Apparatus for inhibiting formation of calcium based crystal and apparatus for water treatment using the same

Abstract

An apparatus for inhibiting formation of calcium based crystal, in which formation of calcium based crystals is inhibited by adding an optimal amount of magnesium to raw water having a high concentration of calcium ions and a high variation in calcium ion concentration and an apparatus for water treatment using the same.

Claims

1. An apparatus for water treatment to inhibit formation of calcium based crystal, comprising: a raw water tank operatively connected to a pretreatment tank to store seawater or wastewater containing a high concentration of calcium ions (Ca.sup.2+) as raw water and to supply the raw water to the pretreatment tank; a magnesium supplying device operatively connected to the pretreatment tank to supply magnesium to the pretreatment tank, wherein the magnesium induces a reaction for inhibiting formation of calcium based crystals in the raw water; and a calcium concentration measuring device that measures a concentration of calcium included in the raw water.

2. The apparatus according to claim 1, further comprising a controller to adjust a [Mg.sup.2+]/[Ca.sup.2+] mole ratio of the raw water in the pretreatment tank to 6-10, wherein Ca.sup.2+, Mg.sup.2+, CO.sub.3.sup.2−, SO.sub.4.sup.2−in the raw water are kept in an ion state to inhibit formation of calcium based crystals.

3. The apparatus according to claim 1, further comprising: a control device, wherein the control device stores an optimal [Mg.sup.2+]/[Ca.sup.2+] mole ratio value, calculates an amount of magnesium to be added to the pretreatment tank using the optimal mole ratio value and the concentration of calcium in the raw water measured by the calcium concentration measuring device, and controls an amount of magnesium supplied by the magnesium supplying device based on the calculated amount of magnesium.

4. The apparatus according to claim 1, wherein the magnesium supplying device supplies MgCl.sub.2.Math.6H.sub.2O.

5. The apparatus according to claim 1, wherein the raw water tank stores seawater.

6. The apparatus according to claim 1, wherein the raw water tank stores wastewater.

7. An apparatus for water treatment to inhibit formation of calcium based crystal, comprising: a raw water tank operatively connected to a pretreatment tank to store seawater or wastewater containing a high concentration of calcium ions (Ca.sup.2+) as raw water and to supply the raw water to the pretreatment tank; a magnesium supplying device operatively connected to the pretreatment tank to supply magnesium to the pretreatment tank, wherein the magnesium induces a reaction for inhibiting formation of calcium based crystals in the raw water; a membrane device operatively connected to the pretreatment tank to produce treated water after the calcium based crystals in the raw water are inhibited from forming; and a calcium concentration measuring device that measures a concentration of calcium included in the raw water.

8. The apparatus according to claim 1, further comprising a reverse osmosis membrane operatively connected to the raw water tank to supply the raw water.

9. The apparatus according to claim 7, wherein the raw water tank stores seawater.

10. The apparatus according to claim 7, further comprising a reverse osmosis membrane operatively connected to the raw water tank to supply the raw water.

11. The apparatus according to claim 7, further comprising a controller to adjust a [Mg.sup.2+]/[Ca.sup.2+] mole ratio of the raw water in the pretreatment tank to 6-10, wherein Ca.sup.2+, Mg.sup.2+, CO.sub.3.sup.2−, SO.sub.4.sup.2−in the raw water are kept in an ion state to inhibit formation of calcium based crystals.

12. The apparatus according to claim 7, further comprising: a control device, wherein the control device stores an optimal [Mg.sup.2+]/[Ca.sup.2+] mole ratio value, calculates an amount of magnesium to be added to the pretreatment tank using the optimal mole ratio value and the concentration of calcium in the raw water measured by the calcium concentration measuring device, and controls an amount of magnesium supplied by the magnesium supplying device based on the calculated amount of magnesium.

13. The apparatus according to claim 7, wherein the magnesium supplying device supplies MgCl.sub.2.Math.6H.sub.2O.

14. The apparatus according to claim 7, wherein the membrane device separates concentrated water using a membrane.

15. The apparatus according to claim 7, wherein the membrane device is a membrane device using a reverse osmosis membrane or a membrane device with a membrane distillation membrane.

16. The apparatus according to claim 7, wherein the raw water tank stores wastewater.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 is a configuration diagram of an apparatus for inhibiting formation of calcium based crystal according to an embodiment of the present disclosure.

(2) FIG. 2 shows an apparatus for water treatment using an apparatus for inhibiting formation of calcium based crystal according to an embodiment of the present disclosure.

(3) FIG. 3 illustrates experimental results showing volumetric concentration factor (VCF) changes as a function of [Mg.sup.2+]/[Ca.sup.2+] mole ratio.

(4) FIG. 4A to FIG. 4C illustrate experimental results showing a change in scaling depending on added or no magnesium.

DETAILED DESCRIPTION

(5) The present disclosure proposes technology that inhibits the formation of calcium based crystals by optimizing the Mg/Ca ratio in raw water, thereby retarding or preventing scale formation caused by Ca component in the raw water.

(6) In the present disclosure, ‘raw water’ refers to seawater or wastewater containing a high concentration of Ca components. As mentioned above in ‘Description of the Related Art’, seawater has a higher concentration of metal ions containing calcium (Ca) than fresh water and a change in the concentration of metal ions depending on the climate. Additionally, in a membrane distillation process for raw water containing a high concentration of metal ions, applied to minimize the discharge of concentrated water, the corresponding raw water has a high metal ion concentration and a variation in metal ion concentration.

(7) The present disclosure presents technology that adjusts the [Mg.sup.2+]/[Ca.sup.2+] mole ratio in raw water to 6-10 with an addition of an optimal amount of magnesium (Mg) to the raw water, thereby inhibiting the formation of calcium based crystals, and through this, preventing the membrane contamination with scales.

(8) The calcium based crystals are CaCO.sub.3 and CaSO.sub.4, and calcium ions (Ca.sup.2+) in the raw water react with salts such as CO.sub.3.sup.2− and SO.sub.4.sup.2− to form CaCO.sub.3 and CaSO.sub.4. When magnesium ions (Mg.sup.2+) are present in the raw water, the binding of Ca.sup.2+ to salts (CO.sub.3.sup.2− or SO.sub.4.sup.2−) is inhibited by Mg.sup.2+. This is because Mg.sup.2+ can also bind to the salts (CO.sub.3.sup.2− or SO.sub.4.sup.2−). That is, Ca.sup.2+ and Mg.sup.2+ compete in the binding to salts. As described above, when an optimal amount of Mg.sup.2+ is present in the raw water, formation of calcium based crystals such as CaCO.sub.3 and CaSO.sub.4 is inhibited due to the competitive relationship with Ca.sup.2+.

(9) The present disclosure identifies through experiments that when the [Mg.sup.2+]/[Ca.sup.2+] mole ratio in raw water is adjusted to 6-10, formation of calcium based crystals is minimized, and when the [Mg.sup.2+]/[Ca.sup.2+] mole ratio in raw water is adjusted to 6-10 in a pretreatment process of a seawater desalination process or a pretreatment process of a membrane process for raw water containing a high concentration of metal ions, scale formation on the membrane is effectively inhibited.

(10) Hereinafter, an apparatus for inhibiting formation of calcium based crystal according to an embodiment of the present disclosure and an apparatus for water treatment using the same will be described in detail with reference to the accompanying drawings.

(11) Referring to FIG. 1, the apparatus for inhibiting formation of calcium based crystal according to an embodiment of the present disclosure includes a raw water tank 110, a pretreatment tank 120, a magnesium supplying device 130, a calcium concentration measuring device 140 and a control device 150.

(12) The raw water tank 110 stores raw water that needs to inhibit scaling. The raw water stored in the raw water tank 110 is seawater or wastewater containing a high concentration of calcium ions (Ca.sup.2+). The seawater contains a variety of metal ions including a high concentration of calcium ions.

(13) The pretreatment tank 120 is supplied with the raw water from the raw water tank 110 and magnesium from the magnesium supplying device 130 together to induce a reaction for inhibiting the formation of calcium based crystals, for example, CaCO.sub.3, CaSO.sub.4, in the raw water.

(14) After the raw water containing a high concentration of calcium ions or the seawater is supplied to the pretreatment tank 120, when magnesium (Mg) is supplied to the pretreatment tank 120, calcium ions (Ca.sup.2+) and magnesium ions (Mg.sup.2+) compete in the binding to salts. That is, calcium ions (Ca.sup.2+) bind to salts (CO.sub.3.sup.2− or SO.sub.4.sup.2−) to form calcium based crystals such as CaCO.sub.3, CaSO.sub.4, and when calcium ions (Ca.sup.2+) and magnesium ions (Mg.sup.2+) coexist, magnesium ions (Mg.sup.2+) also tend to bind to salts (CO.sub.3.sup.2− or SO.sub.4.sup.2−), and thus formation of calcium based crystals such as CaCO.sub.3 and CaSO.sub.4 is inhibited. Due to the competitive relationship between calcium ions (Ca.sup.2+) and magnesium ions (Mg.sup.2+), Ca.sup.2+, Mg.sup.2+, CO.sub.3.sup.2−, SO.sub.4.sup.2− in the raw water are kept in an ion state, thereby inhibiting or retarding the formation of calcium based crystals.

(15) As the competitive relationship between calcium ions (Ca.sup.2+) and magnesium ions (Mg.sup.2+) in the binding to salts (CO.sub.3.sup.2− or SO.sub.4.sup.2−) is maximized, formation of calcium based crystals is inhibited, and it is necessary to adjust the [Mg.sup.2+]/[Ca.sup.2+] mole ratio in raw water to 6-10 to inhibit the formation of calcium based crystals through the competitive relationship.

(16) When the [Mg.sup.2+]/[Ca.sup.2+] mole ratio is smaller than 6, inhibition of the formation of calcium based crystals is limited, and when the [Mg.sup.2+]/[Ca.sup.2+] mole ratio is larger than 10, the effect of inhibition on the formation of calcium based crystals does not increase and magnesium based crystals are formed and precipitated. The numerical limitation of the [Mg.sup.2+]/[Ca.sup.2+] mole ratio is supported by the experimental results as described below.

(17) The magnesium supplying device 130 serves to supply magnesium (Mg) to the pretreatment tank 120, and an amount of magnesium supplied to the pretreatment tank 120 is controlled by the control device 150. The magnesium supplied by the magnesium supplying device 130 may be supplied in the form of MgCl.sub.2.6H.sub.2O.

(18) The calcium concentration measuring device 140 serves to measure the concentration of calcium included in the raw water, and the measured calcium concentration in the raw water is transmitted to the control device 150. The calcium concentration measuring device 140 may selectively include a variety of devices to measure the quantitative values of the components of a material.

(19) The control device 150 stores an optimal [Mg.sup.2+]/[Ca.sup.2+] mole ratio value, calculates an amount of magnesium to be added to the pretreatment tank 120 using the optimal mole ratio value and the concentration of calcium in the raw water measured by the calcium concentration measuring device 140, and controls an amount of magnesium supplied by the magnesium supplying device 130 based on the calculated amount of magnesium. In this instance, the optimal [Mg.sup.2+]/[Ca.sup.2+] mole ratio value is set to 6-10 as described above.

(20) As described above, when the optimal [Mg.sup.2+]/[Ca.sup.2+] mole ratio value is set to 6-10, an amount of magnesium corresponding to the optimal [Mg.sup.2+]/[Ca.sup.2+] mole ratio value is supplied to the pretreatment tank 120 in response to the concentration of calcium in the raw water, to maximize the competitive relationship between calcium ions (Ca.sup.2+) and magnesium ions (Mg.sup.2+) in the binding to salts (CO.sub.3.sup.2− or SO.sub.4.sup.2−), thereby inhibiting the formation of calcium based crystals.

(21) Subsequently, an apparatus for water treatment using an apparatus for inhibiting formation of calcium based crystal according to an embodiment of the present disclosure will be described.

(22) Referring to FIG. 2, the apparatus for water treatment using an apparatus for inhibiting formation of calcium based crystal according to an embodiment of the present disclosure includes a raw water tank 110, a pretreatment tank 120 and a membrane device 160, and further includes a magnesium supplying device 130, a calcium concentration measuring device 140 and a control device 150.

(23) The raw water tank 110 stores raw water containing a high concentration of calcium ions (Ca.sup.2+), and the membrane device 160 performs a membrane process on the raw water containing a high concentration of calcium ions (Ca.sup.2+) to minimize the discharge of concentrated water.

(24) The raw water in the raw water tank 110 is seawater or wastewater containing a high concentration of calcium ions (Ca.sup.2+), and particularly, concentrated water discharged by a reverse osmosis process of a water treatment process may correspond to the raw water. The seawater or the concentrated water discharged by a reverse osmosis process of a water treatment process is concentrated impurities, and contains a high concentration of calcium ions (Ca.sup.2+).

(25) The membrane device 160 is prone to scaling and may be contaminated with scales on the membrane surface due to the membrane process performed on the concentrated water discharged by the reverse osmosis process of the water treatment process or the seawater. The membrane device 160 may correspond to any one of a membrane device using a reverse osmosis membrane and a membrane device with a membrane distillation membrane or any type of membrane device of filtering concentrated water using a membrane.

(26) The configuration of the pretreatment tank 120, the magnesium supplying device 130, the calcium concentration measuring device 140 and the control device 150 is applied to prevent the membrane of the membrane device 160 from being contaminated with scales due to the process performed on highly concentrated raw water. The configuration of the pretreatment tank 120, the magnesium supplying device 130, the calcium concentration measuring device 140 and the control device 150 has substantially the same role as that of the apparatus for inhibiting formation of calcium based crystals.

(27) The pretreatment tank 120 is supplied with raw water from the raw water tank 110 and magnesium from the magnesium supplying device 130 together to inhibit the formation of calcium based crystals in the raw water.

(28) After the raw water containing a high concentration of calcium ions or the seawater is supplied to the pretreatment tank 120, when magnesium (Mg) is supplied to the pretreatment tank 120, calcium ions (Ca.sup.2+) and magnesium ions (Mg.sup.2+) compete in the binding to salts. Due to the competitive relationship between calcium ions (Ca.sup.2+) and magnesium ions (Mg.sup.2+), Ca.sup.2+, Mg.sup.2+, CO.sub.3.sup.2−, SO.sub.4.sup.2− in the raw water are kept in an ion state, thereby inhibiting or retarding the formation of calcium based crystals.

(29) As the competitive relationship between calcium ions (Ca.sup.2+) and magnesium ions (Mg.sup.2+) in the binding to salts (CO.sub.3.sup.2− or SO.sub.4.sup.2−) is maximized, formation of calcium based crystals is inhibited, and it is necessary to adjust the [Mg.sup.2+]/[Ca.sup.2+] mole ratio in the raw water to 6-10 to inhibit the formation of calcium based crystals through the competitive relationship. When the [Mg.sup.2+]/[Ca.sup.2+] mole ratio is smaller than 6, inhibition of the formation of calcium based crystals is limited, and when the [Mg.sup.2+]/[Ca.sup.2+] mole ratio is larger than 10, magnesium based crystals are formed and precipitated.

(30) The magnesium supplying device 130 serves to supply magnesium (Mg) to the pretreatment tank 120, and an amount of magnesium supplied to the pretreatment tank 120 is controlled by the control device 150. The magnesium supplied by the magnesium supplying device 130 may be supplied in the form of MgCl.sub.2.6H.sub.2O.

(31) The calcium concentration measuring device 140 serves to measure the concentration of calcium included in the raw water, and the measured concentration of calcium in the raw water is transmitted to the control device 150. The calcium concentration measuring device 140 may selectively include a variety of devices to measure the quantitative values of the components of a material.

(32) The control device 150 stores an optimal [Mg.sup.2+]/[Ca.sup.2+] mole ratio value, calculates an amount of magnesium to be added to the pretreatment tank 120 using the optimal mole ratio value and the concentration of calcium in the raw water measured by the calcium concentration measuring device 140, and controls an amount of magnesium supplied by the magnesium supplying device 130 based on the calculated amount of magnesium. In this instance, the optimal [Mg.sup.2+]/[Ca.sup.2+] mole ratio value is set to 6-10 as described above.

(33) As described above, when the optimal [Mg.sup.2+]/[Ca.sup.2+] mole ratio value is set to 6-10, an amount of magnesium corresponding to the optimal [Mg.sup.2+]/[Ca.sup.2+] mole ratio value is supplied to the pretreatment tank 120 in response to the concentration of calcium in the raw water, to maximize the competitive relationship between calcium ions (Ca.sup.2+) and magnesium ions (Mg.sup.2+) in the binding to salts (CO.sub.3.sup.2− or SO.sub.4.sup.2−), thereby inhibiting the formation of calcium based crystals. The formation of calcium based crystals in the raw water is inhibited by this principle, and when a membrane process is performed by the membrane device 160, it is possible to inhibit or retard scale formation on the membrane surface even though the distillation process is performed on the raw water containing a high concentration of calcium ions.

(34) The apparatus for inhibiting formation of calcium based crystal according to an embodiment of the present disclosure and the apparatus for water treatment using the same have been hereinabove described. Hereinafter, the present disclosure will be described in more detail through experimental examples.

Experimental Example 1: Change in Membrane Permeability as a Function of [Mg.SUP.2+.]/[Ca.SUP.2+.] Mole Ratio

(35) After the [Mg.sup.2+]/[Ca.sup.2+] mole ratio in the seawater is adjusted to 5, 6, 7, 10 with an addition of MgCl.sub.2.6H.sub.2O to seawater, a change in membrane permeability is observed.

(36) Referring to FIG. 3, when the [Mg.sup.2+]/[Ca.sup.2+] mole ratio is 5 or more, membrane permeability is 0.2 at volumetric concentration factor (VCF) of 3.4, and when the [Mg.sup.2+]/[Ca.sup.2+] mole ratio is 6, membrane permeability is 0.2 at VCF of 3.6 or more. In detail, when the [Mg.sup.2+]/[Ca.sup.2+] mole ratio is 6, VCF is 3.6, and when the [Mg.sup.2+]/[Ca.sup.2+] mole ratio is 7 and 10, VCF is 4.1.

Experimental Example 2: Change in Scaling Depending on Added or No Magnesium

(37) For each of seawater, seawater added with Na.sub.2CO.sub.3 and NaOH, and seawater added with MgCl.sub.2, a change in scale formation on the membrane surface with the increasing VCF is observed.

(38) FIG. 4A is a SEM image of the membrane surface in the case of seawater, FIG. 4B is a SEM image of the membrane surface in the case of seawater added with Na.sub.2CO.sub.3 and NaOH, and FIG. 4C is a SEM image of the membrane surface in the case of seawater added with MgCl.sub.2.

(39) As shown in FIG. 4A to FIG. 4C, it can be seen that less scales are formed on the membrane surface in seawater added with Na.sub.2CO.sub.3 and NaOH than seawater, and scaling is inhibited better when MgCl.sub.2 is added to seawater.

(40) These results can be verified through the EDS results. As shown in the following Table 1, when MgCl.sub.2 is added to seawater, a very small amount of calcium (Ca) of 0.1% is detected and oxygen (O) is not detected at VCF of 3.0, and these results demonstrate that calcium based crystals such as CaCO.sub.3 and CaSO.sub.4 are scarcely formed.

(41) TABLE-US-00001 TABLE 1 <Components of each of seawater, seawater added with Na.sub.2CO.sub.3 and NaOH, and seawater added with MgCl.sub.2> Normal Mg added seawater (NS) Softened NS NS d) (Atomic %) (Atomic %) (Atomic %) VCFs 2.0 3.5 2.0 6.2 3.0 4.1 Ca 19 17 — 4 0.1 18 Mg — — 8 4 — — C 19 — 40 46 46 — F 8 — 35 14 52 — O 54 68 16 27 — 66 S — 15 — 1 — 16 Cl — — 1 3 0.2 — Na — — — — 0.2 —

DETAILED DESCRIPTION OF MAIN ELEMENTS

(42) TABLE-US-00002 110: Raw water tank 120: Pretreatment tank 130: Magnesium supplying device 140: Calcium concentration measuring device 150: Control device 160: Membrane device