises an electronic control unit (<NUM>) which is connected to the first sensor (<NUM>), to the second sensor (<NUM>) and optionally, if the device comprises the third sensor, to the third sensor (<NUM>), and which comprises an internal data memory and a data processing unit, and
g. the device is configured to determine a ratio between the measured electrical conductivity and/or resistance of the second stream and the measured electrical conductivity and/or resistance of
the first stream and use the ratio as an indicator for the exhaustion state of the filter (<NUM>).