Water treatment process and water treatment system

• US 9,914,652 B2
• Filed: 03/30/2015
• Issued: 03/13/2018
• Est. Priority Date: 07/05/2013
• Status: Expired due to Fees

• Current Assignee: Mitsubishi Heavy Industries Engineering, Ltd. (Mitsubishi Heavy Industries, Ltd.)
• Original Assignee: Mitsubishi Heavy Industries, Ltd.
• Inventors: Eda, Masayuki, Okino, Susumu, Yoshiyama, Ryuji, Sakurai, Hideaki, Ukai, Nobuyuki, Suzuki, Hideo, Nakashoji, Hiroshi, Yoshioka, Shigeru
• Primary Examiner(s): Perrin, Clare M
• Application Number:
  US14/672,754
• Publication Number:
  US 20150203379A1
• Time in Patent Office: 1,079 Days
• Field of Search: None
• CPC Class Codes: B01D 19/0005 with one or more auxiliary substances
• CPC Class Codes: B01D 2311/04 Specific process operations in the feed stream; Feed pretreatment
• CPC Class Codes: B01D 2311/12 Addition of chemical agents
• CPC Class Codes: B01D 2311/18 pH control
• CPC Class Codes: B01D 2311/2642 Aggregation, sedimentation, flocculation, precipitation or coagulation
• CPC Class Codes: B01D 2311/2649 Filtration
• CPC Class Codes: B01D 2311/2657 Deaeration
• CPC Class Codes: B01D 61/025 Reverse osmosis; Hyperfiltration
• CPC Class Codes: B01D 61/04 Feed pretreatment
• CPC Class Codes: B01D 61/42 Electrodialysis; Electro-osmosis ; Electro-ultrafiltration; Membrane capacitive deionization
• CPC Class Codes: B01D 65/08 Prevention of membrane fouling or of concentration polarisation
• CPC Class Codes: B01D 9/0036 Crystallisation on to a bed of product crystals; Seeding
• CPC Class Codes: C02F 1/04 by distillation or evaporation
• CPC Class Codes: C02F 1/20 by degassing, i.e. liberation of dissolved gases degasification of liquids in general B01D19/00; arrangement of degassing apparatus in boiler feed supply F22D
• CPC Class Codes: C02F 1/42 by ion-exchange ion-exchange in general B01J
• CPC Class Codes: C02F 1/441 by reverse osmosis
• CPC Class Codes: C02F 1/442 by nanofiltration
• CPC Class Codes: C02F 1/4691 Capacitive deionisation
• CPC Class Codes: C02F 1/4693 electrodialysis
• CPC Class Codes: C02F 1/52 by flocculation or precipitation of suspended impurities C02F1/463 takes precedence
• CPC Class Codes: C02F 1/5281 : Installations for water purification using chemical agents
• CPC Class Codes: C02F 1/66 : by neutralisation; pH adjustment for degassing C02F1/20; using ion-exchange C02F1/42; for flocculation or precipitation of suspended impurities C02F1/52; for removing dissolved compounds C02F1/58
• CPC Class Codes: C02F 2001/007 : Processes including a sedimentation step
• CPC Class Codes: C02F 2001/5218 : Crystallization
• CPC Class Codes: C02F 2101/10 : Inorganic compounds
• CPC Class Codes: C02F 2101/101 : Sulfur compounds
• CPC Class Codes: C02F 2103/023 : Water in cooling circuits
• CPC Class Codes: C02F 2209/06 : pH
• CPC Class Codes: C02F 5/10 : using organic substances
• CPC Class Codes: C02F 9/00 : Multistage treatment of water, waste water or sewage
• CPC Class Codes: Y02A 20/124 : Water desalination
• CPC Class Codes: Y02A 20/131 : Reverse-osmosis

Abstract

Provided are a water treatment system and a water treatment process, which are capable of reproducing water containing salts with high water recovery. In the water treatment system (400) and the water treatment process of the present invention, after a calcium scale inhibitor and a silica scale inhibitor are supplied to water to be treated containing Ca ions, SO₄ ions, carbonate ions, and silica, and the water to be treated is separated in a second demineralizing section (210) into second concentrated water in which the Ca ions, the SO₄ ions, the carbonate ions, and the silica are concentrated and treated water. In a second crystallizing section (220), seed crystals of gypsum are supplied to the second concentrated water, whereby gypsum is crystallized and removed from the second concentrated water.

Claims

1. A water treatment process, comprising:

a first scale inhibitor supplying step of supplying a calcium scale inhibitor which is a scale inhibitor for inhibiting the deposition of a scale containing calcium and a silica scale inhibitor which is a scale inhibitor for inhibiting the deposition of silica to water containing Ca²⁺ ions, SO₄²⁻

ions, carbonate ions and silica;

a first demineralizing step of separating the water into first concentrated water in which the Ca²⁺ ions, the SO₄²⁻

ions, the carbonate ions and the silica are concentrated and treated water after the first scale inhibitor supplying step; and

a first crystallizing step of supplying seed crystals of gypsum to the first concentrated water so that gypsum is crystallized from the first concentrated water, wherein the water treatment process further comprises, after the first crystallizing step;

a second scale inhibitor supplying step of supplying the calcium scale inhibitor to the water;

a first pH adjusting step of adjusting the water to a pH of 10 or more at which the silica is soluble in the water;

a second demineralizing step of separating the water into second concentrated water in which the Ca²⁺ ions, the SO₄²⁻

ions, the carbonate ions and the silica are concentrated and treated water after the second scale inhibitor supplying step and the first pH adjusting step; and

a second crystallizing step of supplying seed crystals of gypsum to the second concentrated water so that gypsum is crystallized from the second concentrated water.

2. The water treatment process according to claim 1, comprising a second pH adjusting step of adjusting the first concentrated water to a pH of 6.0 or less at which a scale inhibition function of the calcium scale inhibitor is reduced, thereby promoting the deposition of the gypsum in the first crystallizing step.

3. The water treatment process according to claim 2, wherein, after the first crystallizing step, the first concentrated water after the adjustment of the pH in the second pH adjusting step is adjusted to a pH of 4.0 or more at which the calcium scale inhibitor exhibits its function.

4. The water treatment process according to claim 1, comprising a second pH adjusting step of adjusting the first concentrated water to a pH of 10 or more at which the silica is soluble in the first crystallizing step.

5. The water treatment process according to claim 1, comprising, after the second crystallizing step, a downstream side demineralizing step of performing separation into concentrated water and treated water, and recovering the separated treated water.

6. The water treatment process according to claim 1, comprising an upstream side precipitating step of precipitating at least calcium carbonate from the water so that the concentration of the calcium carbonate in the water is reduced, before the first scale inhibitor supplying step.

7. The water treatment process according to claim 6, comprising a deaerating step of removing CO₂ from the water before the upstream side precipitating step or after the upstream side precipitating step and before the first scale inhibitor supplying step.

8. The water treatment process according to claim 1,

wherein the water contains metal ions;

and

wherein the process comprises a first precipitating step of precipitating at least one of calcium carbonate and a metal compound so that the concentration of at least one of the calcium carbonate and the metal ions is reduced from the first concentrated water, after the first crystallizing step.

9. The water treatment process according to claim 8, wherein at least one of seed crystals of the silica and a precipitant for the silica is supplied to the first concentrated water in the first precipitating step.

10. The water treatment process according to claim 1,

wherein the water contains metal ions;

and

wherein the process comprises a second precipitating step of precipitating at least one of calcium carbonate and a metal compound so that the concentration of at least one of the calcium carbonate and the metal ions is reduced from the second concentrated water, after the second crystallizing step.

11. The water treatment process according to claim 10, wherein at least one of seed crystals of the silica and a precipitant for the silica is supplied to the second concentrated water in the second precipitating step.

12. The water treatment process according to claim 11, wherein, when the water contains Mg²⁺ ions, the amount of the precipitant for the silica to be supplied is adjusted according to the concentration of the Mg²⁺ ions.

13. The water treatment process according to claim 9, wherein, when the water contains Mg²⁺ ions, the amount of the precipitant for the silica to be supplied is adjusted according to the concentration of the Mg²⁺ ions.

14. The water treatment process according to claim 8,

wherein, when the water contains Mg²⁺ ions, the first concentrated water in the first precipitating step is adjusted to a pH of 10 or more at which a magnesium compound is deposited so that the concentration of the Mg²⁺ ions is reduced, and

wherein, after the first precipitating step, the first concentrated water is adjusted to a pH of less than 10 at which the magnesium compound is soluble.

15. The water treatment process according to claim 10,

wherein, when the water to be treated contains Mg²⁺ ions, the second concentrated water in the second precipitating step is adjusted to a pH of 10 or more at which a magnesium compound is deposited so that the concentration of the Mg²⁺ ions is reduced, and

wherein, after the second precipitating step, the second concentrated water is adjusted to a pH of less than 10 at which the magnesium compound is soluble.

16. The water treatment process according to claim 6,

wherein, when the water contains Mg²⁺ ions, the water in the upstream side precipitating step is adjusted to a pH of 10 or more at which a magnesium compound is deposited so that the concentration of the Mg²⁺ ions is reduced, and

wherein, after the upstream side precipitating step, the water is adjusted to a pH of less than 10 at which the magnesium compound is soluble.

17. The water treatment process according to claim 5, wherein moisture is evaporated from the concentrated water in the downstream side demineralizing step, so that a solid in the concentrated water is recovered.

18. A water treatment system, comprising:

a first scale inhibitor supplying section that supplies a calcium scale inhibitor which is a scale inhibitor for inhibiting the deposition of a scale containing calcium and a silica scale inhibitor which is a scale inhibitor for inhibiting the deposition of silica to water containing Ca²⁻

ions, SO₄²⁻

ions, carbonate ions and silica;

a first demineralizing section that is positioned on a downstream side of the first scale inhibitor supplying section and separates the water into first concentrated water in which the Ca²⁺ ions, the SO₄²⁻

ions, the carbonate ions and the silica are concentrated and treated water; and

a first crystallizing section including a first crystallizing tank that is positioned on a downstream side of the first demineralizing section and crystallizes gypsum from the first concentrated water and a first seed crystal supplying section that supplies seed crystals of gypsum to the first crystallizing tank,

wherein the water treatment system comprises, on a downstream side of the first crystallizing section with respect to the water;

a second scale inhibitor supplying section that supplies the calcium scale inhibitor to the water;

a first pH adjusting section that supplies a pH adjuster to the water to adjust the pH of the water to 10 or more such that the silica is soluble in the water;

a second demineralizing section that is positioned on a downstream side of the second scale inhibitor supplying section and the first pH adjusting section and separates the water into first concentrated water in which the Ca²⁺ ions, the SO₄²⁻

ions, the carbonate ions and the silica are concentrated and treated water; and

a second crystallizing section including a second crystallizing tank that is positioned on a downstream side of the second demineralizing section and crystallizes gypsum from the second concentrated water and a second seed crystal supplying section that supplies seed crystals of gypsum to the second crystallizing tank.

19. The water treatment system according to claim 18, comprising a second pH adjusting section that is positioned on a downstream side of the first demineralizing section and supplies a pH adjuster to the first concentrated water to adjust the pH of the first concentrated water to 6.0 or less such that a scale inhibition function of the calcium scale inhibitor is reduced, and the precipitation of the gypsum is promoted.

20. The water treatment system according to claim 19, comprising, on a downstream side of the first crystallizing section, a third pH adjusting section that supplies a pH adjuster to the first concentrated water after the adjustment of the pH in the second pH adjusting section to adjust the pH of the first concentrated water to 4.0 or more such that the calcium scale inhibitor achieves a function.

21. The water treatment system according to claim 18, comprising a second pH adjusting section that is positioned on a downstream side of the first demineralizing section and supplies a pH adjuster to the first concentrated water to adjust the pH of the first concentrated water to 10 or more such that the silica is soluble in the first concentrated water in the first crystallizing section.

22. The water treatment system according to claim 18, comprising, on a downstream side of the second crystallizing section, a downstream side demineralizing section that separates the second concentrated water discharged from the second crystallizing section into concentrated water and treated water.

23. The water treatment system according to claim 18, comprising, on an upstream side of the first scale inhibitor supplying section, an upstream side precipitating section that precipitates at least calcium carbonate from the water so that the concentration of the calcium carbonate in the water is reduced.

24. The water treatment system according to claim 23, comprising a first deaerating section that removes CO₂ from the water on an upstream side of the upstream side precipitating section or on a downstream side of the upstream side precipitating section and on an upstream side of the first scale inhibitor supplying section.

25. The water treatment system according to claim 18,

wherein the water contains metal ions;

and

wherein the system comprises, on a downstream side of the first crystallizing section, a first precipitating section that precipitates at least one of calcium carbonate and a metal compound.

26. The water treatment system according to claim 25, wherein at least one of seed crystals of the silica and a precipitant for the silica is supplied to the first precipitating section.

27. The water treatment system according to claim 18,

wherein the water contains metal ions;

and

wherein the system comprises, on a downstream side of the second crystallizing section, a second precipitating section that precipitates at least one of calcium carbonate and a metal compound.

28. The water treatment system according to claim 27, wherein at least one of seed crystals of the silica and a precipitant for the silica is supplied to the second precipitating section.

29. The water treatment system according to claim 25, wherein, when the water contains Mg²⁺ ions, the amount of the precipitant for the silica to be supplied is adjusted according to the concentration of the Mg²⁺ ions in the first precipitating section.

30. The water treatment system according to claim 27, wherein, when the water contains Mg²⁺ ions, the amount of the precipitant for the silica to be supplied is adjusted according to the concentration of the Mg²⁺ ions in the second precipitating section.

31. The water treatment system according to claim 25, wherein, when the water contains Mg²⁺ ions, the first concentrated water in the first precipitating section is adjusted to a pH of 10 or more at which a magnesium compound is deposited so that the concentration of the Mg²⁺ ions is reduced, and

wherein, on a downstream side of the first precipitating section, the first concentrated water is adjusted to a pH of less than 10 at which the magnesium compound is soluble.

32. The water treatment system according to claim 27, wherein, when the water contains Mg²⁺ ions, the second concentrated water in the second precipitating section is adjusted to a pH of 10 or more at which a magnesium compound is deposited so that the concentration of the Mg²⁺ ions is reduced, and

wherein, on a downstream side of the second precipitating section, the second concentrated water is adjusted to a pH of less than 10 at which the magnesium compound is soluble.

33. The water treatment system according to claim 23, wherein, when the water contains Mg²⁺ ions, the water in the upstream side precipitating section is adjusted to a pH of 10 or more at which a magnesium compound is deposited so that the concentration of the Mg²⁺ ions is reduced, and

wherein, on a downstream side of the upstream side precipitating section, the water is adjusted to a pH of less than 10 at which the magnesium compound is soluble.

34. The water treatment system according to claim 22, comprising, on a downstream side of the downstream side demineralizing section with respect to the concentrated water, an evaporator that evaporates moisture from the concentrated water to recover the solids in the concentrated water.