WO1999024365A1 - Composition and process for the removal of the phosphate ion content of waters - Google Patents
Composition and process for the removal of the phosphate ion content of waters Download PDFInfo
- Publication number
- WO1999024365A1 WO1999024365A1 PCT/HU1998/000096 HU9800096W WO9924365A1 WO 1999024365 A1 WO1999024365 A1 WO 1999024365A1 HU 9800096 W HU9800096 W HU 9800096W WO 9924365 A1 WO9924365 A1 WO 9924365A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- calcium
- iron compound
- composition
- mass
- parts
- Prior art date
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 51
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 title claims abstract description 25
- 238000000034 method Methods 0.000 title claims abstract description 15
- 229940085991 phosphate ion Drugs 0.000 title claims abstract description 15
- 239000003643 water by type Substances 0.000 title claims abstract description 11
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 18
- 150000002506 iron compounds Chemical class 0.000 claims abstract description 18
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims abstract description 12
- 239000000920 calcium hydroxide Substances 0.000 claims abstract description 11
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 10
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims abstract description 10
- 229910001424 calcium ion Inorganic materials 0.000 claims abstract description 10
- 239000007787 solid Substances 0.000 claims abstract description 8
- 239000005995 Aluminium silicate Substances 0.000 claims abstract description 7
- 229910000323 aluminium silicate Inorganic materials 0.000 claims abstract description 7
- 235000012211 aluminium silicate Nutrition 0.000 claims abstract description 7
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000000292 calcium oxide Substances 0.000 claims abstract description 6
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims abstract description 6
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical class [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims abstract description 5
- 150000002500 ions Chemical class 0.000 claims abstract description 5
- PZZYQPZGQPZBDN-UHFFFAOYSA-N aluminium silicate Chemical compound O=[Al]O[Si](=O)O[Al]=O PZZYQPZGQPZBDN-UHFFFAOYSA-N 0.000 claims abstract 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 14
- 239000010457 zeolite Substances 0.000 claims description 9
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 7
- 229910052742 iron Inorganic materials 0.000 claims description 7
- 229910021536 Zeolite Inorganic materials 0.000 claims description 6
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 3
- 239000011575 calcium Substances 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 3
- 230000003213 activating effect Effects 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 7
- 229910019142 PO4 Inorganic materials 0.000 description 7
- 239000010452 phosphate Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 5
- 238000000746 purification Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- -1 Fe(III) salt anions Chemical class 0.000 description 2
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 2
- JYIBXUUINYLWLR-UHFFFAOYSA-N aluminum;calcium;potassium;silicon;sodium;trihydrate Chemical compound O.O.O.[Na].[Al].[Si].[K].[Ca] JYIBXUUINYLWLR-UHFFFAOYSA-N 0.000 description 2
- 229910001603 clinoptilolite Inorganic materials 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000009837 dry grinding Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229960004887 ferric hydroxide Drugs 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 238000005755 formation reaction Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910000402 monopotassium phosphate Inorganic materials 0.000 description 1
- 235000019796 monopotassium phosphate Nutrition 0.000 description 1
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 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
- C02F1/52—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 invention relates to a composition suitable for removing the phosphate ion content of waters and a process for producing the same.
- the present invention also relates to a process for the removal of the phosphate ion content of water.
- the invention therefore, provides a composition useful for removing the phosphate ion content of waters.
- the composition of the invention contains 0.1-99.9 parts by mass of an iron compound, namely one or more solid hydrous Fe(II) or Fe(III) salts or their oxidized forms, ground together with 99.9-0.1 parts by mass of a porous aluminium silicate containing exchangeable ions (hereinafter: silicate component), and 0.1-10 moles of a solid calcium ion source, namely calcium hydroxide, calcium oxide and/or calcium carbonate per one mole of iron compound.
- silicate component porous aluminium silicate containing exchangeable ions
- An essential feature of the iron compound that can be employed in the composition of the invention is that it should contain bound water. We have found that the substitution of a particular hydrous ferrous/ferric salt with the chemically identical, but anhydrous salt can no longer ensure the desired results.
- the specific nature of the Fe(II) or Fe(III) salt anions is not critical.
- the hydrous ferrous/ferric salts can also be used in a partially oxidized form; such substances are formed from Fe(II) salts exposed to air.
- Fe(II) sulphate heptahydrate is a particularly advantageous choice for an iron compound.
- compositions of the invention can suitably contain 5 to 95, preferably 10 to 90, more preferably 25 to 75 parts by mass of an iron compound.
- the silicate component of the compositions of the invention can be any porous aluminium silicate containing exchangeable ions.
- various natural zeolites and the formations containing them, as well as synthetic zeolites can be mentioned. Natural zeolites, such as clinoptilolite are especially useful on account of their availability and attractive price.
- the quantity of the silicate component in the compositions of the invention is suitably 5 to 95, preferably 10 to 90, more preferably 25 to 75 parts by mass.
- Certain silicate components (such as zeolites) adsorb water when exposed to air, which can only be removed by heat treatment at high temperatures.
- compositions of the invention can contain calcium hydroxide, calcium oxide and/or calcium carbonate as calcium ion source. Of these, calcium hydroxide and a mixture of calcium hydroxide and calcium carbonate have proved especially suitable. These compounds are used as dry solids, the term "dry” also includes air-dry substances according to the above definition.
- the molar ratio of iron to calcium in the compositions of the invention can be suitably 1 :(0.3 to 6), preferably 1 :(0.5 to 3), and more preferably l :(0.9 to 1.2).
- the terms "grinding” and “grinding together” are interpreted in their wide sense in the specification. These terms include every possible mechanochemical activation method.
- the invention furthermore, provides a process for producing a composition useful for removing the phosphate ion content of waters, wherein a mixture of 0.1 to 99.9 parts by mass of an iron compound, namely one or more solid hydrous Fe(II) or Fe(III) salts or the oxidized forms thereof, 99.9 to 0.1 parts by mass of a silicate component, and 0.1 to 10 moles of calcium hydroxide, calcium oxide and/or calcium carbonate per one mole of iron compound is mechanochemicaliy activated.
- the invention provides a process for removing the phosphate ion content of waters, wherein the water to be treated is brought into contact with the composition of the invention.
- a pH of 4 to 8 preferably between 4.5 and 6
- This pH value meets the dischargeability requirements.
- Example 1 The samples listed in Table 1 were prepared by intensely grinding quantities of Fe(II) sulphate heptahydrate, clinoptilolite, calcium hydroxide and/or calcium carbonate in different proportions (the compositions of the invention are denoted by serial numbers, while the control compositions are denoted by letters in the table).
- a sample of the compositions disclosed in Table 1 was added to 100 ml of model solution (aqueous potassium dihydrogen phosphate solution containing 20 ppm orthophosphate ions) in the quantity stated therein, then the phosphate ion concentration of the solution was measured after a period of 24 hours. The measurement results are set forth in Table 1.
- Sample Composition of sample (g) Sample added to Residual phosphate number FeS0 4 .7H 2 0 Clinopti- Ca(0H) 2 CaC0 3 100 ml water (g) content of sample or mark lolite (ppm)
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)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Water Treatment By Sorption (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Priority Applications (8)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB0013638A GB2346875A (en) | 1997-11-07 | 1998-11-06 | Composition and process for the removal of the phosphate ion content of waters |
| DE19882795T DE19882795T1 (de) | 1997-11-07 | 1998-11-06 | Zusammensetzung und Verfahren zum Entfernen des Phosphationengehalts von Wässern |
| AU12537/99A AU749564B2 (en) | 1997-11-07 | 1998-11-06 | Composition and process for the removal of the phosphate ion content of waters |
| NZ504824A NZ504824A (en) | 1997-11-07 | 1998-11-06 | Composition containing an iron compound, an aluminium silicate and a calcium source useful for the removal of the phosphate ion content of waters |
| DK200000761A DK200000761A (da) | 1997-11-07 | 2000-05-08 | Komposition og metode til fjernelse af phosphatlonindholdet fra vand |
| FI20001077A FI20001077A (fi) | 1997-11-07 | 2000-05-08 | Seos ja menetelmä fosfaatti-ionisisällön poistamiseksi vedestä |
| SE0001712A SE0001712L (sv) | 1997-11-07 | 2000-05-08 | Komosition och förfarande för avlägsning av innehållet av fosfatjoner i vatten |
| NO20002436A NO20002436L (no) | 1997-11-07 | 2000-05-11 | Sammensetning og fremgangsmÕte for fjerning av fosfationinnholdet i vann |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| HUP9701918 | 1997-11-07 | ||
| HU9701918A HUP9701918A2 (hu) | 1997-11-07 | 1997-11-07 | Készítmény és eljárás vizek foszfátion-tartalmának eltávolítására |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO1999024365A1 true WO1999024365A1 (en) | 1999-05-20 |
Family
ID=89995724
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/HU1998/000096 WO1999024365A1 (en) | 1997-11-07 | 1998-11-06 | Composition and process for the removal of the phosphate ion content of waters |
Country Status (10)
| Country | Link |
|---|---|
| AU (1) | AU749564B2 (hu) |
| DE (1) | DE19882795T1 (hu) |
| DK (1) | DK200000761A (hu) |
| FI (1) | FI20001077A (hu) |
| GB (1) | GB2346875A (hu) |
| HU (1) | HUP9701918A2 (hu) |
| NO (1) | NO20002436L (hu) |
| NZ (1) | NZ504824A (hu) |
| SE (1) | SE0001712L (hu) |
| WO (1) | WO1999024365A1 (hu) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006134215A1 (en) * | 2005-06-17 | 2006-12-21 | Maa- Ja Elintarviketalouden Tutkimuskeskus | Filter material prepared by grinding, comprising calcium hydroxide |
| WO2013020428A1 (zh) * | 2011-08-11 | 2013-02-14 | 四川龙蟒钛业股份有限公司 | 磷化工废水的处理方法 |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3629634A1 (de) * | 1986-08-30 | 1988-03-03 | Swf Auto Electric Gmbh | Elektrische maschine, insbesondere elektromotor |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0003119A1 (de) * | 1978-01-11 | 1979-07-25 | Hoechst Aktiengesellschaft | Flockungsmittel zum Reinigen von Abwässern und Verfahren zu seiner Herstellung |
| JPS57135012A (en) * | 1981-02-13 | 1982-08-20 | Minato Sangyo Kk | Water treating agent |
| US4415467A (en) * | 1981-03-05 | 1983-11-15 | Colloid Piepho | Agent for the purification of waste waters and process for its production |
| EP0612692A1 (en) * | 1993-02-26 | 1994-08-31 | Createrra Inc. | Water purifying substances and method for production thereof |
| JPH08168607A (ja) * | 1994-12-15 | 1996-07-02 | Kanken:Kk | 切削油凝集処理剤 |
| JPH09225208A (ja) * | 1996-02-21 | 1997-09-02 | Kunimine Kogyo Kk | 汚水の処理剤及び処理方法 |
-
1997
- 1997-11-07 HU HU9701918A patent/HUP9701918A2/hu unknown
-
1998
- 1998-11-06 WO PCT/HU1998/000096 patent/WO1999024365A1/en active IP Right Grant
- 1998-11-06 AU AU12537/99A patent/AU749564B2/en not_active Ceased
- 1998-11-06 DE DE19882795T patent/DE19882795T1/de not_active Withdrawn
- 1998-11-06 NZ NZ504824A patent/NZ504824A/en unknown
- 1998-11-06 GB GB0013638A patent/GB2346875A/en not_active Withdrawn
-
2000
- 2000-05-08 DK DK200000761A patent/DK200000761A/da not_active Application Discontinuation
- 2000-05-08 FI FI20001077A patent/FI20001077A/fi unknown
- 2000-05-08 SE SE0001712A patent/SE0001712L/ not_active Application Discontinuation
- 2000-05-11 NO NO20002436A patent/NO20002436L/no not_active Application Discontinuation
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0003119A1 (de) * | 1978-01-11 | 1979-07-25 | Hoechst Aktiengesellschaft | Flockungsmittel zum Reinigen von Abwässern und Verfahren zu seiner Herstellung |
| JPS57135012A (en) * | 1981-02-13 | 1982-08-20 | Minato Sangyo Kk | Water treating agent |
| US4415467A (en) * | 1981-03-05 | 1983-11-15 | Colloid Piepho | Agent for the purification of waste waters and process for its production |
| EP0612692A1 (en) * | 1993-02-26 | 1994-08-31 | Createrra Inc. | Water purifying substances and method for production thereof |
| JPH08168607A (ja) * | 1994-12-15 | 1996-07-02 | Kanken:Kk | 切削油凝集処理剤 |
| JPH09225208A (ja) * | 1996-02-21 | 1997-09-02 | Kunimine Kogyo Kk | 汚水の処理剤及び処理方法 |
Non-Patent Citations (3)
| Title |
|---|
| DATABASE WPI Section Ch Week 8239, Derwent World Patents Index; Class D15, AN 82-82308E, XP002094098 * |
| PATENT ABSTRACTS OF JAPAN vol. 096, no. 011 29 November 1996 (1996-11-29) * |
| PATENT ABSTRACTS OF JAPAN vol. 098, no. 001 30 January 1998 (1998-01-30) * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006134215A1 (en) * | 2005-06-17 | 2006-12-21 | Maa- Ja Elintarviketalouden Tutkimuskeskus | Filter material prepared by grinding, comprising calcium hydroxide |
| WO2013020428A1 (zh) * | 2011-08-11 | 2013-02-14 | 四川龙蟒钛业股份有限公司 | 磷化工废水的处理方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| NO20002436D0 (no) | 2000-05-11 |
| GB2346875A (en) | 2000-08-23 |
| SE0001712L (sv) | 2000-06-20 |
| AU1253799A (en) | 1999-05-31 |
| GB0013638D0 (en) | 2000-07-26 |
| SE0001712D0 (sv) | 2000-05-08 |
| DE19882795T1 (de) | 2001-03-29 |
| NZ504824A (en) | 2001-10-26 |
| HUP9701918A2 (hu) | 2003-03-28 |
| HU9701918D0 (en) | 1998-01-28 |
| DK200000761A (da) | 2000-06-29 |
| NO20002436L (no) | 2000-06-02 |
| FI20001077A (fi) | 2000-06-27 |
| AU749564B2 (en) | 2002-06-27 |
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