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WO2018158943A1 - Inhibiteur de dégradation pour membrane d'osmose inverse et procédé de traitement d'eau - Google Patents

Inhibiteur de dégradation pour membrane d'osmose inverse et procédé de traitement d'eau Download PDF

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Publication number
WO2018158943A1
WO2018158943A1 PCT/JP2017/008545 JP2017008545W WO2018158943A1 WO 2018158943 A1 WO2018158943 A1 WO 2018158943A1 JP 2017008545 W JP2017008545 W JP 2017008545W WO 2018158943 A1 WO2018158943 A1 WO 2018158943A1
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WIPO (PCT)
Prior art keywords
reverse osmosis
osmosis membrane
membrane
urea
water
Prior art date
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Ceased
Application number
PCT/JP2017/008545
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English (en)
Japanese (ja)
Inventor
孝博 川勝
雄介 的場
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Kurita Water Industries Ltd
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Kurita Water Industries Ltd
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Publication date
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Priority to PCT/JP2017/008545 priority Critical patent/WO2018158943A1/fr
Publication of WO2018158943A1 publication Critical patent/WO2018158943A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D65/00—Accessories or auxiliary operations, in general, for separation processes or apparatus using semi-permeable membranes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/56—Polyamides, e.g. polyester-amides
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis

Definitions

  • the reverse osmosis (RO) membrane used in the water treatment field has reduced solute inhibition performance such as desalination rate due to the oxidizing substances present in the RO membrane feed water and substances that increase the redox potential.
  • the present invention relates to an agent that is added to the supply water to suppress a decrease in the solute blocking performance of the RO membrane when there is a risk of it.
  • the present invention also relates to a water treatment method for performing RO membrane treatment using this agent.
  • RO membrane system Separation and purification by RO membrane system is an energy-saving process for systems using evaporation and electrodialysis, and is widely used for desalination of seawater and brine, production of industrial water and ultrapure water, and recovery of wastewater. It has been.
  • fouling occurs in which the RO membrane is contaminated with microorganisms and organic substances.
  • hydrogen peroxide, a bonded halogen agent, or an oxidizing agent such as a halogen agent is used to suppress the growth of microorganisms that cause fouling and to decompose organic substances.
  • a representative example of the bound halogen agent is a bound chlorine agent such as chloramine.
  • halogen agent sodium hypochlorite.
  • sodium hypochlorite sodium hypochlorite.
  • these oxidizing substances may cause deterioration of the RO membrane if the amount used is wrong, invalidation immediately before the RO membrane is insufficient, or heavy metals coexist in the supply water.
  • Patent Document 1 describes that when sodium bisulfite is added for dechlorination, the presence of copper ions raises the oxidation-reduction potential and exceeds 300 mV.
  • Patent Document 2 proposes a method of adding an oxidant as a method of invalidating the oxidizing substance.
  • Patent Document 2 describes that an amino acid that is an oxidant erases a strong oxide without erasing the bonded halogen fungicide.
  • amino acids can eliminate bound halogen fungicides.
  • the present invention suppresses the RO membrane deterioration without reducing the fouling suppression effect of the bonded halogen agent or the like when the RO membrane supply water may deteriorate the RO membrane. It is an object to provide an agent and a water treatment method for performing RO membrane treatment using this agent.
  • the present inventor has intensively studied a mechanism for suppressing the deterioration of the RO membrane, and found that the presence of urea in the RO supply water can suppress the deterioration of the RO membrane.
  • a bound halogen agent When a bound halogen agent is used to suppress fouling of the RO membrane, if a non-oxidizing agent such as an amino acid is used, the bound halogen agent is consumed and the function of suppressing fouling is reduced. If it is urea, the deterioration of the RO membrane can be suppressed without consuming the bound halogen agent.
  • a non-oxidizing agent such as an amino acid
  • a reverse osmosis membrane deterioration inhibitor that is added to a reverse osmosis membrane when supplying supply water having an oxidation-reduction potential exceeding 300 mV to the reverse osmosis membrane, the reverse osmosis membrane containing urea and / or a urea derivative Degradation inhibitor.
  • a water treatment method comprising performing reverse osmosis membrane treatment by adding the reverse osmosis membrane deterioration inhibitor according to any one of [1] to [4] to water supplied to the reverse osmosis membrane.
  • the present invention when the redox potential of the RO membrane feed water is high or the oxidizing substance in the feed water without reducing the effect of the bonded halogen agent used for suppressing the fouling of the RO membrane. It is possible to effectively suppress the deterioration of the RO membrane caused when it is contained.
  • FIG. 6 is a graph showing the change over time in free chlorine concentration and combined chlorine concentration after addition of a deterioration inhibitor in Example I-1 and Comparative Example I-1. 6 is a graph showing changes with time in the TOC concentration after addition of a deterioration inhibitor in Example I-1 and Comparative Example I-1.
  • FIG. 3a is a schematic diagram showing the configuration of the flat membrane test apparatus used in Experiment II.
  • FIG. 3b is a cross-sectional view showing the structure of the closed container of the flat membrane test apparatus.
  • 2 is a graph showing the change over time in the desalting rate in Example II-1 and Comparative Examples II-1 and II-2. 2 is a graph showing the change over time in the desalting rate in Example III-1 and Comparative Example III-1.
  • urea and / or urea derivative may be referred to as “urea (derivative)”.
  • Urea derivatives
  • urea H 2 N—CO—NH 2
  • Urea has a structure close to the amide bond of the aromatic polyamide RO membrane, and has a strong affinity for the amide bond portion.
  • the attack on the amide bond of the oxidizing substance in the oxidizing environment is prevented, and the amide bond cleavage is suppressed. Therefore, by being oxidized, it works differently from an oxidizable substance that reduces the oxidizable substance and reduces the influence of the oxidizable substance.
  • Urea derivatives
  • urea is a low carbon source and is structurally unlikely to decompose due to attack of oxidizing substances. For this reason, the bound halogen agent is hardly consumed, and the fouling suppression effect by the bound halogen agent is not lowered.
  • the RO membrane to be cleaned may be an aromatic polyamide RO membrane or a cellulose acetate RO membrane.
  • the present invention is particularly effective in suppressing deterioration of the aromatic polyamide RO membrane in terms of the adsorption action of urea (derivative) to the amide bond portion of the aromatic polyamide RO membrane.
  • the urea (derivative) used in the present invention is preferably a low molecular compound having a molecular weight of 300 or less.
  • Urea (derivative) Examples of the urea derivative include those represented by the following general formula (I), specifically urea (H 2 N—CO—NH 2 ), biuret (H 2 N—CO—NH—CO). —NH 2 ), polyurea, others, semicarbazide, allantoin, citrulline, thiourea, thiosemicarbazide, thiourea derivatives and the like.
  • R 1 , R 2 , R 3 , and R 4 each independently represents a hydrogen atom, an alkyl group, an aryl group, or —R 5 CONH 2 (wherein R 5 represents a single bond or an alkylene group) Represents an amidoacyl group having
  • Urea (derivative) may be used alone or in combination of two or more.
  • urea derivatives
  • urea and biuret are preferable in terms of RO membrane protection effect, solubility, and availability, and urea is particularly preferable.
  • RO supply water The RO membrane supply water targeted in the present invention (hereinafter sometimes referred to as “RO supply water”) is: (1) Redox potential (ORP) exceeds 300 mV (including substances that increase ORP) Or (2) Supply water that may reduce the solute blocking performance such as the desalination rate of the RO membrane by passing water by containing an oxidizing agent (oxidizing substance).
  • ORP Redox potential
  • Oxidizing substance oxidizing substance
  • the present invention is particularly effective for feed water having an ORP of 400 mV or higher and high RO membrane deterioration.
  • supply water for example, water containing alkali metal ions and transition metal ions such as copper ions and manganese ions such as seawater is added with an oxidizing agent such as sodium hypochlorite to suppress fouling.
  • an oxidizing agent such as sodium hypochlorite
  • feed water pH 5 to 9 to which a reducing agent such as sodium bisulfite is added for dechlorination.
  • Oxidizing agents contained in the feed water containing oxidizing agents include hydrogen peroxide, stabilizing halogens (bonded halogen agents), halogen oxo acids such as peracetic acid, percarbonate, sulfurous acid, hypochlorous acid and their salts (for example, , Alkali metal salts, alkaline earth metal salts), halogens such as chlorine, bromine and iodine, peroxides, and the like.
  • hydrogen peroxide, halogen, stabilized halogen (bonded halogen agent), or one or more of sulfites are preferred.
  • the bonded halogen agent is preferable.
  • bonded halogen agent examples include bonded chlorine agents such as chloramine and monochlororosulmic acid.
  • the content of the oxidizing agent in the feed water is not particularly limited, but is about 0.01 to 1 mg / L for halogen and about 0.1 to 100 mg / L for stabilized halogen.
  • RO feed water preferably has a pH of 6 to 9 from the standpoint of maintaining the blocking performance and suppressing the scale.
  • urea (derivative) is added to the RO supply water that lowers the solute inhibition performance such as the desalination rate of the RO membrane to suppress the degradation of the solute inhibition performance. If the amount of urea (derivative) added to the RO supply water is too small, the effect of suppressing deterioration due to the addition of urea (derivative) cannot be sufficiently obtained. If the amount of urea (derivative) added to the RO supply water is too large, it may become a carbon source for microorganisms or may leak in a large amount to the RO permeate.
  • the amount of urea (derivative) added is in the range of 0.01 to 100 mg / L, particularly 0.1 to 10 mg / L, and is appropriately set according to the degree of ORP of the RO supply water, the type and content of the oxidizing agent It is preferable to do.
  • the water treatment method of the present invention can be carried out according to a conventional method except that urea (derivative) is added to the RO supply water as an RO membrane deterioration inhibitor. Addition of urea (derivative) to the RO supply water may be continuous or intermittent, but it is preferable to add continuously.
  • Comparative Example I-1 The above 1) to 3) were performed using 1 mg / L of aspartic acid as a deterioration inhibitor.
  • Example I-1 1 mg / L of urea was used as a deterioration inhibitor, and the above 1) to 3) were carried out.
  • Fig. 1 shows the changes over time in the free chlorine concentration and the combined chlorine concentration after the deterioration inhibitor was added.
  • the free chlorine concentration was decreased, but the bound chlorine concentration was also decreased, indicating that the bound chlorine agent was consumed.
  • both the free chlorine concentration and the combined chlorine concentration decreased slowly.
  • FIG. 2 shows the change with time in the TOC concentration after the addition of the deterioration inhibitor.
  • This TOC concentration excludes the TOC concentration before adding the deterioration inhibitor as a blank.
  • the initial TOC concentration was higher than that in Example I-1 to which urea was added, and decreased with time. This means that aspartic acid is decomposed by free chlorine or combined chlorine.
  • urea there is almost no change, and it can be seen that urea is hardly affected by free chlorine and bound chlorine.
  • FIG. RO treatment was performed using the flat membrane test apparatus shown to 3a, 3b.
  • the RO membrane used was “ES20” manufactured by Nitto Denko Corporation, and the recovery rate was 80%.
  • RO membrane supply water is supplied from a pipe 11 to a raw water chamber 1A below the flat membrane cell 2 in which the RO membrane of the sealed container 1 is set by a high-pressure pump 4.
  • FIG. As shown in 3b, the sealed container 1 is composed of a lower case 1a on the raw water chamber 1A side and an upper case 1b on the permeate water chamber 1B side, and a flat membrane cell between the lower case 1a and the upper case 1b. 2 is fixed through an O-ring 8.
  • the flat membrane cell 2 is configured such that the permeate side of the RO membrane 2A is supported by the porous support plate 2B.
  • the raw water chamber 1 ⁇ / b> A below the flat membrane cell 2 is stirred by rotating the stirring bar 5 with a stirrer 3.
  • the RO membrane permeated water is taken out from the pipe 12 through the permeated water chamber 1B on the upper side of the flat membrane cell 2.
  • the concentrated water is taken out from the pipe 13.
  • the pressure in the sealed container 1 is adjusted by a pressure gauge 6 provided in the water supply pipe 11 and a pressure adjusting valve 7 provided in the concentrated water outlet pipe 13.
  • Desalination rate [-] 1-conductivity of permeated water / conductivity of concentrated water
  • Comparative Example II-1 1) to 4) were carried out without using a deterioration inhibitor.
  • Comparative Example II-2 1 mg / L of aspartic acid was used as a deterioration inhibitor and 1) to 4) were carried out.
  • Example II-1 1 mg / L of urea was used as a deterioration inhibitor, and 1) to 4) were carried out.
  • Fig. 5 shows the change over time in the desalting rate.
  • Comparative Example II-1 in which no deterioration inhibitor was used, the desalting rate was the lowest.
  • Comparative Example II-2 using aspartic acid as the deterioration inhibitor, the decrease in the desalting rate can be suppressed, but as shown in Experiment I, it is considered that bound chlorine is consumed.
  • Example II-1 using urea as a deterioration inhibitor the decrease in the desalting rate was suppressed, and as shown in Experiment I, bound chlorine was not consumed. It is considered that the effect of suppressing the decrease in the desalination rate can be improved by changing the amount of urea added.
  • FIG. RO treatment was performed using the flat membrane test apparatus shown to 3a, 3b.
  • the RO membrane used was “ES20” manufactured by Nitto Denko Corporation, and the recovery rate was 80%.
  • Comparative Example III-1 1) to 4) were carried out without using a deterioration inhibitor.
  • Example III-1 100 mg / L of urea was used as a deterioration inhibitor, and 1) to 4) were carried out.
  • Fig. 5 shows the change over time in the desalting rate.
  • Comparative Example III-1 in which no deterioration inhibitor is used, the desalination rate is greatly reduced over time, but in Example III-1 in which urea is used as the deterioration inhibitor, reduction in the desalination rate can be suppressed. .

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Organic Chemistry (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)

Abstract

La présente invention permet d'inhiber efficacement la détérioration d'une membrane d'osmose inverse se produisant lorsque le potentiel d'oxydation/réduction de l'eau d'alimentation pour la membrane d'osmose inverse est élevé ou lorsque des substances oxydantes sont incluses dans de l'eau d'alimentation sans abaisser les effets d'un agent de liaison à l'halogène utilisé pour inhiber l'encrassement de la membrane d'osmose inverse. L'invention concerne un inhibiteur de dégradation pour une membrane d'osmose inverse qui est ajouté pour fournir de l'eau lorsque l'eau d'alimentation dans laquelle le potentiel d'oxydation/réduction dépasse 300 mV ou lorsque l'eau d'alimentation comprenant un agent oxydant est fournie à la membrane d'osmose inverse, l'inhibiteur de dégradation comprenant de l'urée et/ou un dérivé d'urée. L'invention concerne également un procédé de traitement d'eau dans lequel un traitement par membrane d'osmose inverse est réalisé en ajoutant cet inhibiteur de dégradation pour une membrane d'osmose inverse à l'eau d'alimentation pour la membrane d'osmose inverse.
PCT/JP2017/008545 2017-03-03 2017-03-03 Inhibiteur de dégradation pour membrane d'osmose inverse et procédé de traitement d'eau Ceased WO2018158943A1 (fr)

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PCT/JP2017/008545 WO2018158943A1 (fr) 2017-03-03 2017-03-03 Inhibiteur de dégradation pour membrane d'osmose inverse et procédé de traitement d'eau

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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08132093A (ja) * 1994-11-09 1996-05-28 Otsuka Chem Co Ltd 洗浄剤組成物
JP2004244345A (ja) * 2003-02-13 2004-09-02 Toray Ind Inc 水処理用殺菌剤、水処理方法および水処理装置
JP2005154551A (ja) * 2003-11-25 2005-06-16 Amtec Co Ltd 除菌洗浄剤組成物
JP2009078218A (ja) * 2007-09-26 2009-04-16 Toray Ind Inc 複合半透膜の製造方法
JP2009183825A (ja) * 2008-02-05 2009-08-20 Kobelco Eco-Solutions Co Ltd 水処理装置
JP2011208138A (ja) * 2010-03-12 2011-10-20 Sanyo Chem Ind Ltd 医療用具用洗浄剤
US20130101683A1 (en) * 2011-10-21 2013-04-25 Nalco Company Use of sulfamic acid or its salts as stabilizers especially in combination with ammonium salt and/or ammine for bleach or other halogen containing biocides in the paper area
WO2015073170A1 (fr) * 2013-11-12 2015-05-21 Ecolab Usa Inc. Composition et procédé pour inhiber l'encrassement biologique d'un dispositif de séparation sur membrane

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08132093A (ja) * 1994-11-09 1996-05-28 Otsuka Chem Co Ltd 洗浄剤組成物
JP2004244345A (ja) * 2003-02-13 2004-09-02 Toray Ind Inc 水処理用殺菌剤、水処理方法および水処理装置
JP2005154551A (ja) * 2003-11-25 2005-06-16 Amtec Co Ltd 除菌洗浄剤組成物
JP2009078218A (ja) * 2007-09-26 2009-04-16 Toray Ind Inc 複合半透膜の製造方法
JP2009183825A (ja) * 2008-02-05 2009-08-20 Kobelco Eco-Solutions Co Ltd 水処理装置
JP2011208138A (ja) * 2010-03-12 2011-10-20 Sanyo Chem Ind Ltd 医療用具用洗浄剤
US20130101683A1 (en) * 2011-10-21 2013-04-25 Nalco Company Use of sulfamic acid or its salts as stabilizers especially in combination with ammonium salt and/or ammine for bleach or other halogen containing biocides in the paper area
WO2015073170A1 (fr) * 2013-11-12 2015-05-21 Ecolab Usa Inc. Composition et procédé pour inhiber l'encrassement biologique d'un dispositif de séparation sur membrane

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