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WO2000037364A1 - Purification d'eau - Google Patents

Purification d'eau Download PDF

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Publication number
WO2000037364A1
WO2000037364A1 PCT/SE1999/002281 SE9902281W WO0037364A1 WO 2000037364 A1 WO2000037364 A1 WO 2000037364A1 SE 9902281 W SE9902281 W SE 9902281W WO 0037364 A1 WO0037364 A1 WO 0037364A1
Authority
WO
WIPO (PCT)
Prior art keywords
zeolite
phthalate
water
phthalates
esters
Prior art date
Application number
PCT/SE1999/002281
Other languages
English (en)
Inventor
Håkan ERIKSSON
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 AU20178/00A priority Critical patent/AU2017800A/en
Publication of WO2000037364A1 publication Critical patent/WO2000037364A1/fr

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Classifications

    • 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
    • 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

Definitions

  • the present invention relates to the field of water purification and, more particularly, to purifying water of phthalates.
  • This primarily concerns water which should be free from, or substantially free from, phthalates to be directly or indirectly used for human consumption, in food production or in pharmaceutical production.
  • the purification according to the invention is interesting when it is a matter of preventing water which contains phthalates from contaminating subsoil water.
  • the novel feature of the invention is the use of hydrophobic zeolites in this context.
  • Esters of phthalic acid are usually called phthalates and have been used as plasticizers in many plastics since the 1930s, as additives in lubricating oils, and in the cosmetics industry.
  • the use of phthalates and their relative stability against decomposition has resulted in phthalates being found as pollutants in the environment. Phthalates can often be detected in food, surface water, subsoil water and drinking-water (1) .
  • the phthalates consist of a great number of esters of phthalic acid. Some of these have an oestrogen-like ac- tivity (1, 2) and phthalates have turned out to have a cumulative effect on the oestrogen content of the body.
  • Silicalite and zeolite Y have three-dimensional pore systems, which are highly accessible whereas the pore system of mordenite is two-dimensional and thus less accessible.
  • both zeolite Y and mordenite belong to the group of zeolites having the greatest pore diameters, that is ⁇ 7 and -7.5 A, respectively, whereas silicalite has pore diameters (two different types of pore) of ⁇ 5.5 A (3) .
  • Hydrophobic zeolites have earlier also been used to adsorb certain specific organic compounds in water.
  • US-patent specification 5,108,617 discloses the adsorption of detergents on hydrophobic zeolites
  • WO 971 15391 the adsorption of, inter alia, phenol and m-cresol
  • PCT/SE99/01065 the adsorption of pesticides.
  • WO87/05592 discloses the adsorption of phenol
  • US-5,316,993 discloses the sintering of hydrophobic zeolites to greater particles and indicates the adsorption of certain organic compounds thereto, however not phtha- lates, and only compounds in gas phase.
  • 10140045 discloses the use of zeolites for the adsorption of hazardous substances, but even if dioctyl phthalate is given as an example of such a hazardous substance, this concerns adsorption in gas phase. Moreover, the zeolite is used together with activated carbon.
  • the invention is thus based on a new use of hydro- phobic zeolites, that is removing phthalates from water.
  • polluted subsoil water is involved, above all water to be used for human consumption, food production or in the pharmaceutical industry.
  • the use may occur according to prior-art principles, which generally means that the solution in question is contacted with the zeolite, such a quantity being used that the desired degree of adsorption of the phthalate on the zeolite is achieved.
  • the invention relates to a method for purifying water of phthalate, especially water polluted with phthalate and intended to be directly or indi- rectly used for human consumption, in food production or in pharmaceutical production or to prevent water that contains phthalates from contaminating subsoil water, characterised by contacting the water with such a quantity of hydrophobic zeolite that the desired degree of adsorption of the phthalate/phthalates is achieved.
  • the method according to the invention can generally be carried out batchwise as well as continuously or semi- continuously .
  • the hydrophobic zeolite is added directly to the solution, whereas another alternative is represented by the case where a column, filter or the like is filled with the hydrophobic zeolite, through which the solution to be purified is allowed to pass.
  • a variety of specific applications may, of course, be used, but they need not be described in more detail since they can be retrieved from the technique known per se . Phthalates are found in very low concentrations as pollutants in water and a zeolite which is to adsorb these substances must exhibit a very strong binding of the phthalates.
  • the zeolites cannot adsorb infi- nite quantities of phthalates, which results in, for instance, a zeolite filter finally also leaking phthalates.
  • the zeolites are inert materials resistant to heat up to 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 on the zeolite takes place.
  • the high binding capacity in respect of phthalates as well as the binding rate and the possibility of easy regeneration of the binding capacity make the hydrophobic zeolites unique materials in the adsorption of phthalates in water.
  • the used zeolite is generally of the type which corresponds to the composition [ ( I2O3) x (Si ⁇ 2) y] , wherein x and y are integers and y/x >15, preferably >100, more preferably >200 and often >1000.
  • hydrophobic (ultra-stable) zeolites of the stated type are preferably selected from the group consisting of silicalite, mordenite and zeolite Y. Taken together, zeolite Y is, however, in most cases particularly preferred. As for the rest, principles known per se apply to the zeolite.
  • zeolitic basic structure other atoms, such as B, P, Fe, Ga and Ge, may to a certain extent replace Al and Si in order to provide the zeolitic basic structure and they can thus also be used in the method according to the invention.
  • Zeolites having a high pro- portion of silicon have strongly hydrophobic properties and are stable in water-based systems in a wide pH range and, moreover, insensitive to oxidising and reducing agents. Furthermore, they resist high pressures and high temperatures without changing.
  • the zeolite can be used as such or in the form of sintered zeolite crystals or in the form of crystals contained or suspended in non-zeolitic materials. In addi- tion, it may be deposited on or otherwise combined with one or more, preferably permeable, non- zeolitic materials .
  • the zeolite cannot adsorb infinite quan- tities of phthalates. Since the zeolites can be heated, they are easy to regenerate, and a preferred embodiment of the invention means that after the desired degree of purification the zeolite is heated to a temperature exceeding 700°C, more preferably exceeding 850°C and most preferably in the range of 900-1100°C. If one also wishes to eliminate possible risks of chemical contamination and biological infection, the corresponding heating can also be carried out by pretreating the zeolite involved.
  • the hydrophobic (ultra-stable) zeolites Thanks to the high degree of binding strength and the high binding rate of phthalates to the hydrophobic (ultra-stable) zeolites, it is possible to use a great water flow in the contact between the water and the zeolite, i.e. a short time of contact, which is preferably in the range of several tens of seconds and up to 20-30 minutes or even less, such as 10 seconds-15 minutes or more preferably 20 seconds-10 minutes, for instance 10 seconds-2 minutes.
  • the contact between the zeolite and the water may take place either by adding the zeolite directly to the water to be purified or by attaching the zeolite to a surface or packing the zeolite in a column or a filter or forming the zeolite to a column or a filter, through which the water is allowed to pass.
  • the amount of zeolite used in relation to the volume of water which is to be purified varies with the specific phthalate which is to be removed and should thus be determined by those skilled in the art for each individual case.
  • use is gen- erally made of 1 kg zeolite per 1000 litres of water or more, preferably 1 kg zeolite per 10,000 litres of water or more, and more preferably 1 kg zeolite per 100,000 litres of water or more.
  • phthalates means monoesters and/or diesters of phthalic acid.
  • aliphatic esters are involved, for instance monoalkyl esters and/or dialkyl esters, but also aromatic esters, for example monoaryl esters and/or diaryl esters or monoalkylaryl esters and/or dialkylaryl esters, can be removed by the method according to the invention.
  • alkyl in the first place relates to alkyl (straight or branched) with 1-8 carbon atoms in the alkyl chain, whereas "aryl” usually relates to "benzyl” .
  • phthalates which in connection with the method according to the invention should bind satisfactorily to zeolites, mention can be made of, in particular, monoethylhexyl phthalate, dimethyl phthalate, dibutyl phthalate, dipentyl phthalate, dihexyl phthalate, diheptyl phthalate, diisopropyl phthalate, di- isobutyl phthalate, disecoctyl phthalate and butylbenzyl phthalate.
  • Each of the columns comprised 1 g hydrophobic zeolite Y particles (USY, 63 - 149 ⁇ m) .
  • a solution was pumped consisting of 10 mg phenol/L in pure water and through the other column 10 mg dibutyl phtha- late/L in pure water.
  • the solutions were pumped through both columns at a flow rate of 300 mL/h and the concentrations of phenol and dibutyl phthalate after the columns were determined by absorbencies at 276 nm and 230 nm, respectively.
  • Example 3 Dibutyl phthalate dissolved in pure water 10 mg/L was pumped through a column containing 1 g hydrophobic zeolite Y (USY particle size 63 - 149 ⁇ m) . The time of contact between the zeolite and the phthalate solution was 30 seconds and totally 34 L phthalate solution were pumped through the column without the phthalate being detected in the outflow from the column (detection by ab- sorbency at 230 nm) .
  • Examples 2 and 3 show that hydrophobic zeolites in a particularly efficient manner can adsorb one of the phthalates that have the highest solubility in water and that other phthalates which have a lower solubility in water and thus are more hydrophobic molecules should bind at least as efficiently to the zeolites. Furthermore, the adsorption of the phthalate on the zeolite in Examples 2 and 3 was considerably greater than what could be expected from the K a ff values presented in Example 1.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Water Treatment By Sorption (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne un procédé destiné à purifier l'eau du (des) phtalate(s) qu'elle contient, et consistant à utiliser une zéolithe hydrophobe, notamment une zéolithe dont la composition est la suivante [(Al2O3)x(SiO2)y], où x et y représentent des nombres entiers et sont supérieurs à 15, de préférence supérieurs à 100.
PCT/SE1999/002281 1998-12-09 1999-12-07 Purification d'eau WO2000037364A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU20178/00A AU2017800A (en) 1998-12-09 1999-12-07 Purification of water

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
SE9804029A SE9804029D0 (sv) 1998-12-09 1998-12-09 Adsorption av ftalater
SE9804029-8 1998-12-09

Publications (1)

Publication Number Publication Date
WO2000037364A1 true WO2000037364A1 (fr) 2000-06-29

Family

ID=20413399

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/SE1999/002281 WO2000037364A1 (fr) 1998-12-09 1999-12-07 Purification d'eau

Country Status (3)

Country Link
AU (1) AU2017800A (fr)
SE (1) SE9804029D0 (fr)
WO (1) WO2000037364A1 (fr)

Cited By (3)

* 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
WO2003040123A1 (fr) * 2001-11-07 2003-05-15 Biosilvio Munkfors Ab Emploi de zeolites comme matrices
CN103159276A (zh) * 2011-12-16 2013-06-19 中国科学院生态环境研究中心 采用疏水交联吸附树脂去除水溶液中三-（2,3-二溴丙基）异氰酸酯的方法

Citations (4)

* 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
US5316993A (en) * 1991-05-27 1994-05-31 Degussa Aktiengesellschaft Molded bodies containing dealuminated zeolite Y and the process for their production
SE505274C2 (sv) * 1995-10-24 1997-07-28 Sten Andersson Användning av en hydrofob zeolit för avlägsnande av för injektionslösningar i läkemedelssammanhang använda konserveringsmedel från en proteinlösning
JPH10140045A (ja) * 1996-11-06 1998-05-26 Lock Paint Kk 被塗物中の有害物質の放散防止に有効な塗料組成物

Patent Citations (4)

* 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
US5316993A (en) * 1991-05-27 1994-05-31 Degussa Aktiengesellschaft Molded bodies containing dealuminated zeolite Y and the process for their production
SE505274C2 (sv) * 1995-10-24 1997-07-28 Sten Andersson Användning av en hydrofob zeolit för avlägsnande av för injektionslösningar i läkemedelssammanhang använda konserveringsmedel från en proteinlösning
JPH10140045A (ja) * 1996-11-06 1998-05-26 Lock Paint Kk 被塗物中の有害物質の放散防止に有効な塗料組成物

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Week 9831, Derwent World Patents Index; AN 1998-357695 *
PATENT ABSTRACTS OF JAPAN *

Cited By (5)

* 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
WO2003040123A1 (fr) * 2001-11-07 2003-05-15 Biosilvio Munkfors Ab Emploi de zeolites comme matrices
CN103159276A (zh) * 2011-12-16 2013-06-19 中国科学院生态环境研究中心 采用疏水交联吸附树脂去除水溶液中三-（2,3-二溴丙基）异氰酸酯的方法

Also Published As

Publication number Publication date
AU2017800A (en) 2000-07-12
SE9804029D0 (sv) 1998-12-09

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