WO1990005705A1 - A process of removing phosphate from water, and a system for use in the process - Google Patents
A process of removing phosphate from water, and a system for use in the process Download PDFInfo
- Publication number
- WO1990005705A1 WO1990005705A1 PCT/DK1989/000266 DK8900266W WO9005705A1 WO 1990005705 A1 WO1990005705 A1 WO 1990005705A1 DK 8900266 W DK8900266 W DK 8900266W WO 9005705 A1 WO9005705 A1 WO 9005705A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- water
- phosphate
- particles
- iron
- process according
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims abstract description 42
- 229910019142 PO4 Inorganic materials 0.000 title claims abstract description 38
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 title claims abstract description 38
- 239000010452 phosphate Substances 0.000 title claims abstract description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 239000002245 particle Substances 0.000 claims abstract description 27
- 239000002351 wastewater Substances 0.000 claims abstract description 18
- 238000002425 crystallisation Methods 0.000 claims abstract description 7
- 230000008025 crystallization Effects 0.000 claims abstract description 7
- 239000007787 solid Substances 0.000 claims abstract description 7
- 239000000243 solution Substances 0.000 claims abstract description 7
- 239000006004 Quartz sand Substances 0.000 claims abstract description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 5
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims abstract description 5
- -1 iron(II) compound Chemical class 0.000 claims abstract description 5
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims abstract description 4
- 239000007864 aqueous solution Substances 0.000 claims abstract description 4
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims abstract description 3
- 229910021577 Iron(II) chloride Inorganic materials 0.000 claims abstract 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 10
- 238000007254 oxidation reaction Methods 0.000 claims description 7
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims description 6
- 230000003647 oxidation Effects 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 2
- 238000000746 purification Methods 0.000 abstract description 14
- 239000010802 sludge Substances 0.000 abstract description 9
- 239000000126 substance Substances 0.000 abstract description 7
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 238000005273 aeration Methods 0.000 abstract description 2
- 238000001556 precipitation Methods 0.000 description 16
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- 239000003153 chemical reaction reagent Substances 0.000 description 5
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 4
- 229910000399 iron(III) phosphate Inorganic materials 0.000 description 4
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 3
- 239000000920 calcium hydroxide Substances 0.000 description 3
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 3
- 239000012047 saturated solution Substances 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000001419 dependent effect Effects 0.000 description 2
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 2
- UCNNJGDEJXIUCC-UHFFFAOYSA-L hydroxy(oxo)iron;iron Chemical compound [Fe].O[Fe]=O.O[Fe]=O UCNNJGDEJXIUCC-UHFFFAOYSA-L 0.000 description 2
- 239000002054 inoculum Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- 229910001463 metal phosphate Inorganic materials 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- 238000010979 pH adjustment Methods 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 229910009112 xH2O Inorganic materials 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 239000005569 Iron sulphate Substances 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 230000001651 autotrophic effect Effects 0.000 description 1
- 230000031018 biological processes and functions Effects 0.000 description 1
- 239000010796 biological waste Substances 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 238000012851 eutrophication Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical class [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 229910052603 melanterite Inorganic materials 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 238000000247 postprecipitation Methods 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
Classifications
-
- 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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
-
- 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
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
Definitions
- the present invention relates to a process of removing phosphate from water, in particular waste water.
- the process according to the invention is characterized by what is stated in the characterizing portion of claim 1.
- the invention further relates to an apparatus for use when carrying out the process.
- a reduction of the phosphate content may be effected by biological and/or chemical methods.
- a biological removal of phosphate may be effected by means of autotrophic microorganisms which under certain conditions accumulate more phosphate than necessary for the metabolic processes. The method, however, demands completely specific operating conditions and microorganism, and it is impossible to observe the demands which today are made on the effluent from purification plants.
- the chemical processes for removal of phosphate can be divided into three groups dependent on the stage in the aggregate purification procedure at which the reagents are dosed: Pre-precipitation, where the reagents are dosed and the precipitated sludge removed before the biological purification is initiated. Simultaneous-precipitation, where the reagents are introduced during the biological purification and where the precipitate is removed together with the biological sludge. Post-precipitation, where the reagents are dosed and the chemical precipitation occurs after the biological purification. In all three precipitation types chemical sludge is produced, resulting in increased sludge production from the purification plants with entailing increased costs. In all three cases the precipitated phosphate is deposited without possibility of reuse, even through it constitutes a potential phosphorus resource.
- 2 021 087 discloses a process for removing phosphorous compounds from waste water, by which it has been sought to solve the above problems by treating the waste water with at least one reagent which forms a crystalline sparingly soluble salt and contacting the water with an inoculum which furthers the crystallization. This contact takes place in a fluidized bed of particles of the inoculum.
- the water to be purified must thus have a chemical composition within certain limits. This goes for the calcium concentration which is adjusted by addition of Ca(OH) 2 or CaCl 2 , and in particular for the pH-value which is critical during the entire course of the process.
- the transient hardness of the water i.e. bicarbonate content
- pH must again be raised to precipitate phosphate, e.g.
- GB publication No. 2 053 884 discloses a method of removing phosphate from waste water in a fluidized bed of metal phosphate particles.
- the phosphate is crystallized as metal phosphate on the metal particles after treatment of the waste water with one or more metal compounds selected from Fe(III)- and Al-compounds.
- it is however necessary to perform several adjustments of pH to make the process proceed satisfactorily and to obtain a purified waste water which without risk can be discharged to the recipient.
- the necessity of adjusting pH is a consequence of the precipitation reaction
- the effluent flow from the mechanical and biological plant must be oxidized prior to the phosphate removal proper. This may be effected either by passing the water over oxidation steps or by blowing air through the water.
- a pH-lowering is superfluous because the velocity decisive stage is not the precipitation of Fe(III) phosphate, but the oxidation of Fe(II) to Fe(III), which proceeds slowly and controllably at normal degrees of acidity.
- the drawing shows a column 1 which in one embodiment is a cylinder having a height of 4 m and a diameter of 60 cm.
- the column is partly filled with a particle material 2 which e.g. may be particles of the same material which it is desired to precipitate, i.e. iron(III)-phosphate.
- a particle material 2 which e.g. may be particles of the same material which it is desired to precipitate, i.e. iron(III)-phosphate.
- Another material which has been found suitable is ordinary quartz sand which is attractive not least for reasons of economy.
- phosphate containing waste water by means of a pump 4 is introduced into the column through a feed tube 5.
- phosphate containing waste water by means of a pump 4 is introduced into the column through a feed tube 5.
- a feed tube 5 From a container 6 an almost saturated solution of a Fe(II) salt is passed into the column 1 by means of a pump 7, and by suitable flow-regulation a solid, stirred or fluidized bed of
- the purified waste water leaves the apparatus via an overflow 8.
- the dosing of the Fe(II) solution may take place immediately above the bottom of the column or it may take place at several levels or at several points at a level dependent upon the selected apparatus size which is not critical .
- the particle material may advantageously be quartz sand, but it is also obvious to use particles of the same compound as it is desired to precipitate, i.e. Fe(III)-phosphate containing particles.
- the particle size is typically a diameter of 0.1-1.0 mm, preferably a diameter of 0.3-0.6 mm. It is desirable to use small particles to achieve a large crystallization area, but large particles to achieve a high hydraulic surface load.
- the metal compound which in aqueous solution is introduced into the column may advantageously be an almost saturated solution of FeSO 4 ⁇ 7H 2 O.
- Fe(II)-salt solutions may well be used, but iron(II) sulphate is particularly advantageous as it is a cheap and easily accessible material which e.g. occurs as by-product in titanium dioxide production.
- Another suitable Fe(II) salt is Fe(II) chloride.
- the reaction is very fast, the typical residence time being some minutes. This is a very short residence time. in waste water context where residence, times of several hours are often used, and it is obvious that in this way a significantly improved utilization of the apparatus is achieved.
- the particles may be used as filler material in the building sector.
- Another possibility is to use the particles for producing phosphoric acid.
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (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)
- Removal Of Specific Substances (AREA)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DK6345/88 | 1988-11-14 | ||
| DK634588A DK634588D0 (da) | 1988-11-14 | 1988-11-14 | Fremgangsmaade til fjernelse af phosphat fra vand og anlaeg til brug ved fremgangsmaaden |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO1990005705A1 true WO1990005705A1 (en) | 1990-05-31 |
Family
ID=8148615
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/DK1989/000266 WO1990005705A1 (en) | 1988-11-14 | 1989-11-13 | A process of removing phosphate from water, and a system for use in the process |
Country Status (3)
| Country | Link |
|---|---|
| AU (1) | AU4631689A (da) |
| DK (1) | DK634588D0 (da) |
| WO (1) | WO1990005705A1 (da) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003038351A1 (en) * | 2001-11-02 | 2003-05-08 | Ozone Manufacturing Pty Ltd | Refrigeration purifiers |
| EP1216209A4 (en) * | 1999-08-06 | 2004-04-21 | Trustees Stevens Inst Tech | An iron powder and sand filtration process for treatment of water contaminated with heavy metals and organic compounds |
| WO2015181205A1 (en) | 2014-05-28 | 2015-12-03 | Biaqua B.V. | Method for removing phosphate from water fractions |
| EP3000788A1 (en) | 2014-09-26 | 2016-03-30 | BiAqua B.V. | Method for removing phosphate from water fractions |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CH227986A (de) * | 1941-02-14 | 1943-07-31 | Licentia Gmbh | Verfahren zum Reinigen von Abwasser. |
| US3488717A (en) * | 1967-08-22 | 1970-01-06 | Dow Chemical Co | Chemical precipitation and flocculation |
| GB2053884A (en) * | 1979-06-30 | 1981-02-11 | Stamicarbon | Removal of phosphorus compounds from waste water |
| AU559116B3 (en) * | 1987-01-09 | 1987-04-02 | Robert James Mcdonald | Wastewater clarifier |
-
1988
- 1988-11-14 DK DK634588A patent/DK634588D0/da not_active Application Discontinuation
-
1989
- 1989-11-13 WO PCT/DK1989/000266 patent/WO1990005705A1/en unknown
- 1989-11-13 AU AU46316/89A patent/AU4631689A/en not_active Abandoned
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CH227986A (de) * | 1941-02-14 | 1943-07-31 | Licentia Gmbh | Verfahren zum Reinigen von Abwasser. |
| US3488717A (en) * | 1967-08-22 | 1970-01-06 | Dow Chemical Co | Chemical precipitation and flocculation |
| GB2053884A (en) * | 1979-06-30 | 1981-02-11 | Stamicarbon | Removal of phosphorus compounds from waste water |
| AU559116B3 (en) * | 1987-01-09 | 1987-04-02 | Robert James Mcdonald | Wastewater clarifier |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1216209A4 (en) * | 1999-08-06 | 2004-04-21 | Trustees Stevens Inst Tech | An iron powder and sand filtration process for treatment of water contaminated with heavy metals and organic compounds |
| WO2003038351A1 (en) * | 2001-11-02 | 2003-05-08 | Ozone Manufacturing Pty Ltd | Refrigeration purifiers |
| WO2015181205A1 (en) | 2014-05-28 | 2015-12-03 | Biaqua B.V. | Method for removing phosphate from water fractions |
| EP3000788A1 (en) | 2014-09-26 | 2016-03-30 | BiAqua B.V. | Method for removing phosphate from water fractions |
Also Published As
| Publication number | Publication date |
|---|---|
| DK634588D0 (da) | 1988-11-14 |
| AU4631689A (en) | 1990-06-12 |
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