JP2018051424A - Magnesium oxide-supported bismuth oxychloride composite material, process for producing the same, water cleaning cartridge, and water cleaner - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a novel material that can more efficiently remove both cations and anions, a water cleaning cartridge and a water cleaner.SOLUTION: A novel composite material 1 includes bismuth oxychloride and magnesium oxide supported on the bismuth oxychloride, and can more efficiently remove phosphate ions and metal ions. A process for producing the composite material 1 includes: a mixing step S1 of mixing a material 10 including a bismuth source 11 and a magnesium source 12; a heating step S2 of heating the mixed material 20 at 100 to 800°C while a chlorine source is present; and a cooling step S3 of cooling the heated material 21.SELECTED DRAWING: Figure 10

Description

  The present invention relates to a material having an ion adsorption capacity, a manufacturing method thereof, a water purification cartridge, and a water purifier.

  In order to remove ions contained in the raw water, a water purifier having an ion exchanger is used. Examples of the ion exchanger include a cation exchange resin for removing metal ions and an anion exchange resin for removing nitrate nitrogen. Patent Document 1 discloses a water purifier filled with a mixture of a cation exchange resin and an anion exchange resin.

Japanese Patent Laid-Open No. 7-60246

  In the water purifier mentioned above, it is necessary to prepare both a cation exchange resin and an anion exchange resin as ion exchangers.

  The present invention has an object to provide a novel material, a water purification cartridge, and a water purifier that can more efficiently remove both cations and anions.

The present invention has an embodiment of a composite material including bismuth oxychloride and magnesium oxide supported on the bismuth oxychloride.
The present invention also includes a mixing step of mixing a material containing a bismuth source and a magnesium source, a heating step of heating the mixed material at 100 to 800 ° C. in the presence of a chlorine source, and the heated material. And a cooling step of cooling the bismuth oxychloride, and a method for producing a composite material comprising bismuth oxychloride and magnesium oxide supported on the bismuth oxychloride.

Furthermore, this invention has the aspect of the water purification cartridge provided with the said composite material and the accommodating part which was able to go in and out and accommodated the said composite material.
Furthermore, the present invention includes the composite material, a storage portion that stores the composite material, a water inlet, and a water outlet, and water to be treated flows from the water inlet into the storage portion. It has the aspect of the water purifier from which the water processed with the said composite material in a part flows out from the said water outlet.

  ADVANTAGE OF THE INVENTION According to this invention, the novel composite material, water purification cartridge, and water purifier which can remove a phosphate ion and a metal ion more efficiently can be provided.

The flowchart which shows typically the example of the manufacturing method of the composite material containing the bismuth oxychloride and the magnesium oxide carry | supported by this bismuth oxychloride. FIG. 2A is a diagram schematically showing an example of a system kitchen incorporating a faucet having a water purifier, and FIG. 2B is a vertical sectional view showing an example of a water purifier incorporating a water purification cartridge. The graph which shows the result of having measured the phosphate ion removal ability of each composite material sample which changed heating temperature. The graph which shows the result of having measured the phosphate ion removal ability of each composite material sample which changed the molar ratio of bismuth and magnesium. The graph which shows the result of having measured the metal ion removal ability of each composite material sample which changed the molar ratio of bismuth and magnesium. The graph which shows the result of having measured the metal ion removal ability of each composite material sample which changed the molar ratio of bismuth and magnesium. The graph which shows the example of the powder X-ray-diffraction pattern of a composite material sample. The graph which shows the example of the powder X-ray diffraction pattern of the composite material sample when changing heating temperature. The graph which shows the example of the powder X-ray diffraction pattern of the composite material sample when changing the molar ratio of bismuth and magnesium. The example of the SEM photograph of a composite material sample. The example of the SEM photograph of a composite material sample. The example of the SEM photograph of a composite material sample. The example of the SEM photograph of a composite material sample. An example of a gray image obtained by analyzing a composite material sample by EDX. The example of an EDX image which shows distribution of magnesium of a composite material sample. The example of an EDX image which shows distribution of oxygen of a composite material sample. The example of an EDX image which shows distribution of the bismuth of a composite material sample. The example of an EDX image which shows distribution of chlorine of a composite material sample.

  Embodiments of the present invention will be described below. Of course, the following embodiments are merely examples of the present invention, and all the features shown in the embodiments are not necessarily essential to the means for solving the invention.

(1) Summary of technology included in the present invention:
First, the outline | summary of the technique included in this invention is demonstrated with reference to the example shown by the figure of this application. In addition, the figure of this application is a figure which shows an example typically, The expansion ratio of each direction shown by these figures may differ, and each figure may not match.

[Aspect 1]
The present technology has an embodiment of a composite material 1 including bismuth oxychloride and magnesium oxide supported on the bismuth oxychloride as supported by FIG. 10 and the like. When this composite material 1 was tested, it was found that there was a novel property that more efficiently removes both phosphate ions and metal ions from the liquid. Therefore, this aspect can provide a novel composite material capable of more efficiently removing phosphate ions and metal ions.

Here, in the present application, “supporting” means that one substance A supports another substance B.
The composite material of Embodiment 1 may include a material different from bismuth oxychloride and magnesium oxide.

[Aspect 2]
By the way, as illustrated in FIG. 7 and the like, the composite material 1 has an intensity peak at 2θ = 11.0 ° to 13.0 ° in the powder X-ray diffraction pattern, and 2θ = 25.0 ° to 27. There may be an intensity peak at 0.0 ° and an intensity peak at 2θ = 33.0 ° to 34.0 °. This aspect can provide a suitable composite material that removes phosphate ions and metal ions.
Here, in the present application, “Min to Max” means a minimum value Min and a maximum value Max.

[Aspect 3]
As shown in FIGS. 4 and 5, the composite material 1 may have a molar ratio of magnesium to bismuth of 3/7 or more and 9 or less. This aspect can also provide a suitable composite material that removes phosphate ions and metal ions.

[Aspect 4]
Further, as illustrated in FIG. 1 and the like, the present technology includes a mixing step S1 in which a material 10 including a bismuth source 11 and a magnesium source 12 is mixed, and the mixed material 20 in a state where a chlorine source is present. A composite material 1 including bismuth oxychloride and magnesium oxide supported on the bismuth oxychloride, including a heating step S2 for heating at ˜800 ° C. and a cooling step S3 for cooling the heated material 21. It has the aspect of a manufacturing method. This aspect can provide a method for producing a novel composite material capable of more efficiently removing phosphate ions and metal ions.

[Aspect 5]
Further, as illustrated in FIG. 2B and the like, the present technology includes a water purification cartridge 30 that includes the composite material 1 and a storage portion (for example, a case 40) in which water can enter and exit and stores the composite material 1. It has an aspect. This aspect can provide a novel water purification cartridge capable of more efficiently removing phosphate ions and metal ions.

[Aspect 6]
Furthermore, the present technology includes the composite material 1, a storage unit (40) that stores the composite material 1, a water inlet 111, and a water outlet 112, and water to be treated is supplied from the water inlet 111 to the water. It has the aspect of the water purifier 100 which flows into the storage part (40) and the water treated with the composite material 1 in the storage part (40) flows out from the water outlet 112. This aspect can provide a novel water purifier that can more efficiently remove phosphate ions and metal ions.

(2) Example of method for producing magnesium oxide-supported bismuth oxychloride composite material:
FIG. 1 shows a method for producing a magnesium oxide-supported bismuth oxychloride composite material containing bismuth oxychloride (BiOCl in stoichiometric ratio) and magnesium oxide supported in the bismuth oxychloride (MgO in stoichiometric ratio). An example is schematically shown. In this manufacturing method, the mixing step S1 for mixing the material 10 containing the bismuth source 11 and the magnesium source 12, and heating for heating the mixed material 20 at 100 to 800 ° C. in the presence of oxygen in the presence of the chlorine source. Step S2 and a cooling step S3 for cooling the heated material 21 are included.

As the bismuth source 11, bismuth halide such as bismuth chloride (BiCl _{3 in} stoichiometric ratio) or bismuth bromide, bismuth hydroxide, bismuth carbonate, bismuth nitrate, bismuth sulfide, or the like can be used.

The magnesium source 12 includes magnesium hydroxide (stoichiometric Mg (OH) ₂ ), magnesium chloride (stoichiometric MgCl ₂ ), magnesium bromide such as magnesium bromide, magnesium carbonate, magnesium nitrate, and the like. Can be used.

Here, the number of moles of bismuth contained in the bismuth source 11 is M _Bi and the number of moles of magnesium contained in the magnesium source 12 is M _Mg . When the test was conducted, the ratio of the number of moles of magnesium M _{Mg to} the number of moles M _Bi of bismuth R _{Mg / Bi} = M _Mg / M _Bi was set to 3/7 or more and 9 or less, the composite material 1 was phosphoric acid. It has been found that both the ion PO ₄ ³⁻ and the metal ions are dramatically removed.

Crystalline bismuth oxychloride contained in the composite material 1, a layered structure, the chlorine ions Cl contained in the interlayer ^- is presumed to exert phosphate ion removal ability by being replaced with phosphate ions.
Magnesium oxide contained in the composite material 1 has an unstable portion of charge generated due to minute pores or defects such as magnesium on the surface, and this unstable portion of charge adsorbs metal ions to adsorb metal ions. It is presumed to exhibit ion removal ability.

When a magnesium source is not used, the metal ion removal ability by magnesium oxide mentioned above cannot be obtained. In addition, the bismuth source melted by heating (for example, the melting point of bismuth chloride is about 230 ° C.) is easily evaporated, so that the crystal growth of bismuth oxychloride is suppressed, and the ability to remove phosphate ions by the bismuth oxychloride crystals described above is also suppressed. I guess that. When a magnesium source is used, it is presumed that a magnesium source or a derivative thereof is dissolved in a bismuth source melted by heating to suppress transpiration of the bismuth source, and crystals of bismuth oxychloride are easily grown. When R _{Mg / Bi} ≧ _3/7 using the magnesium source 12, magnesium oxide in the composite material sufficiently adsorbs metal ions at the unstable portion of the charge, and magnesium hydroxide produced from magnesium oxide. There hydroxide ions OH ^- are presumed to adsorb phosphoric acid ion by dissociation.

When a bismuth source is not used, the phosphate ion removal ability by the bismuth oxychloride crystals described above cannot be obtained. In addition, it is presumed that the unstable portion of the charge formed on the surface of the magnesium oxide is suppressed, and the metal ion removal ability by the magnesium oxide described above is also suppressed. When R _{Mg / Bi} ≦ 9 using the bismuth source 11, the chlorine ions contained between the layers of the bismuth oxychloride crystals are sufficiently substituted with phosphate ions, and the charge formed on the surface of the magnesium oxide is reduced. It is presumed that the stable part sufficiently adsorbs metal ions.

From the above, the molar ratio R _{Mg / Bi} is preferably 3/7 or more and 9 or less.

The material 10 to be mixed may be only a combination of the bismuth source 11 and the magnesium source 12, but an additive 13 containing no bismuth source and magnesium source may be added. For example, 0.1 to 100 parts by weight of additive 13 may be added to 100 parts by weight of the combination of bismuth source 11 and magnesium source 12. The additive 13 may be a cation source such as an iron source or a calcium source. In this case, the ratio of the number of moles of cations to the total number of moles of bismuth and magnesium (M _Bi + M _Mg ) may be 0.001 or more and 1 or less.

  In order to produce bismuth oxychloride in the heating step S2, it is preferable that at least one of the materials 11, 12, and 13 described above has a chlorine source. As the chlorine source, bismuth chloride, magnesium chloride, iron chloride, calcium chloride, and the like can be used.

  The properties of the bismuth source 11, the magnesium source 12, and the optional additive 13 are preferably powder, but may be in the form of a lump if these materials 11, 12, and 13 can be powdered in the mixing step S1. When these materials 11, 12, and 13 are in powder form, the particle size of the materials 11, 12, and 13 is preferably a particle size that passes through a metal mesh sieve having an opening of 500 μm, and passes through a metal mesh sieve having an opening of 75 μm. More preferred is the particle size to be used. When these materials 11, 12, and 13 are granular, the average particle diameter of the materials 11, 12, and 13 is preferably 1 to 500 μm, and more preferably 1 to 75 μm. Here, the granular concept includes a powdery concept. The average particle diameter is 50% particle diameter (D50, median diameter) specified in JIS K1474: 2007 (activated carbon test method) for particles of 50 μm or more, and JIS K5600-9-3: 2006 for particles of less than 50 μm. From JIS Z8819-2 (Expression of Particle Size Measurement Results-Part 2: From Particle Size Distribution Based on (General Coating Test Method-Part 9: Powder Coating-Section 3: Measurement Method of Particle Size Distribution by Laser Diffraction) Part 2: The average particle diameter from the particle diameter distribution or the calculation of the average particle diameter and moment) is defined as a weighted volume average particle diameter.

  In the mixing step S1, the material 10 containing the bismuth source 11, the magnesium source 12, and the additive 13 as necessary is mixed. For this mixing, mixer, blender, horizontal cylinder type, V type, double cone type, square solid type, S type, continuous V type, ball mill type, rocking type, cross rotary type, ribbon type, screw type, rotor type , Pug mill type, planetary type, turbine type, high speed flow type, rotating disk type, etc. can be used. In the mixing step S1, the material 10 may be pulverized. For this pulverization, a pulverizer such as a ball mill, a bead mill, a rod mill, a disk mill, a ring mill, a high-pressure homogenizer, a shear mixer, a kneader, a planetary rotary mixer, a jet mill, an attrition mill, and a high-speed mixer can be used. In addition, grinding the material 10 with a mortar or the like is included in the grinding.

  In the heating step S2, the mixed material 20 (including the bismuth source 11, the magnesium source 12, and the optional additive 13) in the presence of the chlorine source is 100 in an oxygen-existing environment (for example, in the atmosphere). Heat at ~ 800 ° C. This produces crystals of bismuth oxychloride (BiOCl in stoichiometric ratio) from the bismuth source and chlorine source in the presence of oxygen, and magnesium oxide (MgO in stoichiometric ratio) from the magnesium source in the presence of oxygen. And bismuth oxychloride crystals serve as a carrier, and magnesium oxide is supported on bismuth oxychloride. For the heating in the heating step S2, heating devices such as various firing devices, various annealing devices, a hot plate, and an oven can be used. It is preferable that the heating device has a temperature control function and a temperature increase rate control function.

  The low temperature side of the heating temperature is required to be 100 ° C. or higher in terms of growing bismuth oxychloride crystals exhibiting phosphate ion removal ability, and is preferably 150 ° C. or higher from the point of sufficiently increasing the crystals of bismuth oxychloride. 200 ° C. or higher is more preferable, and 250 ° C. or higher is more preferable. The high temperature side of the heating temperature needs to be 800 ° C. or lower in order to suppress the decomposition of bismuth oxychloride crystals, and is preferably 550 ° C. or lower from the viewpoint of sufficiently securing the crystal size of bismuth oxychloride. More preferably, it is 450 ° C. or less.

In the cooling step S3, the material 21 (including the bismuth source 11, the magnesium source 12, and the optional additive 13) heated in the heating step S2 is cooled. This cooling may be natural cooling or forced cooling such as forced air cooling.
The composite material 1 containing bismuth oxychloride and magnesium oxide supported on the bismuth oxychloride is generated by the above-described steps S1 to S3.

  The composite material 1 obtained in the cooling step S3 may be pulverized in the pulverization step S4 as necessary. For this pulverization, a pulverizer such as a ball mill, a bead mill, a rod mill, a disk mill, a ring mill, a high-pressure homogenizer, a shear mixer, a kneader, a planetary rotary mixer, a jet mill, an attrition mill, and a high-speed mixer can be used.

7 to 9 are graphs showing examples of results obtained by performing powder X-ray diffraction measurement of a composite material sample by an X-ray diffraction wide angle method (XRD) using CuKα as an X-ray source. The composite material sample whose powder X-ray diffraction pattern is shown in FIG. 7 is a sample obtained by mixing bismuth chloride and magnesium hydroxide at a molar ratio R _{Mg / Bi} = 4, heating at 450 ° C., and naturally cooling. It is. The composite material sample whose powder X-ray diffraction pattern is shown in FIG. 8 is a sample obtained by changing the ultimate temperature during heating to 250 ° C., 350 ° C., and 450 ° C. The composite material sample showing the powder X-ray diffraction pattern in FIG. 9 is a sample obtained by changing the molar ratio R _{Mg / Bi} to 1/9, 1/4, 3/7, and 1. 7 to 9, the horizontal axis represents 2θ (°), and the vertical axis represents diffraction intensity. FIGS. 7 to 9 also show the diffraction intensities of magnesium oxide (stoichiometric MgO) crystals and bismuth oxychloride (stoichiometric BiOCl) crystals.

  In the example of the powder X-ray diffraction pattern shown in FIGS. 7 to 9, the bismuth oxychloride crystal has intensity peaks at 2θ = 12 °, 2θ = 26 °, and 2θ = 33-34 °. The sample also shows intensity peaks at around 2θ = 12 °, 2θ = 26 °, and 2θ = 33 to 34 °. Both of the composite material samples have an intensity peak at 2θ = 11.0 ° to 13.0 ° and an intensity peak at 2θ = 25.0 ° to 27.0 ° in the powder X-ray diffraction pattern, In addition, there is an intensity peak at 2θ = 33.0 ° to 34.0 °. Therefore, the composite material obtained by the manufacturing method described above has crystals of bismuth oxychloride, and has an intensity peak at 2θ = 11.0 ° to 13.0 ° in the powder X-ray diffraction pattern, and 2θ = 25. There is an intensity peak at 0.0 ° to 27.0 °, and an intensity peak at 2θ = 33.0 ° to 34.0 °.

  On the other hand, an intensity peak corresponding to the magnesium oxide crystal is not observed in the composite material sample. From this, it is presumed that the magnesium oxide contained in the composite material sample does not have a long-range order like a crystal and is in an amorphous (amorphous) state with a short-range order. Therefore, it is estimated that the composite material 1 obtained by the manufacturing method described above mainly contains bismuth oxychloride crystals and amorphous magnesium oxide supported on the crystals.

FIG. 10 shows an example of a photograph in which the surface of the composite material sample is taken with an SEM (scanning electron microscope). The composite material sample shown in FIG. 10 is a sample obtained by mixing bismuth chloride and magnesium chloride at a molar ratio R _{Mg / Bi} = 1, heating at 450 ° C., and naturally cooling.
In the center of the photograph shown in FIG. 10 and the powdery portion around it, powdery magnesium oxide is shown. Crystals of bismuth oxychloride are shown in the crystal part around the powdery part.

Here, it is confirmed by analysis by EDX (energy dispersive X-ray spectroscopy) that bismuth and chlorine are present in the crystal part and magnesium is present in the powder part. doing. Moreover, it has confirmed that oxygen exists in the part in which magnesium exists. Furthermore, when the magnesium hydroxide solid is heated, decomposition starts, the dissociation pressure of water vapor becomes 1 atm at 350 ° C., and magnesium oxide becomes red when heated.
Mg (OH) ₂ → MgO + H ₂ O
Since the elements contained in the composite material sample are bismuth, magnesium, chlorine, and oxygen, the powdery portion can be said to be magnesium oxide.

  As mentioned above, the composite material 1 obtained by the manufacturing method mentioned above is a novel composite material containing bismuth oxychloride and magnesium oxide supported on the bismuth oxychloride, and removes phosphate ions and metal ions. Material.

(3) Examples of water purifiers:
The composite material 1 mentioned above can be used for a water purification cartridge and a water purifier.
FIG. 2A schematically shows an example of a system kitchen incorporating a faucet having a water purifier. Of course, the application place of the water purifier is not limited to the system kitchen. In the system kitchen 200 shown in FIG. 2A, a concave sink 210 and a faucet 300 are incorporated in a counter 201 extending horizontally. The faucet 300 has a water discharge head 301 to which the water purifier 100 is attached, and discharges purified water from a water discharge port 303 at the tip of the water discharge head 301 when an operation for discharging purified water is performed at the operation unit 312. A water supply pipe 203 is connected to the lower part of the water purifier 100 via a connection pipe 314. As shown in FIG. 2B, the water discharge head 301 includes a water discharge pipe 302 connected to the water outlet 112 of the housing case 101.

  FIG. 2B is a cross-sectional view showing an example of a water purifier incorporating a water purification cartridge. In the water purifier 100 shown in FIG. 2B, the water purification cartridge 30 is detachably fixed in the housing case 101. The storage case 101 includes, for example, an upper case 102, a lower case 103, and an inner wall member 104. A water discharge pipe 302 is inserted into the upper end portion of the upper case 102. The inner wall member 104 is fitted in the lower case 103 and penetrates the counter 201 and protrudes downward. A connecting pipe 314 is connected to the lower end portion of the inner wall member 104. The upper case 102 is detachable from the lower case 103 and the upper end portions of the inner wall member 104. When the upper case 102 is removed from the lower case 103 and the inner wall member 104, the water purification cartridge 30 can be attached to and detached from the housing case 101. The composite material 1 is housed in the case 40 of the water purification cartridge 30. The water purifier 100 purifies the raw water that has flowed from the water inlet 111 through the water-permeable inflow portion 42 with the composite material 1 and discharges the raw water from the water outlet 112. Thereby, phosphate ions and metal ions are removed from the raw water.

(4) Example:
EXAMPLES Hereinafter, although an Example is shown and this invention is demonstrated concretely, this invention is not limited by the following examples.

[Example 1]
As the magnesium source, magnesium hydroxide (manufactured by Wako Pure Chemical Industries, Ltd., content: 95% by weight) was used. As the bismuth source, bismuth chloride (Wako Pure Chemical Industries, Ltd., content 97% by weight) was used.
The molar ratio _{Mg / Bi} was 1, and 0.7802 g of magnesium hydroxide (magnesium 12.7 mmol) and 4.1320 g of bismuth chloride (bismuth 12.7 mmol) were mixed in a mortar for 1 hour, and the mixture was transferred to a crucible. The temperature was raised to the ultimate temperature at a heating rate of 450 ° C./hr and heated at the ultimate temperature for 5 hours. Then, it allowed to cool naturally and obtained the composite material sample for every test section.
(Test section 1-1) Achieving temperature 150 ° C
(Test section 1-2) Achieving temperature 250 ° C
(Test section 1-3) Achieving temperature 350 ° C
(Test section 1-4) Ultimate temperature 450 ° C
(Test section 1-5) Achieving temperature 550 ° C

[Example 2]
Magnesium chloride hexahydrate (manufactured by Wako Pure Chemical Industries, Ltd., content 97% by weight) was used as the magnesium source. The same bismuth chloride as in Example 1 was used as the bismuth source.
The molar ratio _{Mg / Bi} is 1, 2.1003 g of magnesium chloride hexahydrate (10.0 mmol of magnesium) and 3.2527 g of bismuth chloride (10.0 mmol of bismuth) are mixed in a mortar for 1 hour, and the mixture is transferred to a crucible. The temperature was raised at a temperature rising rate of 450 ° C./hr to the temperature reached in each test section, and heated at the temperature reached for 5 hours. Then, it allowed to cool naturally and obtained the composite material sample for every test section.
(Test section 2-1) Achieving temperature 150 ° C
(Test section 2-2) Achieving temperature 250 ° C
(Test section 2-3) Achieving temperature 350 ° C
(Test section 2-4) Final temperature 450 ° C
(Test section 2-5) Achieving temperature 550 ° C

(Measurement of phosphate ion adsorption)
For the ion chromatograph, ICS-2100 manufactured by Thermo Fisher Scientific Inc. was used.
Disodium hydrogen phosphate was prepared to 100 mg / L with distilled water, 1.00 g of the composite material sample was added to 100 mL of this 100 mg / L disodium hydrogen phosphate aqueous solution, and the mixture was stirred for 24 hours. Thereafter, the filtrate was taken out, the molar concentration of phosphate ions was measured by ion chromatography, and the number of moles of phosphate ions adsorbed by a 1.00 g composite material sample was determined. The result is shown in FIG.

  As shown in FIG. 3, it was confirmed that phosphate ions were removed from the aqueous solution in all test sections. Although not shown, it was confirmed that phosphate ions were removed from the aqueous solution even at an ultimate temperature of 600 ° C. Further, it was found that when the ultimate temperature was 250 to 450 ° C., a more preferable phosphate ion removing ability was obtained. A more preferable reached temperature is 350 to 450 ° C., and a particularly preferable reached temperature is 450 ° C.

(Powder X-ray diffraction measurement)
FIG. 8 shows the results of the powder X-ray diffraction measurement of the composite material sample by the X-ray diffraction wide angle method (XRD) using CuKα as the X-ray source for the test sections 1-2, 1-3, and 1-4. It is a graph to show. As shown in FIG. 8, it was confirmed that intensity peaks were observed in the vicinity of 2θ = 12 °, 2θ = 26 °, and 2θ = 33 to 34 °. Even in test section 1-5 (attainment temperature 550 ° C.), intensity peaks are observed in the vicinity of 2θ = 12 °, 2θ = 26 °, and 2θ = 33 to 34 °, but the intensity of 2θ = 33 to 34 ° is observed. The peak was weak. This tendency is the same as in Example 2 (using magnesium chloride).

(Photographing the surface of a composite material sample)
FIG. 10 shows a photograph of the surface of the composite material sample in the test section 2-4 (the reached temperature of Example 2 at 450 ° C.) taken with an SEM (scanning electron microscope). In the center of the photograph shown in FIG. 10 and the powdery portion around it, powdery magnesium oxide is shown. In the crystal part around this powdery part, a layered crystal of bismuth oxychloride is shown. Therefore, the crystal of the layer structure of bismuth oxychloride carries amorphous magnesium oxide. Similar structures were found in the remaining test sections. In test sections 1-1 and 2-1 (attainment temperature 150 ° C.) and test sections 1-5 and 2-5 (attainment temperature 550 ° C.), the crystals of bismuth oxychloride were smaller than in the remaining test sections.

  From the powder X-ray diffraction pattern and the SEM photograph, it is presumed that the phosphate ion removal ability was exhibited by replacing the chlorine ions contained between the layered crystals of bismuth oxychloride with phosphate ions. In addition, the adsorption amount of phosphate ions decreased between the ultimate temperature of 150 ° C and the ultimate temperature of 550 ° C compared with the ultimate temperature of 250-450 ° C. This is presumably because the crystals of bismuth oxychloride were small. The It is presumed that the crystal growth of bismuth oxychloride is slower when the ultimate temperature is 150 ° C. than when the ultimate temperature is 250 ° C. or higher. In the case where the ultimate temperature is 550 ° C., it is assumed that the crystals of bismuth oxychloride are partially decomposed.

[Example 3]
The same magnesium hydroxide as in Example 1 was used as the magnesium source, the same bismuth chloride as in Example 1 was used as the bismuth source, and the ratio of magnesium (Mg) to bismuth (Bi), Mg: Bi, was changed as follows. Magnesium oxide and bismuth chloride were mixed in a mortar for 1 hour, the mixture was transferred to a crucible, heated to 450 ° C. at a heating rate of 450 ° C./hr in the atmosphere, and heated at an ultimate temperature of 450 ° C. for 5 hours.
(Comparative test section 3-1) 0:10,
(Test section 3-2) 1: 9 (R _{Mg / Bi} = _1/9 ),
(Test section 3-3) 2: 8 (R _{Mg / Bi} = 1/4),
(Test Section 3-4) 3: 7 (R _{Mg / Bi} = _3/7 ),
(Test section 3-5) 5: 5 (R _{Mg / Bi} = 1),
(Test Section 3-6) 8: 2 (R _{Mg / Bi} = 4),
(Test Section 3-7) 9: 1 (R _{Mg / Bi} = 9),
(Comparative test section 3-8) 10: 0.
Then, it allowed to cool naturally and obtained the composite material sample for every test section.

[Example 4]
The same magnesium chloride hexahydrate as in Example 2 was used as the magnesium source, the same bismuth chloride as in Example 1 was used as the bismuth source, and the ratio of magnesium (Mg) to bismuth (Bi) Mg: Bi was changed as follows: Then, mix magnesium chloride hexahydrate and bismuth chloride in a mortar for 1 hour, transfer the mixture to a crucible, raise the temperature to 450 ° C at a heating rate of 450 ° C / hr, and reach the final temperature of 450 ° C for 5 hours. Heated.
(Comparative test section 4-1) 0:10,
(Test section 4-2) 1: 9 (R _{Mg / Bi} = _1/9 ),
(Test section 4-3) 2: 8 (R _{Mg / Bi} = 1/4),
(Test Section 4-4) 5: 5 (R _{Mg / Bi} = 1),
(Test section 4-5) 8: 2 (R _{Mg / Bi} = 4),
(Test section 4-6) 9: 1 (R _{Mg / Bi} = 9),
(Comparative test section 4-7) 10: 0.
Then, it allowed to cool naturally and obtained the composite material sample for every test section.

(Measurement of phosphate ion adsorption)
For the composite material samples of Examples 3 and 4, as in the case of Examples 1 and 2, the number of moles of phosphate ions adsorbed by the 1.00 g composite material sample was determined. The result is shown in FIG. As shown in FIG. 4, the test sections 3-2 to 3-7 and 4-2 to 4-6 in which R _{Mg / Bi} ≧ 1/9 compared to Mg: Bi = 0: 10 without a magnesium source are phosphoric acid. The amount of ion adsorption was large. Moreover, compared with Mg: Bi = 10: 0 without a bismuth source, the test sections 3-4 to 3-7 and 4-4 to 4-6 in which 3/7 ≦ R _{Mg / Bi} ≦ 9 are phosphate ion adsorption amounts. There were many.

(Measurement of metal ion adsorption)
For the ion chromatograph, ICS-2100 manufactured by Thermo Fisher Scientific Inc. was used.
For the composite material samples of Examples 3 and 4 (excluding test sections 3-2 and 4-2), a mixed standard solution (manufactured by Wako Pure Chemical Industries, Ltd., multi-element mixed standard solution) in which each metal ion is 100 μg / L. WV) was added with 0.10 g composite material sample and stirred for 24 hours. Thereafter, the filtrate was taken out, and the molar concentration of phosphate ions was measured by an ion chromatograph to determine the number of moles of adsorbed metal ions per 1 g of the composite material sample. The result of the metal ion adsorption amount of Example 3 is shown in FIG. 5, and the result of the metal ion adsorption amount of Example 4 is shown in FIG.

As shown in FIGS. 5 and 6, the test sections 3-3 to 3-7 and 4-3 to 4-6 in which R _{Mg / Bi} ≧ 3/7 are compared with Mg: Bi = 0: 10 without a magnesium source. There was much metal ion adsorption. Moreover, compared with Mg: Bi = 10: 0 without a bismuth source, the test sections 3-4 to 3-7 and 4-4 to 4-6 in which 3/7 ≦ R _{Mg / Bi} ≦ 9 have a metal ion adsorption amount. There were many.

(Powder X-ray diffraction measurement)
FIG. 7: is a graph which shows the result of having performed the powder X-ray-diffraction measurement of the composite material sample by XRD which uses CuK (alpha) for X-ray source about the test section 3-6 ( _{RMg / Bi} = 4). FIG. 9 is a graph showing the results of the powder X-ray diffraction measurement of the composite material sample by XRD using CuKα as the X-ray source for the test sections 3-2, 3-3, 3-4 and 3-5. is there. As shown in FIGS. 7 and 9, it was confirmed that intensity peaks were observed in the vicinity of 2θ = 12 °, 2θ = 26 °, and 2θ = 33 to 34 °. Even in test section 3-2 (R _{Mg / Bi} = 1/9), intensity peaks are observed in the vicinity of 2θ = 12 °, 2θ = 26 °, and 2θ = 33 to 34 °, but 2θ = 12 °. The intensity peak was weak.

(Photographing the surface of a composite material sample)
FIG. 11 shows a photograph of an SEM image of bismuth oxychloride crystals contained in the composite material sample of Test Section 3-2 ( _{RMg / Bi} = _{1/9 in} Example 3). FIG. 12 shows a photograph of a bismuth oxychloride crystal contained in a composite material sample in Test Section 3-4 (R _{Mg / Bi} = _{3/7 in} Example 3) taken with an SEM. FIG. 13 shows a photograph taken with an SEM of a crystal of bismuth oxychloride contained in a composite material sample in test section 3-5 ( _{RMg / Bi} = 1 in Example 3). As shown in FIGS. 11 to 13, the smaller the molar ratio R _{Mg / Bi} , that is, the smaller the mixing ratio of the magnesium source, the smaller the layered crystal of bismuth oxychloride.

From the powder X-ray diffraction pattern and the SEM photograph, it is presumed that the phosphate ion removal ability was exhibited by replacing the chlorine ions contained between the layered crystals of bismuth oxychloride with phosphate ions. Moreover, the phosphate ion adsorption amount decreased in the case of R _{Mg / Bi} ≦ _1/4 compared with the case of _3/7 ≦ R _{Mg / Bi} ≦ 9 because the bismuth chloride melted by heating was easily evaporated. This is presumably because the crystal growth of bismuth oxychloride was suppressed and the crystals of bismuth oxychloride were small. When R _{Mg / Bi} ≧ 3/7, magnesium hydroxide is dissolved in bismuth chloride melted by heating, and transpiration of bismuth chloride is suppressed, and the ability to remove phosphate ions is exhibited by the crystals of bismuth oxychloride that have grown greatly. In addition, magnesium hydroxide produced from magnesium oxide in the composite material adsorbs phosphate ions by dissociation of hydroxide ions, and metal ions are formed at unstable parts of the charge formed on the surface of magnesium oxide. Is presumed to be sufficiently adsorbed.

Furthermore, when a bismuth source is not used, the ability to remove phosphate ions by layered crystals of bismuth oxychloride is not obtained, and the unstable portion of the charge formed on the surface of magnesium oxide is suppressed, thereby removing metal ions. It is speculated that this is also suppressed. When R _{Mg / Bi} ≦ 9, chlorine ions contained between layers of bismuth oxychloride crystals are sufficiently substituted with phosphate ions, and magnesium oxide sufficiently adsorbs metal ions at unstable charge portions. Guessed.

(EDX analysis)
14 to 18 show images obtained by analyzing the surface of the composite material sample in the test section 3-4 (R _{Mg / Bi} = 3/7 in Example 3) by EDX. 14 is a gray image of the sample surface, FIG. 15 is an image showing the distribution of magnesium, FIG. 16 is an image showing the distribution of oxygen, FIG. 17 is an image showing the distribution of bismuth, and FIG. It is an image which shows distribution of chlorine. Since the oxygen threshold shown in FIG. 16 is lower than the thresholds of the remaining elements, oxygen is distributed throughout. As shown in FIGS. 15 and 16, a bright portion of the oxygen distribution overlaps the magnesium distribution. As shown in FIGS. 17 and 18, bismuth and chlorine are widely distributed, and the distribution of chlorine overlaps the distribution of bismuth. Since the magnesium source becomes magnesium oxide when heated in the presence of oxygen, magnesium oxide is present in the portion where the magnesium is distributed.

  From the powder X-ray diffraction pattern, SEM photograph, and EDX analysis, it was confirmed that the composite material sample contained bismuth oxychloride and magnesium oxide supported on the bismuth oxychloride. This sample is a novel composite material that can remove phosphate ions and metal ions more efficiently.

(5) Conclusion:
As described above, according to the present invention, according to various aspects, it is possible to provide a technology such as a novel magnesium oxide-supported bismuth oxychloride composite material that can remove phosphate ions and metal ions more efficiently. it can. Needless to say, the above-described basic functions and effects can be obtained even with the technology consisting only of the constituent elements according to the independent claims.
In addition, the configurations disclosed in the above-described examples are mutually replaced or the combination is changed, the known technology and the configurations disclosed in the above-described examples are mutually replaced or the combinations are changed. The configuration described above can also be implemented. The present invention includes these configurations and the like.

1 ... Composite material,
11 ... bismuth source, 12 ... magnesium source, 13 ... additive,
30 ... Water purification cartridge, 40 ... Case (accommodating part), 42 ... Inflow part,
100 ... Water purifier, 111 ... Water inlet, 112 ... Water outlet, 300 ... Water faucet,
S1 ... Mixing step, S2 ... Heating step, S3 ... Cooling step, S4 ... Crushing step.

Claims (6)

  A composite material comprising bismuth oxychloride and magnesium oxide supported on the bismuth oxychloride.   In the powder X-ray diffraction pattern, there is an intensity peak at 2θ = 11.0 ° to 13.0 °, an intensity peak at 2θ = 25.0 ° to 27.0 °, and 2θ = 33.0. The composite material according to claim 1, wherein the composite material has an intensity peak at from ˜34.0 °.   The composite material according to claim 1 or 2, wherein a molar ratio of magnesium to bismuth is 3/7 or more and 9 or less. A mixing step of mixing a material containing a bismuth source and a magnesium source;
Heating the mixed material at 100-800 ° C. in the presence of a chlorine source;
A cooling step for cooling the heated material;
And a method for producing a composite material containing bismuth oxychloride and magnesium oxide supported on the bismuth oxychloride. The composite material according to any one of claims 1 to 3,
A storage section in which water can enter and exit, and stores the composite material;
Water purification cartridge with The composite material according to any one of claims 1 to 3,
A housing portion containing the composite material;
A water inlet,
Water outlet,
A water purifier in which water to be treated flows into the housing portion from the water inlet, and water treated with the composite material in the housing portion flows out from the water outlet.