JP6823401B2 - 低分子有機物含有水の処理方法および逆浸透膜の改質方法 - Google Patents
低分子有機物含有水の処理方法および逆浸透膜の改質方法 Download PDFInfo
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- JP6823401B2 JP6823401B2 JP2016162961A JP2016162961A JP6823401B2 JP 6823401 B2 JP6823401 B2 JP 6823401B2 JP 2016162961 A JP2016162961 A JP 2016162961A JP 2016162961 A JP2016162961 A JP 2016162961A JP 6823401 B2 JP6823401 B2 JP 6823401B2
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- reverse osmosis
- osmosis membrane
- water
- treatment
- weight organic
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- 238000001223 reverse osmosis Methods 0.000 title claims description 216
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims description 186
- 238000000034 method Methods 0.000 title claims description 66
- 239000000126 substance Substances 0.000 title claims description 52
- 239000000203 mixture Substances 0.000 claims description 91
- -1 sulfamic acid compound Chemical class 0.000 claims description 74
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 73
- 229910052794 bromium Inorganic materials 0.000 claims description 71
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 65
- 229920002647 polyamide Polymers 0.000 claims description 61
- CUILPNURFADTPE-UHFFFAOYSA-N hypobromous acid Chemical compound BrO CUILPNURFADTPE-UHFFFAOYSA-N 0.000 claims description 52
- 239000007800 oxidant agent Substances 0.000 claims description 31
- 239000004952 Polyamide Substances 0.000 claims description 23
- 239000003513 alkali Substances 0.000 claims description 14
- 239000005416 organic matter Substances 0.000 claims description 13
- JGJLWPGRMCADHB-UHFFFAOYSA-N hypobromite Chemical compound Br[O-] JGJLWPGRMCADHB-UHFFFAOYSA-N 0.000 claims description 10
- 238000005342 ion exchange Methods 0.000 claims description 10
- 230000001954 sterilising effect Effects 0.000 claims description 10
- 238000004659 sterilization and disinfection Methods 0.000 claims description 10
- 239000012298 atmosphere Substances 0.000 claims description 8
- 239000011261 inert gas Substances 0.000 claims description 8
- DKSMCEUSSQTGBK-UHFFFAOYSA-N bromous acid Chemical compound OBr=O DKSMCEUSSQTGBK-UHFFFAOYSA-N 0.000 claims description 6
- 230000003647 oxidation Effects 0.000 claims description 6
- 238000007254 oxidation reaction Methods 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 5
- 230000000087 stabilizing effect Effects 0.000 claims description 5
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- 230000006641 stabilisation Effects 0.000 claims description 3
- 238000011105 stabilization Methods 0.000 claims description 3
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- 239000003607 modifier Substances 0.000 description 27
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 18
- 239000000460 chlorine Substances 0.000 description 18
- 229910052801 chlorine Inorganic materials 0.000 description 18
- 239000007795 chemical reaction product Substances 0.000 description 16
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 230000000903 blocking effect Effects 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 11
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 11
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 description 11
- 230000001590 oxidative effect Effects 0.000 description 11
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
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- 239000007864 aqueous solution Substances 0.000 description 4
- CODNYICXDISAEA-UHFFFAOYSA-N bromine monochloride Chemical compound BrCl CODNYICXDISAEA-UHFFFAOYSA-N 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 238000007872 degassing Methods 0.000 description 4
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- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000005708 Sodium hypochlorite Substances 0.000 description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
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- 238000002347 injection Methods 0.000 description 3
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- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
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- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 102100035925 DNA methyltransferase 1-associated protein 1 Human genes 0.000 description 2
- 101000930289 Homo sapiens DNA methyltransferase 1-associated protein 1 Proteins 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- ISFLYIRWQDJPDR-UHFFFAOYSA-L barium chlorate Chemical compound [Ba+2].[O-]Cl(=O)=O.[O-]Cl(=O)=O ISFLYIRWQDJPDR-UHFFFAOYSA-L 0.000 description 2
- XTEGARKTQYYJKE-UHFFFAOYSA-M chlorate Inorganic materials [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 description 2
- XTEGARKTQYYJKE-UHFFFAOYSA-N chloric acid Chemical compound OCl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-N 0.000 description 2
- 229940005991 chloric acid Drugs 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- OSVXSBDYLRYLIG-UHFFFAOYSA-N dioxidochlorine(.) Chemical compound O=Cl=O OSVXSBDYLRYLIG-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
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- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
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- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- VKJKEPKFPUWCAS-UHFFFAOYSA-M potassium chlorate Chemical compound [K+].[O-]Cl(=O)=O VKJKEPKFPUWCAS-UHFFFAOYSA-M 0.000 description 2
- 238000003672 processing method Methods 0.000 description 2
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- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid Chemical class NS(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 description 2
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- 229940124530 sulfonamide Drugs 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
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- 229910019142 PO4 Inorganic materials 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 description 1
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- 125000003118 aryl group Chemical group 0.000 description 1
- HPEWZLCIOKVLBZ-UHFFFAOYSA-N barium hypochlorite Chemical compound [Ba+2].Cl[O-].Cl[O-] HPEWZLCIOKVLBZ-UHFFFAOYSA-N 0.000 description 1
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- BAQKWXACUNEBOT-UHFFFAOYSA-N dibutylsulfamic acid Chemical compound CCCCN(S(O)(=O)=O)CCCC BAQKWXACUNEBOT-UHFFFAOYSA-N 0.000 description 1
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- 230000007613 environmental effect Effects 0.000 description 1
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- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 150000002696 manganese Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- YZVQGLCYZLGIAM-UHFFFAOYSA-N methyl(propyl)sulfamic acid Chemical compound CCCN(C)S(O)(=O)=O YZVQGLCYZLGIAM-UHFFFAOYSA-N 0.000 description 1
- MYMDOKBFMTVEGE-UHFFFAOYSA-N methylsulfamic acid Chemical compound CNS(O)(=O)=O MYMDOKBFMTVEGE-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- RZLUIDROFNIMHF-UHFFFAOYSA-L nickel(2+);dichlorate Chemical compound [Ni+2].[O-]Cl(=O)=O.[O-]Cl(=O)=O RZLUIDROFNIMHF-UHFFFAOYSA-L 0.000 description 1
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- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- SATVIFGJTRRDQU-UHFFFAOYSA-N potassium hypochlorite Chemical compound [K+].Cl[O-] SATVIFGJTRRDQU-UHFFFAOYSA-N 0.000 description 1
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- HLIBNTOXKQCYMV-UHFFFAOYSA-N propylsulfamic acid Chemical compound CCCNS(O)(=O)=O HLIBNTOXKQCYMV-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
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- 159000000008 strontium salts Chemical class 0.000 description 1
- 150000005621 tetraalkylammonium salts Chemical class 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
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Classifications
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- B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
- B01D61/08—Apparatus therefor
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- 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
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- C02F1/441—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
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- B01D67/0093—Chemical modification
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- B01D71/06—Organic material
- B01D71/56—Polyamides, e.g. polyester-amides
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- C—CHEMISTRY; METALLURGY
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/20—Treatment of water, waste water, or sewage by degassing, i.e. liberation of dissolved gases
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- 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
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- C—CHEMISTRY; METALLURGY
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
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Description
R2NSO3H (1)
(式中、Rは独立して水素原子または炭素数1〜8のアルキル基である。)
本実施形態に係るポリアミド系逆浸透膜用改質剤組成物は、「臭素系酸化剤」と「スルファミン酸化合物」との混合物を含む安定化次亜臭素酸組成物を含有するものであり、さらにアルカリを含有してもよい。
本実施形態に係るポリアミド系逆浸透膜用改質剤組成物は、臭素系酸化剤とスルファミン酸化合物とを混合することにより得られ、さらにアルカリを混合してもよい。
窒素雰囲気下で、液体臭素:16.9重量%(wt%)、スルファミン酸:10.7重量%、水酸化ナトリウム:12.9重量%、水酸化カリウム:3.94重量%、水:残分を混合して、安定化次亜臭素酸組成物を調製した。安定化次亜臭素酸組成物のpHは14、有効ハロゲン濃度(有効塩素換算濃度)は7.5重量%であった。安定化次亜臭素酸組成物の詳細な調製方法は以下の通りである。
電極タイプ:ガラス電極式
pH測定計:東亜ディーケーケー社製、IOL−30型
電極の校正:関東化学社製中性リン酸塩pH(6.86)標準液(第2種)、同社製ホウ酸塩pH(9.18)標準液(第2種)の2点校正で行った
測定温度:25℃
測定値:測定液に電極を浸漬し、安定後の値を測定値とし、3回測定の平均値
上記で調製した安定化次亜臭素酸組成物(実施例1)、次亜塩素酸(比較例1)、次亜臭素酸(臭化ナトリウムと次亜塩素酸の混合物)(比較例2)を改質剤としてそれぞれ用いて、ポリアミド系高分子逆浸透膜(日東電工(株)製「SWC4+」、φ75mmの平膜、尿素阻止率=60%に低下させたもの)の改質を行った。改質は、この逆浸透膜を備える逆浸透膜装置に、操作圧1.0MPaで、上記改質剤を10ppm添加した水をpH=4、25±1℃で1時間通水して実施した。その後、操作圧1.0MPaで、尿素(分子量60)をTOC値として10ppmと、10ppmの上記改質剤とを添加した水を、pH=7、25±1℃でCT(Concentration Time)値=14000[ppm・h]となるまで連続通水した。原水および透過水のTOC濃度をTOC計によって測定し、下記の尿素阻止率を算出した。CT値は下記の通り算出した。結果を表1に示す。なお、比較例2では、改質剤として、臭化ナトリウム:15重量%、12%次亜塩素酸ナトリウム水溶液:42.4重量%を水中に別々に添加した。
尿素阻止率[%]=100−[透過水TOC濃度÷{(給水TOC濃度+濃縮水TOC濃度)÷2}×100]
CT値[ppm・h]=(遊離塩素濃度)×(接触時間)
上記で調整した安定化次亜臭素酸組成物として用いて、ポリアミド系高分子逆浸透膜(日東電工(株)製「SWC4+」、φ75mmの平膜、尿素阻止率=60%に低下させたもの)の改質を行った。改質は、この逆浸透膜を備える逆浸透膜装置に、操作圧1.0MPaで、上記改質剤を10ppm添加した水を25±1℃で1時間通水し、逆浸透膜への給水のpHの影響を調べた。
Claims (11)
- 低分子有機物を含有する被処理水を逆浸透膜で処理する逆浸透膜処理工程を含み、
前記逆浸透膜は、臭素系酸化剤とスルファミン酸化合物とを含む安定化次亜臭素酸組成物をポリアミド系の逆浸透膜に接触させて改質された膜であり、
前記ポリアミド系の逆浸透膜への前記安定化次亜臭素酸組成物の接触はpH3超、8未満の範囲で行われることを特徴とする低分子有機物含有水の処理方法。 - 低分子有機物を含有する被処理水を逆浸透膜で処理する逆浸透膜処理工程を含み、
前記逆浸透膜は、臭素とスルファミン酸化合物とを含む安定化次亜臭素酸組成物をポリアミド系の逆浸透膜に接触させて改質された膜であり、
前記ポリアミド系の逆浸透膜への前記安定化次亜臭素酸組成物の接触はpH3超、8未満の範囲で行われることを特徴とする低分子有機物含有水の処理方法。 - 請求項2に記載の低分子有機物含有水の処理方法であって、
前記安定化次亜臭素酸組成物は、水、アルカリおよびスルファミン酸化合物を含む混合液に臭素を不活性ガス雰囲気下で添加する工程を含む方法により得られたものであることを特徴とする低分子有機物含有水の処理方法。 - 請求項1〜3のいずれか1項に記載の低分子有機物含有水の処理方法であって、
前記接触が、前記被処理水のpHより低いpHで行われることを特徴とする低分子有機物含有水の処理方法。 - 請求項1〜4のいずれか1項に記載の低分子有機物含有水の処理方法であって、
前記逆浸透膜処理工程の被処理水について、脱気処理、イオン交換処理、UV殺菌処理のうちの少なくとも1つの処理を行うことを特徴とする低分子有機物含有水の処理方法。 - 請求項1〜5のいずれか1項に記載の低分子有機物含有水の処理方法であって、
前記逆浸透膜処理工程が、前記被処理水を第1逆浸透膜で処理する第1逆浸透膜処理工程と、前記第1逆浸透膜処理工程の透過水を第2逆浸透膜で処理する第2逆浸透膜処理工程とを含み、
前記第1逆浸透膜および前記第2逆浸透膜のうちの少なくとも1つが、前記安定化次亜臭素酸組成物をポリアミド系の逆浸透膜に接触させて改質された膜であることを特徴とする低分子有機物含有水の処理方法。 - 請求項6に記載の低分子有機物含有水の処理方法であって、
前記第1逆浸透膜処理工程の透過水および前記第2逆浸透膜処理工程の透過水のうちの少なくとも1つについて、イオン交換処理、電気式脱塩処理、UV殺菌処理、UV酸化処理、微粒子除去処理、第3逆浸透膜処理のうちの少なくとも1つの処理を行うことを特徴とする低分子有機物含有水の処理方法。 - 低分子有機物を含有する被処理水を逆浸透膜で処理するための逆浸透膜の改質方法であって、
臭素系酸化剤とスルファミン酸化合物とを含む安定化次亜臭素酸組成物をポリアミド系の逆浸透膜に接触させて前記逆浸透膜を改質し、
前記ポリアミド系の逆浸透膜への前記安定化次亜臭素酸組成物の接触はpH3超、8未満の範囲で行われることを特徴とする逆浸透膜の改質方法。 - 低分子有機物を含有する被処理水を逆浸透膜で処理するための逆浸透膜の改質方法であって、
臭素とスルファミン酸化合物とを含む安定化次亜臭素酸組成物をポリアミド系の逆浸透膜に接触させて前記逆浸透膜を改質し、
前記ポリアミド系の逆浸透膜への前記安定化次亜臭素酸組成物の接触はpH3超、8未満の範囲で行われることを特徴とする逆浸透膜の改質方法。 - 請求項9に記載の逆浸透膜の改質方法であって、
前記安定化次亜臭素酸組成物は、水、アルカリおよびスルファミン酸化合物を含む混合液に臭素を不活性ガス雰囲気下で添加する工程を含む方法により得られたものであることを特徴とする逆浸透膜の改質方法。 - 請求項8〜10のいずれか1項に記載の逆浸透膜の改質方法であって、
前記接触が、前記被処理水のpHより低いpHで行われることを特徴とする逆浸透膜の改質方法。
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