JP6386528B2 - 高回収脱塩システムにおけるイオン封鎖によるスケーリング防止 - Google Patents
高回収脱塩システムにおけるイオン封鎖によるスケーリング防止 Download PDFInfo
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- 238000010612 desalination reaction Methods 0.000 title claims description 24
- 238000011084 recovery Methods 0.000 title description 13
- 230000002265 prevention Effects 0.000 title 1
- 230000009919 sequestration Effects 0.000 title 1
- 239000000203 mixture Substances 0.000 claims description 61
- 238000000034 method Methods 0.000 claims description 45
- 239000003446 ligand Substances 0.000 claims description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 38
- 150000001768 cations Chemical class 0.000 claims description 34
- 239000012267 brine Substances 0.000 claims description 23
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 claims description 23
- 230000008569 process Effects 0.000 claims description 13
- 238000004821 distillation Methods 0.000 claims description 10
- 150000002500 ions Chemical class 0.000 claims description 10
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- 239000002244 precipitate Substances 0.000 claims description 7
- 239000013535 sea water Substances 0.000 claims description 7
- 239000011575 calcium Substances 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 239000012528 membrane Substances 0.000 claims description 5
- 238000000108 ultra-filtration Methods 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- 238000011033 desalting Methods 0.000 claims description 4
- 230000014759 maintenance of location Effects 0.000 claims description 4
- 239000011780 sodium chloride Substances 0.000 claims description 4
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 238000007791 dehumidification Methods 0.000 claims description 3
- 239000011777 magnesium Substances 0.000 claims description 3
- 238000005065 mining Methods 0.000 claims description 3
- 238000001223 reverse osmosis Methods 0.000 claims description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- 229910052788 barium Inorganic materials 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- -1 ethylenediaminetetraacetic acid ions Chemical class 0.000 claims description 2
- 238000007701 flash-distillation Methods 0.000 claims description 2
- 239000003208 petroleum Substances 0.000 claims description 2
- 239000011148 porous material Substances 0.000 claims description 2
- 229910052712 strontium Inorganic materials 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims 6
- 239000008213 purified water Substances 0.000 claims 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims 1
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims 1
- 238000000909 electrodialysis Methods 0.000 claims 1
- 229910052749 magnesium Inorganic materials 0.000 claims 1
- 238000000638 solvent extraction Methods 0.000 claims 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims 1
- 239000002351 wastewater Substances 0.000 claims 1
- 239000013505 freshwater Substances 0.000 description 19
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 16
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 9
- 238000010586 diagram Methods 0.000 description 9
- 239000011734 sodium Substances 0.000 description 7
- 239000002904 solvent Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 235000006408 oxalic acid Nutrition 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910001424 calcium ion Inorganic materials 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000000895 extractive distillation Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 101100493705 Caenorhabditis elegans bath-36 gene Proteins 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- QXDMQSPYEZFLGF-UHFFFAOYSA-L calcium oxalate Chemical compound [Ca+2].[O-]C(=O)C([O-])=O QXDMQSPYEZFLGF-UHFFFAOYSA-L 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000012465 retentate Substances 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 230000002000 scavenging effect Effects 0.000 description 1
- 239000003079 shale oil Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- HUAUNKAZQWMVFY-UHFFFAOYSA-M sodium;oxocalcium;hydroxide Chemical compound [OH-].[Na+].[Ca]=O HUAUNKAZQWMVFY-UHFFFAOYSA-M 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
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Description
Na4EDTA + Ca2+ → CaEDTA2− + 4Na+
上式において、EDTAは多座配位子(キレート)の役割を果たし、カルシウム(Ca2+)はスケーリング性イオンである。カルシウムイオンの捕捉は、水性組成物中において4を超えるpHおよび実質的に1を超えるKsを確立することで促進される。上に示したように、1モルのEDTAが1モルの2価金属または遷移金属イオンを捕捉する。具体的には、この場合は、カルシウムイオンをCaEDTA2−として封鎖することにより捕捉するとスケールを形成しない。結果として生成した新たな錯体イオン(CaEDTA2−)の対応する温度下における溶解性は、塩化ナトリウム(NaCl)さえも上回るほど高い。
Claims (17)
- 水性組成物から析出し得る陽イオンを封鎖するための方法において:
水性組成物から析出してスケーリングし得る1価イオンおよび少なくとも1種の溶解した2価陽イオンを含む前記水性組成物に多座配位子を添加する工程と;次いで
前記多座配位子が前記溶解した2価陽イオンと結合して非スケーリング性イオン性錯体を形成できるようにする工程と;次いで
かん水中の前記水性非スケーリング性イオン性錯体を保持し、かつ、水および1価イオンを含む前記水性組成物の残液を通過させる膜で、前記水性組成物から前記水性非スケーリング性イオン性錯体を濾過する工程と;
前記2価陽イオンを前記多座配位子から解放するために、前記濾過したかん水のpHを低下する工程と;
前記陽イオンを解放した後、大部分が閉じたループにおいてさらなる非スケーリング性イオン性錯体を形成するために、前記多座配位子をさらなる水性組成物に再び導入する工程と;
を含むことを特徴とする、方法。 - 請求項1に記載の方法において、前記溶解した2価陽イオンが、カルシウム、バリウム、ストロンチウムおよびマグネシウムの少なくとも1種を含むことを特徴とする方法。
- 請求項1に記載の方法において、前記水性組成物が石油採掘またはガス採掘に由来するフローバック水または随伴水を含むことを特徴とする方法。
- 請求項1に記載の方法において、前記水性組成物が海水および汽水の少なくとも1種を含むことを特徴とする方法。
- 請求項1に記載の方法において、前記水性組成物が廃水を含むことを特徴とする方法。
- 請求項1に記載の方法において、前記多座配位子から前記スケール成分を解放するために、酸を添加することによって前記濾過したかん水のpHを低下することを特徴とする方法。
- 請求項1に記載の方法において、前記非スケーリング性イオン性錯体を含む前記かん水から浄化水を分離する工程をさらに含むことを特徴とする方法。
- 請求項1に記載の方法において、逆浸透、多段フラッシュ蒸留、多重効用蒸留、機械的蒸気再圧縮、電気透析、膜蒸留、直接溶媒抽出および給湿−脱湿から少なくとも1種選択される脱塩プロセスを介して、浄化水を前記水性組成物の他の構成成分から分離する工程をさらに含むことを特徴とする方法。
- 請求項1に記載の方法において、前記溶解した2価陽イオンが前記水性組成物の残液の中で非結合型で残っているのであれば、前記溶解した2価陽イオンが前記水性組成物から析出するであろう温度まで前記水性組成物の残液を加熱する工程をさらに含むことを特徴とする方法。
- 請求項9に記載の方法において、前記水性組成物の残液が少なくとも50℃の温度まで加熱されることを特徴とする方法。
- 請求項1に記載の方法において、前記1価イオンが、NaCl、KCl、Na2SO4およびNa2CO3から選択される、少なくとも1種の溶解した構成成分を含むことを特徴とする方法。
- 請求項1に記載の方法において、イオン性錯体を含むかん水のpHが、前記かん水に酸を添加することによって低下し;前記多座配位子が解放されて除去された後の前記かん水に前記酸を中和する塩基を添加する工程をさらに含むことを特徴とする方法。
- 請求項1に記載の方法において、前記pH低下後に、前記陽イオンから解放される多座配位子の量を増加するために前記イオン性錯体を含む前記かん水を20℃未満に冷却することを特徴とする方法。
- 請求項1に記載の方法において、前記多座配位子がエチレンジアミン四酢酸イオンを含むことを特徴とする方法。
- スケーリング防止脱塩用装置において:
水性組成物から析出してスケーリングし得る1価イオンおよび少なくとも1種の溶解した2価陽イオンを含む前記水性組成物の供給源と;
脱塩システムと;
前記水性組成物供給源から前記水性組成物を前記脱塩システムに供給するように構成された第1導管と;
多座配位子の供給源と;
前記水性組成物中で前記多座配位子を2価陽イオンと結合させて非スケーリング性イオン性錯体を形成するために前記多座配位子供給源から前記多座配位子を前記第1導管に供給するように構成された第2導管と;
前記第1導管と連結し、前記非スケーリング性イオン性錯体を有する前記水性組成物を受けるように構成された濾過装置であって、前記濾過装置が前記水性組成物の残液を通過させるサイズの細孔を有する膜を含み、前記脱塩システムが前記濾過装置から前記水性組成物の残液を受けるように構成された濾過装置と;
pH降下剤の供給源に連結されており、前記2価陽イオンを前記多座配位子から分離するように構成されているpH降下装置と;
前記濾過装置から前記非スケーリング性イオン性錯体を前記pH降下装置に供給するように構成された第3導管と;
を含むことを特徴とする装置。 - 請求項15に記載の装置において、前記第2導管が、前記pH降下装置から前記多座配位子を前記第1導管に供給するように構成されていることを特徴とする装置。
- 請求項16に記載の装置において、前記限外濾過装置が、前記第1導管に連結され、前記水性組成物が前記脱塩システムに供給される前に前記水性組成物の残液から前記非スケーリング性錯体を分離するように構成されていることを特徴とする装置。
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