AU1253799A - 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 PDF

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Publication number
AU1253799A
AU1253799A AU12537/99A AU1253799A AU1253799A AU 1253799 A AU1253799 A AU 1253799A AU 12537/99 A AU12537/99 A AU 12537/99A AU 1253799 A AU1253799 A AU 1253799A AU 1253799 A AU1253799 A AU 1253799A
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Australia
Prior art keywords
calcium
composition according
mass
parts
iron compound
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AU12537/99A
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AU749564B2 (en
Inventor
Gaborne Illes
Denes Kallo
Jozsefne Karacsony
Laszlo Kotai
Gabor Palinkas
Janos Papp
Gyorgy Udvardy
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Magyar Tudomanyos Akademia Kemiai Kutatokozpont
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MTA KEMIAI KUTATOKOZPONT
Magyar Tudomanyos Akademia Kemiai Kutatokozpont
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Publication of AU1253799A publication Critical patent/AU1253799A/en
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Publication of AU749564B2 publication Critical patent/AU749564B2/en
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Classifications

    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/52Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/5236Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents

Description

WO 99/24365 PCT/HU98/00096 COMPOSITION AND PROCESS FOR THE REMOVAL OF THE PHOSPHATE ION CONTENT OF WATERS 5 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. As a result of accumulation, the phosphate content of waters 10 released into the environment causes serious environmental problems. For this very reason, numerous methods have been worked out for the removal of phosphate ions in water, of which the solutions employing iron/zeolite systems are currently considered the most favourable in terms of the chemicals and equipment required and the removal efficiency 15 achieved. The essence of this system lies in that the water to be treated is brought into contact with ferric/ferrous zeolite or a mixture of zeolite and a flocculation agent such as ferric hydroxide with a large specific surface or another ferrous substance. Iron/zeolite-type water purification formulations and their uses are described, among others, in Hungarian 20 Patent Specification No. 195 457 and Japanese Patent Specifications 63 40575-B4 and 07-284762-A2. When preparing known iron/zeolite-type water purification formulations, always the aqueous solution of a ferrous/ferric salt is mixed with zeolite, and, if required, additional chemicals (such as alkalis) are 25 added to the aqueous mixture, then the resulting slurry is precipitated WO 99/24365 PCT/HU98/00096 -2 and/or filtered, and the separated solid is dried. The treatment and dehydration of large volumes of aqueous material require a considerable investment of equipment and energy, which raises the cost of phosphate removal. 5 In the course of our work, we strived to find a technical solution whereby the equipment and energy required for the production of iron/zeolite-type water purification compositions could be significantly reduced, without negatively affecting the effectiveness of the composi tion. 10 In order to eliminate the equipment- and energy-intensive procedures (filtration and dehydration) of the aqueous processes, we attempted to make water purification compositions by dry grinding together air-dry zeolite varieties and hydrous ferrous/ferric salts; the phosphate removing effect of the resulting compositions, however, fell 15 significantly short of that of the aqueous compositions, as expected. Surprisingly, it was found, however, that if these components were ground together in the presence of a calcium ion source, compositions with excellent phosphate removing effect were obtained. The invention, therefore, provides a composition useful for 20 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), 25 and 0.1-10 moles of a solid calcium ion source, namely calcium WO 99/24365 PCT/HU98/00096 -3 hydroxide, calcium oxide and/or calcium carbonate per one mole of iron compound. An essential feature of the iron compound that can be employed in the composition of the invention is that it should contain bound water. 5 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 10 exposed to air. Fe(II) sulphate heptahydrate is a particularly advant ageous choice for an iron compound. The 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. 15 The silicate component of the compositions of the invention can be any porous aluminium silicate containing exchangeable ions. For example, 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 20 attractive price. The quantity of the silicate component in the composi tions 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. Such silicate components should 25 suitably be used in air-dry (i.e., not a previously heat-treated) condition.
WO 99/24365 PCT/HU98/00096 -4 The 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 5 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 inven tion can be suitably 1:(0.3 to 6), preferably 1:(0.5 to 3), and more preferably 1:(0.9 to 1.2). 10 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, 15 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 mechanochemically 20 activated. Finally, 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. For example, it is possible to proceed by passing the water to be treated through a 25 column which contains the composition of the invention or adding the composition to the water to be treated, and, after the required time has WO 99/24365 PCT/HU98/00096 -5 elapsed (and meanwhile mixing the system as appropriate), removing the composition from the treated water by filtration, precipitation or another suitable method. We have found that an especially good phosphate removing effect can be achieved when treating water at a pH of 4 to 8 5 (preferably between 4.5 and 6). This pH value meets the dischargeability requirements. The invention is described in detail in the following examples without any restriction on the scope of protection. Example 1 10 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 15 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. 20 As it can be established from the data in Table 1, neither component of the compositions of the invention can be omitted without a drastic reduction in the overall effect. This also proves that the individual components of the compositions of the invention (iron compound, silicate component and calcium ion source) synergistically enhance one another's 25 activity.
WO 99/24365 PCTIHU98/00096 -6 04 0 C~ ar - 00000 0. U -W CD0 DC 0 0 0 0 0 - - DC CD) CD) 0 4-4 0 o .L - Wln U U) V)l Ll U) f LOI Lfl 41 Q 4 .1 0 Om r. 0 I1 m ml m n m o -4 1 0 N- ul UL L1 UL L 0 L ILn UL rq N (N CN Cr) NN 0 CN (N N N N C1 (Nq (N N (N U) 0.) ~ - N m Ln Wl '0 N o a WO 99/24365 PCTIHU98/00096 -7 0 CL j . . w . l . N w a 0 .- 1 0 r- r- 0)0 0 0 0 C)C ) D 00 0 0 0 U) 00 U '-1 a) 0 : v4 co a-, -- i 0 r-N -4 cN r4C ) 0" fn ..I 0 D 0 0 D 0 0 D 0 D 0 0 D 0 D 0 00D 0 0 0D 0D 0 0 Ln4 C). 4n CD 0) C) N4C 0 0 0 i 0 li U- , Ui U, Ln Un Un U, 0 0 e 0 u N, U, U, U, 0 U , , 0 U (N (N * n w, tfl N U v) V) 4 -4 -4A- -4 -4 -4 -4 WO 99/24365 PCT/HU98/00096 -4B %64 S04 a4 co 0 c CD 0 -I -q w~ 0c a e r-c a a% o- 0o cN cN ar, 0) 0 D N CD r4 4 CcJ A - -j -4 r-4 4 4 0 u M NV CD M O -4 r~- Cq Ul fn 0 ~ -4 o 0 :0000000000 C c~co 0)0 4.4 0 0 0 04 . 0 40 ('4 0) UU -44 0) a) Ud WO 99/24365 PCT/HU98/00096 -9 Example 2 This example was used to test how the phosphate ion removing effect is dependent on the pH of the water. The pH of a 200-ml water sample containing 11.68 ppm phosphate ions was set to the values stated 5 in Table 2 with sulphuric acid or sodium hydroxide, 0.02 grams of composition No. 19 were added to the sample, and the residual phosphate ion content of the water was measured after periods of 24 and 48 hours. The results are set forth in Table 2. 10 Table 2 pH of water sample Residual phosphate ion content (ppm) after 24 hours after 48 hours. 15 3.1 9.2 9.2 5.3 0 0 7.2 5.0 5.0 9.4 8.0 8.0 11.0 8.4 8.3 20 The data in the table demonstrate that phosphate ions can be most effectively removed from solutions having a pH of 4 to 8.

Claims (11)

1. A composition for removing the phosphate ion content of waters, which comprises 0.1 to 99.9 parts by mass of an iron compound 5 selected from the group of solid hydrous Fe(II) and Fe(III) salts and oxidized forms thereof, ground together with 99.9 to 0.1 parts by mass of a porous aluminium silicate containing exchangeable ions, and 0.1 to 10 moles of a calcium ion source selected from the group of calcium hydroxide, calcium oxide and calcium carbonate per one mole of iron 10 compound.
2. The composition according to claim 1, which comprises Fe(II) sulphate heptahydrate as the iron compound.
3. The composition according to claim 1 or 2, which comprises a natural or synthetic zeolite as the aluminium silicate. 15
4. The composition according to any of claims 1 to 3, which comprises a mixture of calcium hydroxide and calcium carbonate as the calcium ion source.
5. The composition according to any of claims 1 to 4, which comprises an iron compound of 25 to 75 parts by mass. 20
6. The composition according to any of claims 1 to 5, which comprises an aluminium silicate of 25 to 75 parts by mass.
7. The composition according to any of claims 1 to 6, which comprises the iron compound and the calcium ion source in a molar ratio of 1:(0.5 to 3) iron:calcium. WO 99/24365 PCT/HU98/00096 - 11
8. The composition according to any of claims 1 to 7, which comprises the iron compound and the calcium ion source in a molar ratio of 1 :(0.9 to 1.2) iron:calcium.
9. A process for producing a composition useful for removing the 5 phosphate ion content of waters, which comprises mechanochemically activating a mixture of 0.1 to 99.9 parts by mass of one or more iron compound(s) selected from the group of solid hydrous Fe(II) and Fe(III) salts and oxidized froms thereof, 99.9 to 0.1 parts by mass of a porous aluminium silicate containing exchangeable ions, and 0.1 to 10 moles of 10 a calcium ion source selected from the group of calcium hydroxide, calcium oxide and calcium carbonate per one mole of iron compound.
10. A process for removing the phosphate ion content of waters, which comprises contacting the water to be treated with a composition according to any of claims 1 to 8. 15
11. The process according to claim 10, which comprises treating water at a pH of 4 to 8.
AU12537/99A 1997-11-07 1998-11-06 Composition and process for the removal of the phosphate ion content of waters Ceased AU749564B2 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
HU9701918 1997-11-07
HU9701918A HUP9701918A2 (en) 1997-11-07 1997-11-07 Method and composition for removing of phosphor contain of water
PCT/HU1998/000096 WO1999024365A1 (en) 1997-11-07 1998-11-06 Composition and process for the removal of the phosphate ion content of waters

Publications (2)

Publication Number Publication Date
AU1253799A true AU1253799A (en) 1999-05-31
AU749564B2 AU749564B2 (en) 2002-06-27

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AU (1) AU749564B2 (en)
DE (1) DE19882795T1 (en)
DK (1) DK200000761A (en)
FI (1) FI20001077A (en)
GB (1) GB2346875A (en)
HU (1) HUP9701918A2 (en)
NO (1) NO20002436L (en)
NZ (1) NZ504824A (en)
SE (1) SE0001712L (en)
WO (1) WO1999024365A1 (en)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3629634A1 (en) * 1986-08-30 1988-03-03 Swf Auto Electric Gmbh ELECTRICAL MACHINE, ESPECIALLY ELECTRIC MOTOR
FI117162B (en) * 2005-06-17 2006-07-14 Maa Ja Elintarviketalouden Tut Filter material for removing phosphor from waste water originating from e.g. scattered settlement and/or leachate, comprises lightweight aggregate, calcium hydroxide and water which have been mixed by grinding during preparation
CN102328984B (en) * 2011-08-11 2013-08-14 四川龙蟒钛业股份有限公司 Processing method of waste water in phosphorus chemical industry

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2801034A1 (en) * 1978-01-11 1979-07-12 Hoechst Ag FLOCCULATING AGENT FOR CLEANING WASTE WATER
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
DE69416015D1 (en) * 1993-02-26 1999-03-04 Createrra Inc Process for the preparation of substances for the purification of water
JPH08168607A (en) * 1994-12-15 1996-07-02 Kanken:Kk Cutting oil flocculating treatment agent
JPH09225208A (en) * 1996-02-21 1997-09-02 Kunimine Kogyo Kk Sewage treating agent and treating method

Also Published As

Publication number Publication date
NO20002436L (en) 2000-06-02
SE0001712D0 (en) 2000-05-08
HUP9701918A2 (en) 2003-03-28
GB2346875A (en) 2000-08-23
NO20002436D0 (en) 2000-05-11
GB0013638D0 (en) 2000-07-26
SE0001712L (en) 2000-06-20
HU9701918D0 (en) 1998-01-28
AU749564B2 (en) 2002-06-27
WO1999024365A1 (en) 1999-05-20
DE19882795T1 (en) 2001-03-29
DK200000761A (en) 2000-06-29
NZ504824A (en) 2001-10-26
FI20001077A (en) 2000-06-27

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