NZ504824A - Composition containing an iron compound, an aluminium silicate and a calcium source useful for the removal of the phosphate ion content of waters - Google Patents

Composition containing an iron compound, an aluminium silicate and a calcium source useful for the removal of the phosphate ion content of waters

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Publication number
NZ504824A
NZ504824A NZ504824A NZ50482498A NZ504824A NZ 504824 A NZ504824 A NZ 504824A NZ 504824 A NZ504824 A NZ 504824A NZ 50482498 A NZ50482498 A NZ 50482498A NZ 504824 A NZ504824 A NZ 504824A
Authority
NZ
New Zealand
Prior art keywords
calcium
iron compound
composition according
mass
parts
Prior art date
Application number
NZ504824A
Inventor
Gaborne Illes
Denes Kallo
Jozsefne Karacsony
Laszlo Kotai
Janos Papp
Gabor Palinkas
Gyorgy Udvardy
Original Assignee
Mta Kemiai Kutatokozpont
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 Mta Kemiai Kutatokozpont filed Critical Mta Kemiai Kutatokozpont
Publication of NZ504824A publication Critical patent/NZ504824A/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

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)

Abstract

A composition for removing the phosphate ion content of water comprises: a) 0.1 to 99.9 parts by mass of an iron compound selected from solid hydrous Fe(II) and Fe(III) salts b) 99.9 to 0.1 parts by mass of a porous aluminum silicate containing exchangeable ions and c) 0.1 to 10 moles of a calcium ion source of calcium carbonate with either calcium oxide or calcium hydroxide or both per mole of the iron compound. The components of the composition are dry grounded together.

Description

New Zealand Paient Spedficaiion for Paient Number 504824 50 4824 WO 99/24365 PCT/HU98/00096 COMPOSITION AND PROCESS FOR THE REMOVAL OF THE PHOSPHATE ION CONTENT OF WATERS 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 floccuiation 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, m US Patent 20 Specification No. 4,772,307.
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 intellectual property office of n.z. 2 1 AUG 2001 RECEIVED 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'.
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 composition.
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 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 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 dry 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 amended sheet n(9 n n 0 <"> ' -> o o -! n ■> n no- i n o o a e a o o i -i -> o o n e o o «"> n tooooooo o » <■> o o " no ooooi^^ no oo carbonate along with either calcium oxide or calcium hydroxide or both 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. s . s 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 advantageous 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.
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 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. Such silicate components should 25 suitably be used in air-dry (i.e., not a previously heat-treated) condition. amended shee1 504824 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 dry solids, the term "dry" also includes air-dry substances according to the above definition.
The molar ratio of iron to calcium m the compositions of the invention can be suitably 1:(0.3 to 6), preferably 1:(0 5 to 3), and more preferably 1 (0 9 to 1.2).
The terms "grinding" and "grinding together" are interpreted m their wide sense in the specification. These terms include every possible mechanochemical activation method.
Unless the context clearly requires otherwise, throughout the description and the claims, the words "comprise", "comprising" and the like, are to be construed in an inclusive sense as opposed to an exclusive or exhaustive sense, that is to say, m the sense of "including, but not limited to" 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 mechanochemically 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 column which contains the composition of the invention or adding the composition to the water to be treated, and, after the required time has 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 (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 The samples listed in Table 1 were prepared by intensely grinding quantities of Fe(II) sulphate heptahydrate, clinoptilolite, calcium hydroxide and 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.
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 activity. amended sheet Teble 1 Sample number Composition of sample (g) FeS04.7HjO Clinoptilolite Ca (OH); CaCOj Sample added to 100 ml water (g) Residual phosphate ' content of sample * (PPm) J J 3 a. o o 3 0 0 > ZP* . iTI z o m 0 U) 1 m rn H 1 2 3 4 6 22.5 22.5 22.5 22.5 22 .5 22.5 31.5 31.5 31.5 31.5 31.5 31.5 1.0 2.0 3.0 4.0 0.1 8.0 7.0 6.0 5.0 4.0 8.0 0.0409 0.0702 0.0401 0.0705 0.0403 0.0706 0.0410 0.0712 0.0412 0.0710 0.400 0.0703 O.30 0.04 0.08 0 0.13 0.12 0.08 0 0.11 0.09 0.39 0 l CJ\ I J O I o o o > a o • o « a • a a o life.
Sample Composition of sample (g) number FeS0«.7Hj0 Clinopti- Ca(Oll)a CaCOj lolite' §htl&"'' ' ~ 7 22.5 31.5 0.5 7.5 $pi*. 3fJ vt'>" ' * ' fife B 22.5 31.5 1.0 6..0 9 11.25 31.5 0.25 3,5 J r /.
V?.*; 1Q 45.0 31.5 0.75 7.0 11 56.5 31.5 1.0 10.5 1 -n ?'v, . a 12 67.5 31.5 1.25 15.0 /<•' m o 05 .X m m H 13 45.0 31.5 1.0 15.0 14 67.5 31.5 1.5 21.5 Sample added Co 100 ml water (g) Residual phosphate content o£ sample (ppm) OQ0009 a 0.0411 3.04 0 O 0.0710 0 - 99 0 9 00 0.0404 1.06 0 o 0.0704 0.0408 0.0709 0 7.4 1.5 DO 3 0 o o O » a o o JO o DO o O 0 o 0.0401 0.72 3 0.0700 0.0417 0 0.12 o o « 0 O O 0 w 1 3 0.0701 0 o 0 J j> O -« 0.0401 0.06 O J l» 0.0700 0 o O O O O J o o 0 o o o 0.0402 0.3 O 0 O 9 o 9 a a • QOO 0.0703 0 0.0409 O.i 0.0703 0 Sample Composition of sample (g) Sample added to Residual phosphate number FeS04.7H20 Clinopti- Ca(QH)j CaCOj 100 ml watsr (g) content of sample* or mark lolite * (ppm) 67.5 31.5 1.5 23.0 0.0403 0.0704 0.1 0 - .J O o D 4 4 4 J CI 'A* 31.5 0.5 7.0 0.0400 0.0703 .0 20.0 ■D O JO o ■JO a 'B' 31.5 * 0.0408 0.0701 19.8 20.0 o o JO 5 0 0 J o ao 'C' 22,5 7.5 - 0.0407 .1 I j 0.0702 12.1 00 9 <J *D* - 0.5 8.0 0.0405 14.8 1 9 9 9 Q O i 9 •y 0.0703 12 .8 O o o m o VJ *E* 22.5 31.5 - - 0.0400 0.0702 19.0 17.2 o o w o X H * o a n m Measured after a period of 48 hours O J O 3 J J 9 9 9 9 O 9 9 ◦ • 9 9 9

Claims (14)

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 in Table 2 with sulphuric acid or sodium hydroxide, 0.02 grams of composition No. 15 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. Table 2 pH of water sample Residual phosphate ion content (ppm) after 24 hours after 48 hours- 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 The data in the table demonstrate that phosphate ions can be most effectively removed from solutions having a pH of 4 to 8. What is claimed is:
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 selected from the group of solid hydrous Fe(II) and Fe(III) salts and oxidized forms thereof, ground dry 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 namely calcium carbonate along with either calcium oxide or calcium hydroxide or both per one mole of iron 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.
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.
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 50 4824 WO 99/2436o 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 m 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 removmg 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 composes treating water at a pH of 4 to 8
12. A composition according to claim 1 substantially as herein described with reference to any one of Samples 1-18
13. A process according to claim 9, substantially as herein described with reference to Example 1.
14. A process according to claim 10, substantially as herein described with reference to Example 2.
NZ504824A 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 NZ504824A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
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 (1)

Publication Number Publication Date
NZ504824A true NZ504824A (en) 2001-10-26

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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

Country Status (10)

Country Link
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

Family Cites Families (6)

* 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
EP0612692B1 (en) * 1993-02-26 1999-01-20 Createrra Inc. Method for production of water purifying substances
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
GB2346875A (en) 2000-08-23
SE0001712D0 (en) 2000-05-08
HU9701918D0 (en) 1998-01-28
NO20002436D0 (en) 2000-05-11
AU749564B2 (en) 2002-06-27
DK200000761A (en) 2000-06-29
DE19882795T1 (en) 2001-03-29
HUP9701918A2 (en) 2003-03-28
SE0001712L (en) 2000-06-20
WO1999024365A1 (en) 1999-05-20
FI20001077A (en) 2000-06-27
GB0013638D0 (en) 2000-07-26
AU1253799A (en) 1999-05-31

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