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WO1999065826A1 - Procede permettant de purifier de l'eau contenant des pesticides - Google Patents

Procede permettant de purifier de l'eau contenant des pesticides

Info

Publication number
WO1999065826A1
WO1999065826A1 PCT/SE1999/001065 SE9901065W WO9965826A1 WO 1999065826 A1 WO1999065826 A1 WO 1999065826A1 SE 9901065 W SE9901065 W SE 9901065W WO 9965826 A1 WO9965826 A1 WO 9965826A1
Authority
WO
WIPO (PCT)
Prior art keywords
zeolite
water
pesticides
purification
alkyl
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/SE1999/001065
Other languages
English (en)
Inventor
Håkan ERIKSSON
Kåre LARSSON
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.)
ORDIO AB
Original Assignee
ORDIO AB
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 ORDIO AB filed Critical ORDIO AB
Priority to AU48141/99A priority Critical patent/AU4814199A/en
Publication of WO1999065826A1 publication Critical patent/WO1999065826A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B01J20/16—Alumino-silicates
    • B01J20/18—Synthetic zeolitic molecular sieves
    • B01J20/186—Chemical treatments in view of modifying the properties of the sieve, e.g. increasing the stability or the activity, also decreasing the activity

Definitions

  • the present invention relates to the field of water purification and more particularly to purifying water of pesticides and their decomposition products.
  • This pri- marily concerns water which should be free from pesticides to be used for human consumption (drinking water) or in food production (e.g. when feeding animals or as process water in the food industry) and which originates from water supplies polluted with pesticides.
  • the novel feature of the invention is the use of hydrophobic zeolites in this connection.
  • MAC maximum acceptable concentration
  • control agents for instance, Lindane, DDT, Dimethoate, Mecoprop, Triazines (Atrazine, Simazine, Terbutylazine etc) , Chlorotoluron, Isoproturon, 2,4-D, MCPA, Bentazon, Dichloroprop, Primi- carb, Dicambra, Dichlobenil and Malathion.
  • a great problem in removing these pesticides is due to the fact that the pesticides which occur as pollution in water supplies are present in very low concentrations in the water (however not sufficiently low for the above- mentioned purpose) , and therefore an agent which is to adsorb these substances must provide a very strong binding of the pesticides in question. Too low a binding strength results in the pesticides, which initially were adsorbed to the agent, being released and leaking out again to the water which is to be consumed. In other terms, great demands are put on agents for the purification of water for this purpose.
  • the present invention relates to an alternative to activated carbon as adsorbent for this purpose, namely hydrophobic zeolites. Besides constituting an alternative in this application, the zeolites have also been found to yield important advantages compared to activated carbon, which will be described in more detail below.
  • Zeolites which can be generally defined as alu- minium silicates with spatial-reticular structure, are, of course, known per se, and as an example of literature on zeolites mention can be made of Breck, D.W. (1974) Zeolite Molecular Sieves, Wiley, New York.
  • hydrophobic (ultrastable) zeolites is also generally known per se, the degree of hydrophobicity being defined by the ratio of Si/Al, wherein hydrophobic zeolites have a high silicon content and thus few structural charge carriers.
  • hydrophobic zeolites as adsorbents for certain specific substances is also previously known.
  • US-patent specification 5,108,617 discloses the adsorption of detergents to hydrophobic zeolites
  • WO 97/15391 discloses the adsorption of preservatives, such as phenol and cresol , from protein solutions.
  • the zeolite used therein has been dealuminised m a completely different way than the zeolite used according to the present invention, namely by a special S ⁇ Cl 4 treatment, which results m a product having a completely different structure and thus entirely different qualities.
  • the present invention generally relates to a method for purifying water of pesticides and their decomposition products using a zeolite.
  • the great field of application m this connection is water from water supplies, which are polluted with control agents, i.e. pesticides of different kind, and m which the water should be free from pesticides to be used for human consumption or m food production (when feeding animals or as process water m the food industry) .
  • the method is characterised by carrying out the purification with a view to removing pesticides having a Log P value (distribution coefficient m a two-phase system of octanol-water) which is > 1.5, contacting the water with a hydrophobic zeolite which has the composition [ (A10 2 ) x (S ⁇ 0 2 ) y ] , wherein x and y are integers and y/x >15, and which is directly synthesised as a hydrophobic zeolite or obtained by treating the corre- spondmg hydrophilic zeolite m cationic form, m particular m alkali metal form, preferably Na form, by means of at least two sequences of ion exchange-calcination for conversion to a hydrophobic zeolite, and carrying out the purification until a total concentration of pesticides present m the water of not more than 0.5 ⁇ g/1.
  • zeolites As indicated above and as will be described below m more detail, a special type of hydrophobic zeolites has thus been found to be usable for the adsorption of pesticides having complex ring structures and often branches, i.e. very bulky compounds, and at a very high degree of binding kinetics.
  • the very high degree of binding kinetics allows the water flow which is to be purified to keep a very high flow rate compared to the adsorbent which is currently used m practice, i.e. activated carbon, which, of course, presents great advantages.
  • activated carbon i.e. activated carbon
  • zeolites are inert materials resistant to heat up to about 1100°C. This enables the binding capacity of the zeolites to be easily regenerated by heating, so that a combustion of the material which has been adsorbed to the zeolite takes place.
  • the high binding capacity m respect of pesticides as well as the binding rate and the possibility of easy regeneration of the binding capacity make these zeolites unique m the adsorption of pesticides m water.
  • the zeolites used are generally of the type which corresponds to the composition [ (A10 2 ) x (S ⁇ 0 2 ) y ] , wherein x and y are integers and y/x >15, preferably >100, more preferably >200 and often >1000.
  • hydrophobic zeolites of the above kind are preferably selected from the group consisting of silicalite, mordenite and zeolite Y.
  • the usability of the zeolites is limited by the size and accessibility of the pores in the zeolite crystals, silicalite and zeolite Y having three-dimensional pore systems, which are highly accessible, whereas the pore system m mordenite is one-dimensional and thus somewhat less accessible.
  • both mordenite and zeolite Y belong to the zeolites having the greatest pore diameters, that is ⁇ 7.5 A and s7 A, respectively, wnereas silicalite has pore diameters (two different types of pores) of ⁇ 5.5 A.
  • zeolite Y is, however, m most cases particularly preferred.
  • zeolites contain a certain amount of water molecules.
  • hydrophobic zeolites are prepared by modification of synthetically derived hydrophilic zeolites, from which a great or a small portion of the Al molecules has been removed to render the zeolite hydrophobic.
  • Zeolites having a great portion of silicon or silicon dioxide have strong hydrophobic capacities and they are stable m water-based systems within a wide pH range and also insensitive to oxidising and reducing agents. Furthermore, they resist high pressures and high tempera- tures without changing.
  • the zeolite used m the method according to the present invention can be described as follows.
  • hydrophilic zeolite m alkali metal form preferably Na form. It appears from that mentioned above that it is a common method to remove a great or a small portion of Al molecules from synthetically prepared hydrophilic zeolites. The important thing in this case is, however, to treat the nydrophilic zeolite, which is present m alkali metal form, by means of a series or a sequence of ion change and calcination opera- tions so as to obtain the hydrophobic zeolite.
  • the preparation involves at least two sequences of ion exchange and calci- nation, preferably two or three, .e. two or three ion- exchange operations and two and three calcination operations, respectively, the sequences generally ending with a calcination.
  • the ion exchange thus usually comprises ammonium- ion exchange and the last ion-exchange step is generally carried out with the aid of an acid to convert the zeolite to the H form.
  • the last calcination is preferably performed at a temperature exceeding 600°C, more preferably exceeding 700°C and most preferably m the range of 700°C-1000°C, m particular 700°C-850°C.
  • the preceding calcination step(-s) is/are generally carried out at a lower temperature than the final calcination, for instance, m the range of 500°C-700°C, such as 500°C-600°C.
  • Sodium zeolite Y hydrophilic
  • an ammonium ion e.g. ammonium sulfate
  • a level exceeding 50% e.g. 80% (equivalents NH 4 + /total cationic equivalents).
  • the zeolite which has been ammonium-ion exchanged and contains sodium residues is heated to at least 500°C, e.g. 540°C (about 3 h) , which results m a material corresponding to a regular decationised zeolite.
  • the calcinated zeolite from step 2 is treated once more with ammonium ions (e.g. ammonium sulfate), e.g. at about 100°C, for further reduction of the cationic content m question.
  • ammonium ions e.g. ammonium sulfate
  • the zeolite from step 3 is calcinated at a temperature in the range of 700°C-850°C, e.g. acout 815°C for 3 h.
  • the hydrophobic zeolite used m the method according to the invention can, however, also oe obtained by direct synthesismg of a hydrophobic zeolite, i.e. without any intermediate dealummisation from a hydrophilic zeolite. Methods for such direct synthesis are also known per se and can be used for the preparation of a hydrophobic zeolite having qualities or characteristics similar to those of the above-mentioned ultrastable or superstable zeolite.
  • GB 1,117,568 thus discloses direct synthesis of a hydrophobic zeolite and details of the preparation thereof as well as such a zeolite can be retrieved from said specification.
  • the zeo- lite is generally thermally stable up to 1000°C, which, for instance, can be proved by means of X-ray powder diffraction studies and/or adsorption measuring. Further- more, it preferably contains less than 1 % by weight alkali metal (m particular Na) , and more preferably less than 0.5 % by weight .
  • the zeolite can be used as such or in the form of sintered zeolite crystals or m the form of crystals contained or suspended m non- zeolitic material.
  • it can be deposited on or otherwise suitably combined with one or more, preferably permeable, non- zeolitic materials.
  • a usable non-zeolitic material mention can be made of agarose .
  • the method according to the invention can m general be carried out batchwise as well as continuously or semi- contmuously .
  • the hydropho- bic zeolite is added directly to the solution which is to be purified, while another alternative is represented by the case m which the hydrophobic zeolite is put or packed into a column or a filter or formed to a column or a filter, through which the aqueous solution which is to be purified is allowed to pass
  • Different specific applications can, of course, be used, but they should not need any further presentation, as they can be retrieved from prior-art technique known per se .
  • zeolites used cannot, of course, adsorb infinite amounts of pesticides, and, if action is not taken, they will eventually leak them out.
  • a preferred embodiment of the method according to the invention involves heating of the zeolite, after the desired degree of purification, or even during the purification, to a temperature exceeding 700°C, more preferably exceeding 850°C and most preferably in the range of 900-1100°C. If possible risks of chemical contamination and biological infection are to be eliminated as well, it is also possible to carry out the corresponding heating by pre-treating the zeolite involved.
  • Another alternative m connection with regenera- tion concerns the treatment of the zeolite with so-called supercritical carbon dioxide, where the supercritical carbon dioxide functions as a solvent and elution agent, the eluted substances being reusable.
  • the method according to the m- vention is m particular intended for the purification of water having very low concentrations of pesticides.
  • the purification is often to be carried out on water containing not more than 10 ⁇ g/1 of the pesticide wnich is to be exposed to purification.
  • the mven- tion it has been found that it is possible to carry out a purification until a very low concentration of said pesticides, which means that the purification is performed until the total concentration of pesticides present in the water is not more than 0.5 ⁇ g/1.
  • Each one of the pesticides is also preferably subjected to purification until not more than 0.1 ⁇ g/1.
  • the method according to the invention it is, as previously suggested, possible to use a great water flow m the contact between the water and the zeolite, i.e. a short time of contact, which is preferably in the range of about ten seconds and up to 20-30 minutes or even less, such as 10 seconds-15 minutes or more preferably 20 seconds-10 minutes. Satisfactory results can often be obtained even m the range of 10 seconds- 2 minutes .
  • the amount of zeolite used m relation to the volume of water which is to be purified varies with the specific pesticide which is to be removed and should thus be de- termmed by the one skilled m the art for each individual case.
  • m the method use is generally made of 1 kg zeolite per 100 litres of water or more, preferably 1 kg zeolite per 1000 litres of water or more, and more preferably 1 kg zeolite per 10,000 litres of water or more.
  • the adsorption to the zeolite is stronger when the pesticide is non-ionised.
  • This can, for instance, be achieved by adjusting or regulating the pH value of the aqueous solution, so that it is preferably m the range of 1-9, and more preferably 2-9.
  • the pH can be adjusted to a value m the range of 1-3. In other words, this adjustment is carried out if needed, i.e. if the pH initially deviates from the desired pH and/or if the pesticide contains said lonisable group (or groups) .
  • the term pesticide is used in connection with the invention m a conventional sense, i.e.
  • the term refers to a substance or a mixture of substances intended to prevent, fight, repel or alleviate the effect of an mfestant (injurious animal, harmful insect, harmful plant etc) .
  • an mfestant injurious animal, harmful insect, harmful plant etc.
  • the term includes, for instance, herbicides, insecticides, fungicides, biocides, algicides etc.
  • the method is, however, advantageously used for purifying water of primarily herbicides, insecticides and fungicides, m particular herbicides and insecticides.
  • the method according to the invention m particular allows removal of heterocyclic, preferably heteroaromatic, pesticides having 1,2 or 3 N atoms in the ring and a molecular weight of >200, in particular in the range of 200-300, or aromatic compounds having a molecular weight of >200, in particular in the range of 200-300.
  • Another group of pesticides which are removable with the aid of the method are alicyclic compounds, in particular halogen(e.g. Cl) -substituted, and with a molecular weight of >200, such as 200-300.
  • interesting pesticides can be defined according to any one of the following general formulae :
  • R ⁇ is halogen, preferably Cl ,
  • R 2 is H or -NH- (Ci -Ce -alkyl ) and R 3 is H or -NH- (Cx-Cg- alkyl )
  • R 4 is H or halogen (preferably Cl ) ,
  • R 5 is H , halogen (preferably Cl ) or C ⁇ -C 5 - alkyl ,
  • R 6 is H or Ci-Cg- alkyl
  • R 7 is H or Ci-Cg-alkyl wherein: R 8 is H or halogen (preferably Cl) R 9 is H, halogen (preferably Cl) or
  • C ⁇ -C 6 -alkyl and Rio is H or C ⁇ -C 6 -alkyl.
  • halogen is, as mentioned above, represented by fluorine, chlorine and iodine
  • C ⁇ -C 6 - alkyl is a straight or branched alkyl group having 1-6 carbon atoms, i.e. methyl,' etyl , propyl , butyl, pentyl and hexyl (propyl up to hexyl also include normal, iso, sec and tert groups) .
  • R 4 , R 5/ R 8 and R 9 can also be present in any free position in the benzene ring.
  • EXAMPLE 1 The herbicide terbutylazine was solubilised in pure water in a concentration of 1 mg/1 (lppm) .
  • the terbutylazine solution was filtrated through a column containing 1 g USY particles of a size of 63-125 ⁇ m at a flow rate of 240 ml/h.
  • USY "Ultra Stable Zeolite Y” from the Japanese company Tosoh, i.e. in accordance with the invention.
  • the concentration of terbutylazine in the filtrate emanating from the column was determined by adsorption at 225 nm, the results being presented in Fig. 1.
  • the flow rate used in this example yielded a residence time in the column of 30 s, which was sufficient for the adsorption of the specified amount of terbutylazine under the detection level .
  • the herbicide terbutylazine in an amount of 10 mg/1 in pure water was incubated with different amounts of USY or activated carbon (CarboTech, Pool) for 15 minutes and 120 minutes, the results being shown in Fig. 2.
  • the adsorption capacity of the zeolites depends on the binding strength between the zeolite and the pesti- cide, and this example illustrates the binding strength m the form of the affinity constant between a zeolite and a few pesticides (herbicides) wnich have all been reported as pollutants m groundwater.
  • a zeolite filter would thus adsorb these pesticides with the same satis- factory efficiency as m the case of atrazine m Example 3.
  • a 20 ppm aqueous solution of atrazine was pumped through a filter consisting of 30 mg zeolite particles
  • EXAMPLE 6 The experiments in Example 5 were repeated but with a 100 ppm aqueous solution of 2 , 6-dichlorobenzamide solution. Also in this case, the time of contact was 5 s. The absorbency of the remaining 2 , 6-dichlorobenzamide content was measured at 220 nm. The results are shown in Fig. 4 and again the extraordinary binding kinetics of the zeolite according to the invention are confirmed.

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Analytical Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Water Treatment By Sorption (AREA)
  • Treatment Of Water By Ion Exchange (AREA)

Abstract

La présente invention concerne un procédé de purification d'eau contenant des pesticides ainsi que des produits de décomposition de ces derniers, et plus particulièrement d'eau destinée à être utilisée pour l'alimentation humaine ou dans la production d'aliments. Le procédé consiste à effectuer la purification en vue d'éliminer les pesticides ayant une valeur Log P (coefficient de distribution dans un système à deux phases octanol-eau) qui est > 1,5, à mettre en contact l'eau avec une zéolite hydrophobe représentée par la composition [(AlO2)x(SiO2)y], dans laquelle x et y représentent des entiers et x/y ⊃15, qui est directement synthétisée sous forme de zéolite hydrophobe ou obtenue par le biais du traitement de la zéolite hydrophobe correspondante sous forme cationique, en particulier sous forme de métal alcalin, de préférence sous forme Na, au moyen d'au moins deux séquences de calcination par échange d'ions pour la transformer en zéolite hydrophobe, puis à effectuer la purification jusqu'à ce que la concentration totale des pesticides présents dans l'eau ne dépasse pas 0,5 νg/l.
PCT/SE1999/001065 1998-06-16 1999-06-15 Procede permettant de purifier de l'eau contenant des pesticides Ceased WO1999065826A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU48141/99A AU4814199A (en) 1998-06-16 1999-06-15 A method for purifying water of pesticides

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
SE9802140-5 1998-06-16
SE9802140A SE9802140D0 (sv) 1998-06-16 1998-06-16 Zeoliter för adsorption

Publications (1)

Publication Number Publication Date
WO1999065826A1 true WO1999065826A1 (fr) 1999-12-23

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PCT/SE1999/001065 Ceased WO1999065826A1 (fr) 1998-06-16 1999-06-15 Procede permettant de purifier de l'eau contenant des pesticides

Country Status (3)

Country Link
AU (1) AU4814199A (fr)
SE (1) SE9802140D0 (fr)
WO (1) WO1999065826A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003002461A1 (fr) * 2001-06-28 2003-01-09 Enitecnologie S.P.A. Procede se basant sur l'utilisation de zeolites pour le traitement d'eau contaminee
WO2005070534A1 (fr) * 2004-01-22 2005-08-04 Indian Institute Of Technology Composition adsorbante, dispositif et procede de decontamination des eaux renfermant des pesticides
WO2007048921A1 (fr) * 2005-10-28 2007-05-03 Agro Industrie Recherches Et Developpements A.R.D. Utilisation d'un biomatériau pour la dépollution de milieux contaminés
CN111377577A (zh) * 2019-12-18 2020-07-07 华北水利水电大学 一种农药生产用废水处理设备

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1987005592A1 (fr) * 1986-03-13 1987-09-24 Anox Aktiebolag Utilisation de zeolithes hydrophobes comme materiau d'adsorption dans la purification biologique d'eaux usees
US5108617A (en) * 1989-09-05 1992-04-28 Hakan Eriksson Method of using zeolites for adsorbing detergents
DE4327981A1 (de) * 1992-08-20 1994-02-24 Pall Corp Mischfilterbettzusammensetzung und Verwendungsverfahren
WO1995005239A1 (fr) * 1993-08-14 1995-02-23 Wilhelm Söndgen Gmbh Filtres pour eau et solutions aqueuses et procede de filtration approprie
WO1997015391A1 (fr) * 1995-10-24 1997-05-01 Sten Andersson Utilisation de zeolites hydrophobes, seringue et procede pour eliminer les conservateurs d'une solution de polypeptides

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1987005592A1 (fr) * 1986-03-13 1987-09-24 Anox Aktiebolag Utilisation de zeolithes hydrophobes comme materiau d'adsorption dans la purification biologique d'eaux usees
US5108617A (en) * 1989-09-05 1992-04-28 Hakan Eriksson Method of using zeolites for adsorbing detergents
DE4327981A1 (de) * 1992-08-20 1994-02-24 Pall Corp Mischfilterbettzusammensetzung und Verwendungsverfahren
WO1995005239A1 (fr) * 1993-08-14 1995-02-23 Wilhelm Söndgen Gmbh Filtres pour eau et solutions aqueuses et procede de filtration approprie
WO1997015391A1 (fr) * 1995-10-24 1997-05-01 Sten Andersson Utilisation de zeolites hydrophobes, seringue et procede pour eliminer les conservateurs d'une solution de polypeptides

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003002461A1 (fr) * 2001-06-28 2003-01-09 Enitecnologie S.P.A. Procede se basant sur l'utilisation de zeolites pour le traitement d'eau contaminee
AU2002352657B2 (en) * 2001-06-28 2008-01-03 Enitecnologie S.P.A Process based on the use of zeolites for the treatment of contaminated water
EA010694B1 (ru) * 2001-06-28 2008-10-30 ЭНИТЕКНОЛОДЖЕ С.п.А. Способ обработки загрязнённой воды, основанный на использовании цеолитов
WO2005070534A1 (fr) * 2004-01-22 2005-08-04 Indian Institute Of Technology Composition adsorbante, dispositif et procede de decontamination des eaux renfermant des pesticides
US7968493B2 (en) 2004-01-22 2011-06-28 Indian Institute Of Technology Method for the preparation of adsorption compositions including gold or silver nanoparticles
WO2007048921A1 (fr) * 2005-10-28 2007-05-03 Agro Industrie Recherches Et Developpements A.R.D. Utilisation d'un biomatériau pour la dépollution de milieux contaminés
FR2892645A1 (fr) * 2005-10-28 2007-05-04 Agro Ind Rech S Et Dev A R D S Utilisation d'un biomateriau pour la depollution de milieux contamines
CN111377577A (zh) * 2019-12-18 2020-07-07 华北水利水电大学 一种农药生产用废水处理设备

Also Published As

Publication number Publication date
SE9802140D0 (sv) 1998-06-16
AU4814199A (en) 2000-01-05

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