JP6444083B2 - Water purifier cartridge and water purifier - Google Patents

Description

  The present invention relates to a water purifier cartridge and a water purifier.

  As soft water effects, (a) mellow the taste of tea and coffee, (b) prevent scales from cooking utensils, etc. (c) improve the foaming of soap, (d) water into containers such as glasses For example, the generation of marks is suppressed. For this reason, conventionally, water purifiers having a softening function have been widely used. As such a water purifier, for example, a water purifier filled with a cation exchange resin in a container is used.

  Patent Document 1 (Japanese Patent Laid-Open No. 2014-100635) discloses a water purifier in which a cylindrical container is filled with a Na-type strongly acidic cation exchange resin (Amberjet (registered trademark) 1220) having a low crosslinking degree. (Paragraph [0057]).

JP 2014-100653 A

  When a strongly acidic cation exchange resin comes into contact with water, elution of components derived from impurities and the like occurs. This elution increases as the contact time between the strongly acidic cation exchange resin and water increases. In particular, in water purifiers, it is necessary to prevent as much as possible the elution of substances that adversely affect human health and the living environment as specified in the tap water quality standard items.

  Since the water supplied to the water purifier is basically tap water, the present inventors investigated the eluate from the strong acid cation exchange resin due to contact between the tap water and the strong acid cation exchange resin. As a result, it was found that formaldehyde is eluted from the strongly acidic cation exchange resin by contacting the tap water with the strongly acidic cation exchange resin regardless of the presence or absence of residual chlorine in the tap water. Therefore, it is considered that the elution of formaldehyde is not caused by oxidative decomposition of the strongly acidic cation exchange resin due to residual chlorine or the like.

  Moreover, generally the usage method of a water purifier is not continuous but becomes intermittent use. For example, when the water purifier is used at home, the sleeping hours at midnight are unused. The longer this unused time, the higher the eluate concentration of the water purifier outlet water immediately after the start of the next morning, and the higher the formaldehyde concentration. Therefore, in the water purifier after being stopped for a certain period of time, it was necessary to suppress the elution of formaldehyde from the strongly acidic cation exchange resin at the start of use.

  The present invention has been made in view of the above problems. That is, the present invention relates to a water purifier cartridge and a water purifier that suppresses the elution of formaldehyde into treated water (water after passing through the water purifier) even when the use is stopped after being stopped for a certain period of time. The purpose is to provide.

One embodiment is:
It is a cartridge for a water purifier filled with a strong acid cation exchange resin having a crosslinking degree of 16 to 24% alone, and the concentration of formaldehyde in the treated water when raw water is passed is suppressed to 0.013 mg / L or less. The present invention relates to a water purifier cartridge and a water purifier.
In another embodiment, raw water is passed through a cartridge for water purifier alone filled with a strong acid cation exchange resin having a crosslinking degree of 16 to 24%, and the treated water in which the formaldehyde concentration is suppressed to 0.013 mg / L or less. It is related with the manufacturing method of the treated water characterized by manufacturing.

  Even if it is a case where use is started after stopping use for a fixed time, the cartridge for water purifiers and water purifier which suppress elution of formaldehyde to treated water can be provided.

  One embodiment relates to a water purifier cartridge filled with a strongly acidic cation exchange resin having a crosslinking degree of 16 to 24%. Other embodiment is related with the water purifier provided with the cartridge for water purifiers which arrange | positioned activated carbon and strong acid cation exchange resin in this order in the water flow direction, and the housing which accommodates the cartridge for water purifiers. Formaldehyde is considered to elute into the treated water when a part of the structure of the strongly acidic cation exchange resin is released or reacted by desorption or decomposition. Thus, by setting the degree of cross-linking of the strongly acidic cation exchange resin to 16 to 24%, it is possible to suppress part of the resin structure from desorbing, decomposing, reacting, and the like. As a result, it can suppress effectively that formaldehyde elutes in treated water (water after passing through a water purifier). If the degree of cross-linking is less than 16%, the structural strength of the strongly acidic cation exchange resin becomes insufficient, and elution of formaldehyde tends to occur. On the other hand, when the degree of cross-linking exceeds 24%, the ion exchange rate becomes slow, or the regeneration rate of the strongly acidic cation exchange resin becomes slow.

  The degree of crosslinking of the strongly acidic cation exchange resin is determined by the content of the crosslinking agent in the raw material for the strongly acidic cation exchange resin. For example, in the case of a methacrylic, acrylic or styrene strongly acidic cation exchange resin, the degree of crosslinking is determined by the content of divinylbenzene as a crosslinking agent in the raw material.

  The strongly acidic cation exchange resin can have any structure among a gel type structure, a macroporous type structure, and a porous type structure. Preferably, the strongly acidic cation exchange resin may have a macroporous structure or a porous structure.

  The gel type structure, the macroporous type structure and the porous type structure can be distinguished by the following method.

The strongly acidic cation exchange resin may be in a salt form or an H form. Type strongly acidic cation exchange resin of the salt form is not particularly limited, for example, a Na type strong acidic cation exchange resin, K-type strongly acidic cation exchange resin. A desired H form or salt form can be obtained by passing a solution corresponding to the strongly acidic cation exchange resin (for example, HCl aqueous solution in H form, NaOH aqueous solution in Na form, KOH aqueous solution in K form). Can be passed through).

  The matrix structure of the strongly acidic cation exchange resin is not particularly limited, and for example, it can be a methacrylic, acrylic or styrene strong acid cation exchange resin.

  As the strongly acidic cation exchange resin, a commercially available one can be used as long as the degree of crosslinking is 16 to 24%. Examples of the strongly acidic cation exchange resin having a gel type structure include Amberjet 1060, 1600 (Amberjet; registered trademark), Diaion SK116 (Diaion; registered trademark), and Purolite C100X16MBH (Purolite; registered trademark). Examples of the strongly acidic cation exchange resin having a macroporous structure include Amberlite 200C, 200CT (AMBERLITE; registered trademark), and Amberlex 210 (AMBEREX; registered trademark).

  It is good also as a water purifier cartridge which provided activated carbon in the front | former stage (upstream side with respect to a water flow direction) of strong acid cation exchange resin, and has arrange | positioned activated carbon and strong acid cation exchange resin in this order, and this. This activated carbon can remove organic substances other than the cation component in water, dissolved oxygen, residual chlorine, and the like, thereby further improving the purity of water.

  The form of the water purifier is not particularly limited. For example, the water purifier has a housing, a raw water inlet provided in the upper part of the housing, and a water outlet provided in the lower part of the housing, and a water purifier cartridge is disposed in the housing. The cartridge for equipment can be one that communicates with the raw water inlet and the purified water outlet. Although it does not specifically limit as a kind of water purifier, For example, a pot type, a faucet direct connection type, a stationary type, or an undersink type water purifier can be used.

  EXAMPLES Hereinafter, although this invention is demonstrated further in detail with reference to an Example, this invention is not limited by these Examples.

[Example 1]
Na type strongly acidic cation exchange resin (trade name; Amberlite (registered trademark) 200CT (Dow Chemical Co., Ltd.) in an acrylic column having an inner diameter of 4.6 cm and a height of 100 cm and having a macroporous structure with a crosslinking degree of 20%. The product was filled with 900 ml of Sagamihara-shi water having a water temperature of 23 ° C. at SV60 BV / hour for 15 minutes. Then, it is left for 24 hours (in a room immersed in a room adjusted to 23 ° C.), and again the tap water at 23 ° C. is passed for 1 minute at SV60 BV / hour, and the effluent water (treated water) is collected. The formaldehyde concentration was analyzed. The formaldehyde concentration was determined by a method using solvent extraction of formaldehyde, derivatization of formaldehyde, and gas chromatography mass spectrometry according to JIS S 3200-7: 2004 Annex 9.

[Example 2]
In Example 1, the Na-type strongly acidic cation exchange resin was changed to a strongly acidic cation exchange resin (trade name; Amberjet (registered trademark) 1060 (manufactured by Dow Chemical Company)) having a gel-type structure with a crosslinking degree of 16%. did. Except for this, water was passed through in the same manner as in Example 1 to measure the formaldehyde concentration.

[Example 3]
Water was passed in the same manner as in Example 1 except that the water supplied to the water purifier was changed to Sagamihara City water from which residual chlorine and dissolved oxygen were removed, and the formaldehyde concentration was measured. Residual chlorine was removed with activated carbon, and dissolved oxygen was removed with a degassing membrane.

[Example 4]
Water was passed in the same manner as in Example 2 except that the water supplied to the water purifier was changed to Sagamihara City water from which residual chlorine and dissolved oxygen were removed, and the formaldehyde concentration was measured. The residual chlorine and dissolved oxygen were removed in the same manner as in Example 3.

[Comparative Example 1]
In Example 1, the Na-type strongly acidic cation exchange resin used was changed to a strongly acidic cation exchange resin (Amberjet (registered trademark) 1220; manufactured by Dow Chemical Co., Ltd.) having a gel-type structure with a crosslinking degree of 8%. did. Except for this, water was passed through in the same manner as in Example 1 to measure the formaldehyde concentration.

[Comparative Example 2]
In Example 3, the Na-type strongly acidic cation exchange resin used was changed to a strongly acidic cation exchange resin (Amberjet (registered trademark) 1220; manufactured by Dow Chemical Co., Ltd.) having a crosslinking degree of 8% and a gel-type structure. did. Except for this, water was passed through in the same manner as in Example 3 to measure the formaldehyde concentration.

[Comparative Example 3]
In Example 1, the Na-type strongly acidic cation exchange resin used was changed to a strongly acidic cation exchange resin (Amberjet (registered trademark) 1024; manufactured by Dow Chemical Co., Ltd.) having a gel degree structure with a crosslinking degree of 12%. did. Except for this, water was passed through in the same manner as in Example 1 to measure the formaldehyde concentration.

(result)
Table 1 shows the types of strong acidic cation exchange resins used in Examples 1 to 4 and Comparative Examples 1 to 3, and Table 2 shows the formaldehyde concentration in the treated water after passing through the water purifier. The formaldehyde concentration in the feed water before passing through the water purifier was less than 0.005 mg / L for both Sagamihara city water and Sagamihara city water from which residual chlorine and dissolved oxygen were removed.

  From the results of Table 2, in any of the examples and comparative examples, the concentration of formaldehyde in the treated water may increase as compared with the feed water (Sagamihara city water and Sagamihara city water from which residual chlorine and dissolved oxygen have been removed). I understand. However, in all Examples, the formaldehyde concentration in the treated water was lower than the formaldehyde concentration in the treated water in the comparative example. From the inventor's previous investigation, the formaldehyde concentration in the treated water increased as the immersion time of the strongly acidic cation exchange resin in water increased, so the formaldehyde concentration in the treated water in the examples was reduced as described above. This is probably because elution of formaldehyde from the strongly acidic cation exchange resin into the treated water was suppressed. In Examples 3 and 4 and Comparative Example 2, formaldehyde was eluted in the treated water despite the use of Sagamihara city water from which residual chlorine and dissolved oxygen were removed as the feed water. Is considered to be eluted in the treated water by a mechanism different from the oxidative degradation of the strongly acidic cation exchange resin due to chlorine, dissolved oxygen, or the like.

Claims (5)

  It is a cartridge for a water purifier filled with a strong acid cation exchange resin having a crosslinking degree of 16 to 24% alone, and the concentration of formaldehyde in the treated water when raw water is passed is suppressed to 0.013 mg / L or less. Features a water purifier cartridge. A water purifier cartridge in which activated carbon and a strong acid cation exchange resin are arranged in this order in the direction of water flow, and the strong acid cation exchange resin is filled with a strong acid cation exchange resin having a crosslinking degree of 16 to 24% as the strong acid cation exchange resin. And the formaldehyde concentration in the treated water when raw water is passed is suppressed to 0.013 mg / L or less . The cartridge for water purifier according to claim 1 or 2, wherein the strongly acidic cation exchange resin has a porous structure or a macroporous structure . The water purifier cartridge according to any one of claims 1 to 3,
A housing for housing the water purifier cartridge;
A water purifier characterized by comprising   The raw water is passed through a cartridge for a water purifier alone filled with a strongly acidic cation exchange resin having a crosslinking degree of 16 to 24% to produce treated water in which the formaldehyde concentration is suppressed to 0.013 mg / L or less. To produce treated water.