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WO2010019116A1 - Ammonia removal apparatus and method - Google Patents

Ammonia removal apparatus and method Download PDF

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Publication number
WO2010019116A1
WO2010019116A1 PCT/US2008/009709 US2008009709W WO2010019116A1 WO 2010019116 A1 WO2010019116 A1 WO 2010019116A1 US 2008009709 W US2008009709 W US 2008009709W WO 2010019116 A1 WO2010019116 A1 WO 2010019116A1
Authority
WO
WIPO (PCT)
Prior art keywords
ions
substantial portion
permeate
wastewaters
ammonia
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/US2008/009709
Other languages
French (fr)
Inventor
Frank S. Craft, Sr.
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Basin Water Inc
Original Assignee
Basin Water Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Basin Water Inc filed Critical Basin Water Inc
Priority to PCT/US2008/009709 priority Critical patent/WO2010019116A1/en
Publication of WO2010019116A1 publication Critical patent/WO2010019116A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
    • C01C1/00—Ammonia; Compounds thereof
    • C01C1/02—Preparation, purification or separation of ammonia
    • C01C1/022—Preparation of aqueous ammonia solutions, i.e. ammonia water
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
    • B01D61/027—Nanofiltration
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F9/00—Multistage treatment of water, waste water or sewage
    • 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
    • C02F1/20—Treatment of water, waste water, or sewage by degassing, i.e. liberation of dissolved gases
    • 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
    • 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
    • C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
    • C02F2001/425—Treatment of water, waste water, or sewage by ion-exchange using cation exchangers
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/16—Nitrogen compounds, e.g. ammonia
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/10—Nature of the water, waste water, sewage or sludge to be treated from quarries or from mining activities
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2303/00—Specific treatment goals
    • C02F2303/16—Regeneration of sorbents, filters
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents

Definitions

  • the present invention relates to an apparatus and method for removing ammonia from wastewaters, and in particular, to removing ammonia from wastewaters associated with mining and other industrial activities.
  • Ammonia may be removed from mining and other industrial wastewaters using stripping tower.
  • the pH of the wastewater stream is raised to convert to convert NH 3 in the wastewater to NH 4 OH.
  • the water is typically neutralized by acid addition.
  • Conventional ammonia stripping also often requires that the water temperature be elevated in order to reduce the effluent ammonia to the required specification.
  • the present invention is an apparatus and method for removing ammonia from mining and other industrial wastewaters comprising (1 ) a membrane separation system with molecular weight cutoff above around 200 (nanofiltration) to reject most of divalent ions but pass most of the ammonium and other monovalent ions with the permeate (filtrate), (2) a water softening system (cation exchange resin in sodium form regenerated with salt brine), (3) one or more strong acid cation NH 3 removal column(s), (4) an alkaline (5-10% NaOH or other alkaline solution) storage tank for regeneration of the NH 3 removal column(s), and (5) a stripping tower for ammonia (NH 4 OH) removal.
  • a membrane separation system with molecular weight cutoff above around 200 (nanofiltration) to reject most of divalent ions but pass most of the ammonium and other monovalent ions with the permeate (filtrate)
  • a water softening system cation exchange resin in sodium form regenerated with salt brine
  • the membrane system rejects divalent ions well, such as hardness, but does not reject NH 3 well.
  • the softener adsorbs most of the divalent ions that the membrane passes, but the NH 3 passes through the softener.
  • the NH 3 loads well on the NH 3 removal column because the divalent ions have been mostly eliminated and will not impede NH 3 loading.
  • sodium which would be exchanged for divalent ions during water softening
  • Sodium also impedes NH 3 loading on the cation resin in the NH 3 columns. If hardness (Ca + Mg) plus sodium is reasonably low (less than approximately 500), the membrane system is not necessary.
  • the present invention reuses the alkaline regenerant solution after the ammonia has been stripped from it with only about 5% loss of regenerant per regeneration cycle.
  • the alkaline regenerant solution of the present invention is maintained at a pH near 14 for the most expedient conversion of NH 3 to NH 4 OH at relatively low temperature.
  • Fig. 1 is a block diagram of an embodiment of the present invention.
  • the present invention is an apparatus and method for removing ammonia from mining and other industrial wastewaters.
  • the wastewater 11 is pumped by pump 12 to membrane separation system 10.
  • Membrane separation system 10 is preferably a nanofiltration system with molecular weight cutoff above around 200.
  • Most of the divalent ions in the wastewater 11 are rejected in reject line 13 but most of the ammonium and other monovalent ions are passed in permeate line 14.
  • the permeate 14 is fed to water softening system 20.
  • Water softening system 20 is preferably a cation exchange resin in sodium form.
  • the resin is regenerated with salt brine 15.
  • the effluent 21 from water softening system 20 is passed to a strong acid cation NH 3 removal column 30.
  • the NH 3 removal column 30 may actually comprise one or more columns.
  • the removal column 30 is regenerated with an alkaline solution stored in one or more storage tanks 40, 50.
  • the alkaline solution is preferably 5-10% NaOH or other alkaline solution.
  • the alkaline solution is maintained at a pH near 14 for the most expedient conversion of NH 3 to NH 4 OH at relatively low temperature.
  • the alkaline solution is stripped of ammonium hydroxide in stripping tower 61 using air blown by blower 60.
  • the present invention only strips NH 3 from the relatively small volume of alkaline regenerant solution from the NH 3 removal media rather than stripping the NH 3 from a large volume of water.
  • strippers for stripping the NH 3 may be used with the present invention.
  • the Liqui-Cel® membrane contactors (Celgard LLC, Charlotte NC) may be used for stripping NH 3 from the alkaline regenerant solution.
  • Any type of apparatus or method capable of stripping NH 3 from an alkaline solution may also be used at the stripper in the practice of the present invention.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Water Supply & Treatment (AREA)
  • Nanotechnology (AREA)
  • Analytical Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Environmental & Geological Engineering (AREA)
  • Physical Water Treatments (AREA)

Abstract

An apparatus and method for removing ammonia from mining and other industrial wastewaters having a nanofiltration membrane separation system (10) to reject most divalent ions but pass most ammonium and other monovalent ions with the permeate (14) to a water softening system (20) with the effluent (21) to one or more strong acid cation NH3 removal column(s) (30). Alkaline storage tank(s) (40, 50) provide for the regeneration of the NH3 removal column(s) (30). A stripping tower (61) is provided for ammonia (NH4OH) removal.

Description

Description Ammonia Removal Apparatus And Method
Technical Field
The present invention relates to an apparatus and method for removing ammonia from wastewaters, and in particular, to removing ammonia from wastewaters associated with mining and other industrial activities.
Background Art
Ammonia may be removed from mining and other industrial wastewaters using stripping tower. The pH of the wastewater stream is raised to convert to convert NH3 in the wastewater to NH4OH. After stripping, the water is typically neutralized by acid addition. Conventional ammonia stripping also often requires that the water temperature be elevated in order to reduce the effluent ammonia to the required specification.
Disclosure of Invention
The present invention is an apparatus and method for removing ammonia from mining and other industrial wastewaters comprising (1 ) a membrane separation system with molecular weight cutoff above around 200 (nanofiltration) to reject most of divalent ions but pass most of the ammonium and other monovalent ions with the permeate (filtrate), (2) a water softening system (cation exchange resin in sodium form regenerated with salt brine), (3) one or more strong acid cation NH3 removal column(s), (4) an alkaline (5-10% NaOH or other alkaline solution) storage tank for regeneration of the NH3 removal column(s), and (5) a stripping tower for ammonia (NH4OH) removal.
The membrane system rejects divalent ions well, such as hardness, but does not reject NH3 well. The softener adsorbs most of the divalent ions that the membrane passes, but the NH3 passes through the softener. The NH3 loads well on the NH3 removal column because the divalent ions have been mostly eliminated and will not impede NH3 loading. Also, because of the use of nanofiltration for the bulk of the divalent ion removal, sodium (which would be exchanged for divalent ions during water softening) is minimized. Sodium also impedes NH3 loading on the cation resin in the NH3 columns. If hardness (Ca + Mg) plus sodium is reasonably low (less than approximately 500), the membrane system is not necessary.
Conventional ammonia strippers treat the water stream, requiring a large stripping tower. The present invention system only strips the alkaline regenerant solution from the NH3 removal media, which is roughly 1 % of the volume of the treated water, requiring a much smaller stripper, which operates only about 5% of the time that the water is being treated.
It is necessary to raise the pH of the stream to approximately 11.5 to convert NH3 to NH4OH with conventional ammonia strippers. After stripping, the water is typically neutralized by acid addition. Therefore, chemical feed systems and pH controls are necessary as well as the chemical costs associated with the continuous pH adjustments. The present invention reuses the alkaline regenerant solution after the ammonia has been stripped from it with only about 5% loss of regenerant per regeneration cycle.
Conventional ammonia stripping often requires that the water temperature be elevated, with inherent energy cost, in order to reduce the effluent ammonia to the required specification. The alkaline regenerant solution of the present invention is maintained at a pH near 14 for the most expedient conversion of NH3 to NH4OH at relatively low temperature.
Calcium and other divalent ions which contribute to scaling and impede ammonia stripping are diverted around the NH3 removal column so that the scaling potential of the stripping tower is greatly minimized or eliminated and stripping efficiency is enhanced.
These and other features, objects and advantages of the present invention will become better understood from a consideration of the following detailed description of the preferred embodiments and appended claims in conjunction with the drawings as described following:
Brief Description Of Drawings
Fig. 1 is a block diagram of an embodiment of the present invention.
Best Mode for Carrying Out the Invention With reference to Fig. 1 , the preferred embodiment of the present invention may be described as follows.
The present invention is an apparatus and method for removing ammonia from mining and other industrial wastewaters. The wastewater 11 is pumped by pump 12 to membrane separation system 10. Membrane separation system 10 is preferably a nanofiltration system with molecular weight cutoff above around 200. Most of the divalent ions in the wastewater 11 are rejected in reject line 13 but most of the ammonium and other monovalent ions are passed in permeate line 14. The permeate 14 is fed to water softening system 20. Water softening system 20 is preferably a cation exchange resin in sodium form. The resin is regenerated with salt brine 15. The effluent 21 from water softening system 20 is passed to a strong acid cation NH3 removal column 30. If hardness (Ca + Mg) plus sodium in the wastewater is reasonably low (less than approximately 500), the membrane system 10 is not necessary. The NH3 removal column 30 may actually comprise one or more columns. The removal column 30 is regenerated with an alkaline solution stored in one or more storage tanks 40, 50. The alkaline solution is preferably 5-10% NaOH or other alkaline solution. The alkaline solution is maintained at a pH near 14 for the most expedient conversion of NH3 to NH4OH at relatively low temperature. The alkaline solution is stripped of ammonium hydroxide in stripping tower 61 using air blown by blower 60.
As noted above, the present invention only strips NH3 from the relatively small volume of alkaline regenerant solution from the NH3 removal media rather than stripping the NH3 from a large volume of water. Although one embodiment of the invention is described above with respect to stripping the NH3 using a stripping tower, other strippers for stripping the NH3 may be used with the present invention. For example, the Liqui-Cel® membrane contactors (Celgard LLC, Charlotte NC) may be used for stripping NH3 from the alkaline regenerant solution. Any type of apparatus or method capable of stripping NH3 from an alkaline solution may also be used at the stripper in the practice of the present invention.
The present invention has been described with reference to certain preferred and alternative embodiments that are intended to be exemplary only and not limiting to the full scope of the present invention as set forth in the appended claims.

Claims

Claims
1. An apparatus for removing ammonia from wastewaters containing divalent ions and monovalent ions including ammonium ions, comprising: a nanofiltration membrane separation system for passing in a permeate a substantial portion of the monovalent ions including ammonium ions in the wastewaters while rejecting a substantial portion of the divalent ions in the wastewaters; a water softening system for receiving the permeate from the membrane separation system and absorbing a substantial portion of divalent ions remaining in the permeate; a strong acid cation ion exchange column for receiving the permeate from the water softening system and for removing a substantial portion of the ammonium ions in the permeate; a storage tank containing an alkaline solution for regeneration of the strong acid cation ion exchange column removal column and producing an ammonium hydroxide brine; and a stripper for stripping ammonium hydroxide from the brine.
2. An apparatus for removing ammonia from wastewaters containing divalent ions and monovalent ions including ammonium ions, comprising: a water softening system for passing a substantial portion of the monovalent ions including ammonium ions in the wastewater while absorbing a substantial portion of divalent ions in the wastewaters; a strong acid cation ion exchange column for receiving the effluent from the water softening system and for removing a substantial portion of the ammonium ions in the effluent; a storage tank containing an alkaline solution for regeneration of the strong acid cation ion exchange column removal column and producing an ammonium hydroxide brine; and a stripper for stripping ammonium hydroxide from the brine.
PCT/US2008/009709 2008-08-14 2008-08-14 Ammonia removal apparatus and method Ceased WO2010019116A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/US2008/009709 WO2010019116A1 (en) 2008-08-14 2008-08-14 Ammonia removal apparatus and method

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/US2008/009709 WO2010019116A1 (en) 2008-08-14 2008-08-14 Ammonia removal apparatus and method

Publications (1)

Publication Number Publication Date
WO2010019116A1 true WO2010019116A1 (en) 2010-02-18

Family

ID=41669096

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2008/009709 Ceased WO2010019116A1 (en) 2008-08-14 2008-08-14 Ammonia removal apparatus and method

Country Status (1)

Country Link
WO (1) WO2010019116A1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2019098206A (en) * 2017-11-29 2019-06-24 オルガノ株式会社 Ammonia concentration method and device

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4695387A (en) * 1985-05-07 1987-09-22 Advanced Separation Technologies Incorporated Removal of ammonia from wastewater
US6146532A (en) * 1996-04-03 2000-11-14 Fraunhofer-Gesellschaft Zur Foerderung Der Angewandten Forschung E.V. Process for the biological purification of wastewater

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4695387A (en) * 1985-05-07 1987-09-22 Advanced Separation Technologies Incorporated Removal of ammonia from wastewater
US6146532A (en) * 1996-04-03 2000-11-14 Fraunhofer-Gesellschaft Zur Foerderung Der Angewandten Forschung E.V. Process for the biological purification of wastewater

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2019098206A (en) * 2017-11-29 2019-06-24 オルガノ株式会社 Ammonia concentration method and device

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