WO1989008092A1 - Removal of organic compounds from fluids - Google Patents

Removal of organic compounds from fluids Download PDF

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Publication number
WO1989008092A1
WO1989008092A1 PCT/AU1989/000079 AU8900079W WO8908092A1 WO 1989008092 A1 WO1989008092 A1 WO 1989008092A1 AU 8900079 W AU8900079 W AU 8900079W WO 8908092 A1 WO8908092 A1 WO 8908092A1
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Prior art keywords
compound
calixarene
aryl
solvated
calixarene compound
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PCT/AU1989/000079
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French (fr)
Inventor
Kevin Peter Wainwright
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The Flinders University Of South Australia
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Publication of WO1989008092A1 publication Critical patent/WO1989008092A1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C65/00—Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
    • C07C65/01—Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups containing hydroxy or O-metal groups
    • C07C65/17—Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups containing hydroxy or O-metal groups containing rings other than six-membered aromatic rings
    • 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
    • C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
    • 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
    • C02F1/68—Treatment of water, waste water, or sewage by addition of specified substances, e.g. trace elements, for ameliorating potable water
    • C02F1/683—Treatment of water, waste water, or sewage by addition of specified substances, e.g. trace elements, for ameliorating potable water by addition of complex-forming compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C39/00—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring
    • C07C39/12—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring polycyclic with no unsaturation outside the aromatic rings
    • C07C39/17—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring polycyclic with no unsaturation outside the aromatic rings containing other rings in addition to the six-membered aromatic rings, e.g. cyclohexylphenol

Definitions

  • This invention relates to the use of calixarenes for the removal of organic compounds from fluids and more particularly to the removal of polar hydrocarbons such as halogenated hydrocarbons from water supplies and gas streams.
  • the invention further relates to a method for the preparation of calixarenes in a form suitable for these purposes.
  • THMs enter the gaseous environment. Filtration through activated carbon also removes THMs, but because of the non-selective adsorbing properties of activated carbon its ability to remove THMs is rapidly suppressed, as filtration proceeds, by the unwanted adsorption of other harmless organic molecules. Accordingly, none of these techniques provides a satisfactory solution to the problem.
  • the approach adopted in accordance with the present invention is to use chemical compounds which are cheap to synthesise, which may be adsorbed onto a solid support, which are water insoluble and stable, and which have the ability to selectively remove THMs both from water as it filters through a bed of the material or is stirred with it, and from a gas stream containing THMs as it passes through a bed containing the material.
  • a process using such chemical compounds could be carried out at major public water treatment plants and/or at the point of consumption by supplying the material for incorporation into domestic water purification systems. It could also be used for the removal of organic compounds, particularly THMs, from industrial influent and effluent water and gas streams.
  • the present invention therefore provides a process for recovering THMs and other organic compounds from industrial processes.
  • a method for the removal of organic com ⁇ ound(s), particularly polar hydrocarbons such as halogenated hydrocarbons, from a fluid such as water or a gas stream which comprises the step of contacting the fluid containing the organic compound(s) with a non-solvated calixarene compound, and subsequently recovering the purified fluid or the organic compound(s) .
  • the non-solvated calixarene compound is adsorbed onto or bound to a solid support when it is contacted with the fluid.
  • Calixarenes form a class of chemical compounds of the general formula (1) :
  • n 1-5;
  • R is H, alkyl, aryl, substituted alkyl or aryl, OH, NH 2/ COOH, or S0 3 H;
  • R' is H, alkyl, aryl, substituted alkyl or aryl, acetyl or SiMe 3 .
  • Preferred calixarene compounds for use in the present invention are compounds of general formula (1) where n is 3, and compounds where R' is H. Particularly preferred is para-t-butyl-calix[6]arene in non-solvated form.
  • the calixarene compounds have been described in the literature as their solvates, particularly their chloroform solvate 8 ' 9 . Generally, these solvates are highly stable and chloroform for example cannot be removed, even by heating under reduced pressure. The solvates probably form because the hydroxy or substituted hydroxy groups of the calixarene compound can hydrogen bond to a hydrocarbon bearing a polar group such as a halogen group.
  • a polar group such as a halogen group.
  • the calixarene compound is used in its non-solvated form, and the present invention also provides a method for the preparation of a calixarene compound in the non-solvated form.
  • This method is characterised in that the synthesis, isolation and purification of the calixarene compound are performed in a volatile, weakly binding solvent.
  • the solvent is one which has been purified to remove strongly binding contaminants, for example chloroform.
  • calixarene compounds have been obtained free from solvent, and in a highly active form.
  • a non-solvated calixarene compound can be prepared by the following procedure: a para-substituted phenol and para-formaldehyde are suspended in purified xylene and the mixture treated with an excess of a metal hydroxide and boiled in an inert atmosphere until the reaction is complete. The solid calixarene is then isolated by extraction with purified toluene as its toluene solvate, and converted into its unsolvated active form by heating under reduced pressure.
  • Preferred volatile, weakly binding solvents for use in the method of the present invention include xylene and toluene, however volatile solvents other than xylene and toluene that bind weakly to a calixarene compound can be used, for example benzene. These solvents can be removed from the calixarene compound without destroying its molecular structure, for example by heating under reduced pressure.
  • calixarene compound has a remarkable propensity for sequestering small organic molecules with high rates of reaction, yielding inclusion compounds of relatively high stability.
  • pure solid calixarene compounds when exposed to water containing trace amounts of trihalomethanes, either being stirred with the water or by having it filtered through the solid compound, were found not particularly effective at sequestering the trihalomethane molecules. This may be due to the hydrophobic nature of the calixarene which prevents effective mixing of the aqueous phase with the agglomerated solid and thus only a small percentage of calixarene molecules are exposed and available for THM -uptake.
  • the calixarene compound is preferably attached to a solid support.
  • a solid support is alumina or silica, however in these cases the capacity of the material to remove contaminants appears to decrease with the through-put of influent fluid.
  • the adsorbed form can be made by physical mixing of the two solids, or by evaporation of a solution, typically -in toluene or diethyl ether, containing the calixarene compound on the surface of the solid support, or by adsorption from a solution of the calixarene compound without removal of the solvent.
  • the calixarene compound could also be chemically bound to these and other solid supports, such as a water insoluble polymer or an ion exchange resin 10 11 .
  • Organic compounds which are contained in fluids such as water and gas streams and which may be removed in accordance with this invention include organic compounds having polar groups attached to the organic moiety. As previously described, these include polar hydrocarbons such as halogenated alkanes (particularly trihalo and/or tetrahalomethanes) , halogenated alkenes and halogenated aromatic compounds. Further features of the present invention, including the preparation of calixarene compounds in non-solvated form and their use in removal of halogenated hydrocarbons from contaminated water and gas streams, will be apparent from the following Examples which are included by way of illustration of the invention. EXAMPLE 1
  • THM uptake experiments were carried out on water from the public supply provided to Flinders University from Happy Valley Reservoir, South Australia. This source contains THMs at a total concentration of c.a. 200 ⁇ g/L. Analyses of water samples before and after exposure to non-solvated t-butyl-calix[6]arene were carried out under - the supervision of the staff of the State Water Laboratory of South Australia. (a) Using non-solvated t-butyl-calix[6]arene adsorbed on granular activated carbon.
  • Analysis of the effluent was carried out on samples taken at various points during the experiment. The THM concentrations found were compared with those for the influent. For the purpose of comparison a blank run using untreated Filtrasorb 400 was carried out in similar fashion.
  • a 0.5% (wt/wt) coating of non-solvated t-butyl- calix[6]arene on coarse sand was made by concentrating to dryness a suspension of each in diethyl ether. 15g of coated sand was dispersed in 50g of untreated sand and the mixture (50ml) transferred to a chromatography column. Contaminated water amounting to 200 bed volumes was then poured through the column at a flow rate which gave a retention time of one minute. Samples of the effluent were taken for analysis and the THM concentrations compared with those in the influent. The experimental results are graphed in Figure 4 which shows that reasonable THM uptake is maintained for about the first 40 bed volumes of water treated. Sand alone shows no THM uptake. (c) Using non-solvated t-butyl-calix[6]arene adsorbed on alumina.
  • Nitrogen gas saturated with chloroform was passed through a bed of non-solvated t-butyl-calix[6]arene.
  • ⁇ -H nuclear magnetic resonance analysis of the calixarene showed the appearance of a resonance consistent with the uptake, from the gas stream, of one molecule of chloroform per molecule of calixarene.

Abstract

A method for the removal of organic compound(s), particularly polar hydrocarbons such as halogenated hydrocarbons, comprises the step of contacting the fluid containing the organic compound(s) with a non-solvated calixarene compounds and subsequently recovering the purified fluid or the organic compound(s). Non-solvated calixarenes and a method for their preparation are disclosed, as well as compositions of non-solvated calixarenes on solid supports.

Description

REMOVAL OF ORGANIC COMPOUNDS FROM FLUIDS
This invention relates to the use of calixarenes for the removal of organic compounds from fluids and more particularly to the removal of polar hydrocarbons such as halogenated hydrocarbons from water supplies and gas streams. The invention further relates to a method for the preparation of calixarenes in a form suitable for these purposes.
Good water quality is generally important both for domestic use and in industry where water is either used or released back into the environment. The chlorination of water supplies for the purpose of improving their microbiological quality has been practised since 1908. However, in 1974, it was discovered that an undesirable side reaction occurs within a chlorinated supply through reaction of the chlorine with naturally occurring humic and fulvic acids 1 2 that results in the formation of trihalomethanes (THMs). As a consequence of this, chloroform and if, bromide ions are present, dichlorobromomethane, chlorodibromomethane and bromoform, are frequently encountered contaminants in water supplies
5 for use in the home and in industry.
Laboratory experiments have shown that in rats and mice chloroform is carcinogenic and suggest that this is probably the case in humans as well 3. In recognition of this, a total THM limit of 100 μg/L has been set in the
10 U.S.A.,4 and the World Health Organisation has recommended a limit of 30μg/L for chloroform.5 In several parts of the world analysis of drinking water supplies has shown levels of THMs far in excess of these recommended limits . For example, in South Australia over a six year
1.5 period to December 1983, total THM levels averaged 258 μg/L with the average chloroform level being 95 μg/L. One sample analysed in this period was found to contain 1122 μg/L of THMs of which 755 μg/L was chloroform.7
In order to reduce the total THM level in water
20 supplies several techniques have been considered.7
Alternative disinfectants are available, but in general these are either too' expensive (for example, ozone), have even more dubious side effects than chlorine (for example, chlorine dioxide) , or are less effective as disinfectants
25 (for example chloramine) . Thus none is a completely satisfactory substitute. Methods for removing the organic precursor material have been considered - flocculation with alum is the most successful, but this approach only lowers the ultimate THM concentration by about 40%.
30 Removal of the THMs after formation by aerating the water has been investigated and can be quite effective if the aerating facility is large enough, particularly for chloroform, the most volatile of the THMs. One shortcoming of this approach is that the aerated water
35 must not be re-chlorinated and consequently it is subject to microbiological growth between the aeration plant and consumption point. Another problem is that volatile THMs enter the gaseous environment. Filtration through activated carbon also removes THMs, but because of the non-selective adsorbing properties of activated carbon its ability to remove THMs is rapidly suppressed, as filtration proceeds, by the unwanted adsorption of other harmless organic molecules. Accordingly, none of these techniques provides a satisfactory solution to the problem. The approach adopted in accordance with the present invention is to use chemical compounds which are cheap to synthesise, which may be adsorbed onto a solid support, which are water insoluble and stable, and which have the ability to selectively remove THMs both from water as it filters through a bed of the material or is stirred with it, and from a gas stream containing THMs as it passes through a bed containing the material.
A process using such chemical compounds could be carried out at major public water treatment plants and/or at the point of consumption by supplying the material for incorporation into domestic water purification systems. It could also be used for the removal of organic compounds, particularly THMs, from industrial influent and effluent water and gas streams. The present invention therefore provides a process for recovering THMs and other organic compounds from industrial processes.
According to the present invention, there is provided a method for the removal of organic comρound(s), particularly polar hydrocarbons such as halogenated hydrocarbons, from a fluid such as water or a gas stream, which comprises the step of contacting the fluid containing the organic compound(s) with a non-solvated calixarene compound, and subsequently recovering the purified fluid or the organic compound(s) . Preferably, the non-solvated calixarene compound is adsorbed onto or bound to a solid support when it is contacted with the fluid.
Calixarenes form a class of chemical compounds of the general formula (1) :
Figure imgf000006_0001
wherein n is 1-5;
R is H, alkyl, aryl, substituted alkyl or aryl, OH, NH2/ COOH, or S03H; and
R' is H, alkyl, aryl, substituted alkyl or aryl, acetyl or SiMe3.
Preferred calixarene compounds for use in the present invention are compounds of general formula (1) where n is 3, and compounds where R' is H. Particularly preferred is para-t-butyl-calix[6]arene in non-solvated form.
The calixarene compounds have been described in the literature as their solvates, particularly their chloroform solvate 8'9. Generally, these solvates are highly stable and chloroform for example cannot be removed, even by heating under reduced pressure. The solvates probably form because the hydroxy or substituted hydroxy groups of the calixarene compound can hydrogen bond to a hydrocarbon bearing a polar group such as a halogen group. The ease of synthesis and favourable physical and chemical properties of the calixarene ring system has led to an examination of its . otential for removing polar hydrocarbons from water and other fluids. Further, the results from Ames tests which have been applied to some of these compounds suggest that they are non-mutagenic8.
In accordance with the present invention, the calixarene compound is used in its non-solvated form, and the present invention also provides a method for the preparation of a calixarene compound in the non-solvated form. This method is characterised in that the synthesis, isolation and purification of the calixarene compound are performed in a volatile, weakly binding solvent. Preferably, the solvent is one which has been purified to remove strongly binding contaminants, for example chloroform. In this aspect of the invention, calixarene compounds have been obtained free from solvent, and in a highly active form.
Methods for the synthesis of solvated calixarene compounds are known in the art. In one embodiment of the present invention, a non-solvated calixarene compound can be prepared by the following procedure: a para-substituted phenol and para-formaldehyde are suspended in purified xylene and the mixture treated with an excess of a metal hydroxide and boiled in an inert atmosphere until the reaction is complete. The solid calixarene is then isolated by extraction with purified toluene as its toluene solvate, and converted into its unsolvated active form by heating under reduced pressure. Preferred volatile, weakly binding solvents for use in the method of the present invention include xylene and toluene, however volatile solvents other than xylene and toluene that bind weakly to a calixarene compound can be used, for example benzene. These solvents can be removed from the calixarene compound without destroying its molecular structure, for example by heating under reduced pressure.
It has been discovered that a solution of a calixarene compound has a remarkable propensity for sequestering small organic molecules with high rates of reaction, yielding inclusion compounds of relatively high stability. In contrast, pure solid calixarene compounds when exposed to water containing trace amounts of trihalomethanes, either being stirred with the water or by having it filtered through the solid compound, were found not particularly effective at sequestering the trihalomethane molecules. This may be due to the hydrophobic nature of the calixarene which prevents effective mixing of the aqueous phase with the agglomerated solid and thus only a small percentage of calixarene molecules are exposed and available for THM -uptake.
In order to obtain high reactivity in a solid phase, which is more convenient to use and will maintain separation between the calixarene compound and the fluid being purified, the calixarene compound is preferably attached to a solid support. By way of example, when the calixarene compound is adsorbed onto the surface of a granular activated carbon, this is a very effective material for removing halogenated hydrocarbons from water. This is also true when the solid support is alumina or silica, however in these cases the capacity of the material to remove contaminants appears to decrease with the through-put of influent fluid. The adsorbed form can be made by physical mixing of the two solids, or by evaporation of a solution, typically -in toluene or diethyl ether, containing the calixarene compound on the surface of the solid support, or by adsorption from a solution of the calixarene compound without removal of the solvent. The calixarene compound could also be chemically bound to these and other solid supports, such as a water insoluble polymer or an ion exchange resin 10 11. THM uptake experiments utilising water contaminated with either chloroform, dichlorobromomethane, chloro- dibromomethane or bromoform at a total concentration of c.a 200 μG/L, and using retention times comparable to those in filtration beds of major water treatment plants (less than c.a. 7 minutes), have shown that removal of THMs is consistently effective when the calixarene compound is in the adsorbed form. By comparison, the effectiveness of untreated carbon in removing THMs declines with the volume of water passed through the filtration bed.
Organic compounds which are contained in fluids such as water and gas streams and which may be removed in accordance with this invention include organic compounds having polar groups attached to the organic moiety. As previously described, these include polar hydrocarbons such as halogenated alkanes (particularly trihalo and/or tetrahalomethanes) , halogenated alkenes and halogenated aromatic compounds. Further features of the present invention, including the preparation of calixarene compounds in non-solvated form and their use in removal of halogenated hydrocarbons from contaminated water and gas streams, will be apparent from the following Examples which are included by way of illustration of the invention. EXAMPLE 1
Preparation of 5.11.17,23 ,29.35-Hexa-tert-butyl -37. 38.39.40,41,42-hexahydroxy-cali rβlarene (hereafter referred to as "t-butyl-calixr6larene"-formula (1), R=tBu. R'=H, n=3) in its non-solvated form
p-Tert-butylphenol (1 mol) and paraformaldehyde (2 mol) were suspended in p-xylene. Excess rubidium hydroxide was added and the mixture heated and stirred at its boiling point for 4 h under an inert atmosphere. The reaction mixture was then cooled and the precipitated solid collected. The solid was washed with p-xylene and then suspended in toluene and shaken with 1 M HCϋ. The toluene layer was separated and a second extraction carried out with further toluene. The toluene extracts were combined, washed with water and then dried over MgS04. Removal of the solvent by distillation followed by drying in vacuo (0.1 mm) at 100°C for 48 h gave the pure product (52%) free of any included solvent. Analysis: Calcd. for
C66H8406: C, 81.44; H, 8.70. Found: C, 81.40; H, 8.40. 13C NMR (CD2CJt2) δ 147.0, 144.2, 126.8, 125.8, 33.7, 32.4, 30.9.
EXAMPLE 2
Removal of THM Contaminants from water
THM uptake experiments were carried out on water from the public supply provided to Flinders University from Happy Valley Reservoir, South Australia. This source contains THMs at a total concentration of c.a. 200 μg/L. Analyses of water samples before and after exposure to non-solvated t-butyl-calix[6]arene were carried out under - the supervision of the staff of the State Water Laboratory of South Australia. (a) Using non-solvated t-butyl-calix[6]arene adsorbed on granular activated carbon. A 1% (wt/wt) coating of non-solvated t-butyl-calix[6]arene on Filtrasorb 400 (10 ml) (supplied by Calgon Carbon Corp.) was made by shaking the two solids together for two minutes. The coated Filtrasorb 400 was placed in a chromatography column (2x40cm) between beds of coarse sand (5cm depth). Contaminated water, amounting to 1000 bed volumes was then passed through the bed at a flow rate corresponding to a retention time of 12 seconds. Analysis of the effluent was carried out on samples taken at various points during the experiment. The THM concentrations found were compared with those for the influent. For the purpose of comparison a blank run using untreated Filtrasorb 400 was carried out in similar fashion.
The experimental results for three different THMs are summarised in Figures 1-3 in which the ability of granular activated carbon treated with non-solvated t-butyl-calix[6]- arene to retain its THM removing properties, over that shown by untreated granular activated carbons, is clearly seen, (b) Using non-solvated t-butyl-calix[6]arene adsorbed on silica.
A 0.5% (wt/wt) coating of non-solvated t-butyl- calix[6]arene on coarse sand was made by concentrating to dryness a suspension of each in diethyl ether. 15g of coated sand was dispersed in 50g of untreated sand and the mixture (50ml) transferred to a chromatography column. Contaminated water amounting to 200 bed volumes was then poured through the column at a flow rate which gave a retention time of one minute. Samples of the effluent were taken for analysis and the THM concentrations compared with those in the influent. The experimental results are graphed in Figure 4 which shows that reasonable THM uptake is maintained for about the first 40 bed volumes of water treated. Sand alone shows no THM uptake. (c) Using non-solvated t-butyl-calix[6]arene adsorbed on alumina.
Results obtained are similar to those described for silica in (b) above, under similar conditions.
EXAMPLE 3
Removal of THM Contaminants from a Gas Stream.
Nitrogen gas saturated with chloroform was passed through a bed of non-solvated t-butyl-calix[6]arene. ^-H nuclear magnetic resonance analysis of the calixarene showed the appearance of a resonance consistent with the uptake, from the gas stream, of one molecule of chloroform per molecule of calixarene.
REFERENCES:
1. Rook, J.J., Water Treat.Exam. (1974), 2_3_: 234.
2. Bellar, T.A. , Lichtenberg, J.J. and Kroner, R.C. J.Amer.Water Works Assoc. (1974), 66:703.
3. "Drinking Water and Health", National Academy of Sciences, Washington, DC, 1977.
4. "National Interim Primary Drinking Water Regulations: Control of Trihalomethanes in Drinking Water", Federal Register, Nov. (1979), 44:68624.
5. "Guidelines for Drinking-water Quality. Vol.l", "Recommendations", World Health Organisation, Geneva, (1984), 77.
6. Nicholson, B.C., Hayes, K.P., and Bursill, D.B. Water (1984) , 11:11.
7. Bursill, D., Morran, J. and Nicholson, B., "Trihalomethanes in South Australian Water Supplies", Engineering and Water Supply βepartment, Salisbury, South Australia, (1985).
8. Gutsche, c.D. Topics in Current Chem. (1984), 123:1.
9. Gutsche, CD., Dhawan, B., No, K.M. and Mathurkrishnan, R. J.Amer.Chem.Soc. (1981), 103 : 3782. 10. Dudler, V., Lindoy, L.F., Sallin, D. and Schlaepfer, C.W. Aust.J.Chem. (1987), 4_Q_:1557.
11. Smid, J. , and Sinta, R. Topics in Current Chem. (1984), 121:105.

Claims

CLAIMS :
1. A method for the removal of organic compound(s) from a fluid, which comprises the step of contacting the fluid containing the organic compound(s) with a non-solvated calixarene compound, and subsequently recovering the purified fluid or the organic compound(s) .
2. A method according to claim 1, wherein the organic compound(s) are polar hydrocarbons.
3. A method according to claim 2, wherein the organic compound(s) are halogenated hydrocarbons.
4. A method according to any of claims 1 to 3, wherein the non-solvated calixarene compound is adsorbed onto or bound to a solid support.
5. A method according to claim 4 wherein the solid support is selected from granular activated carbon, alumina and silica.
6. A method according to claim 4 or claim 5 wherein the fluid is passed through a bed of said calixarene compound adsorbed onto or bound to said solid support.
7. A method according to any of claims 1 to 6 wherein the calixarene compound is a compound of the general formula (1) :
Figure imgf000016_0001
wherein n is 1-5;
R is H, alkyl, aryl, substituted alkyl or aryl, OH, NH2/ COOH, or S03H; and
R' is H, alkyl, aryl, substituted alkyl or aryl, acetyl or SiMe3, in non-solvated form.
8. A method according to claim 7 wherein said calixarene compound is a compound of general formula (1) in which n is 3.
9. A method according to claim 7 wherein said calixarene compound is a compound of general formula (1) in which R1 is H.
10. A method according to claim 7, wherein the calixarene compound is para-t-butyl-calix[6]arene in non-solvated form.
11. A method according to any of claims 1 to 10, wherein said fluid is water.
12. A method according to claim 11 wherein said water contains polar hydrocarbons.
13. A method according to claim 12 wherein said water contains halogenated hydrocarbons.
14. A method according to claim 13 wherein said water contains trihalomethanes and/or tetrahalomethanes.
15. A method according to any of claims 1 to 10, wherein said fluid is a gas stream.
16. A calixarene compound in non-solvated form.
17. A compound according to claim 16 of the general formula (1) :
Figure imgf000017_0001
wherein n is 1-5;
R is H, alkyl, aryl, substituted alkyl or aryl, OH, NH2 COOH, or SO3H; and R' is H, alkyl, aryl, substituted alkyl or aryl, ace yl or SiMβ3, in non-solvated form.
18. A compound according to claim 15 wherein n is 3.
19. A compound according to claim 15 wherein R' is H.
20. Para-t-butyl-calix[6]arene in non-solvated form.
21. A method for the preparation of a compound according to any of claims 16 to 20 in non-solvated form, characterised in that the synthesis, isolation and purification of the calixarene compound are performed in volatile, weakly binding solvent.
22. A method according to claim 21, wherein solvent used during synthesis of the calixarene compound is purified xylene.
23. A method according to claim 21 or claim 22, wherein the solvent used during isolation and/or purification of the calixarene compound is purified toluene.
24. A method according to any of claims 21 to 23, wherein the calixarene compound is converted to the non-solvated form by heating under reduced pressure.
25. A composition comprising a calixarene compound in non-solvated form adsorbed onto or bound to a solid support.
26. A composition according to claim 25 wherein the calixarene compound is a compound as defined in any of claims 17 to 20. 27. A composition according to claim 25 or claim 26, wherein the solid support is selected from granular activated carbon, alumina and silica.
27. A composition according to claim 25, comprising para-t-butyl-calix[6]arene adsorbed on a granular activated carbon support.
PCT/AU1989/000079 1988-02-29 1989-02-28 Removal of organic compounds from fluids WO1989008092A1 (en)

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EP0710675A2 (en) 1994-10-28 1996-05-08 Rohm And Haas Company Improved method for forming polymers
WO1997031698A1 (en) * 1996-02-28 1997-09-04 Transdiffusia S.A. Process for the recovery of volatile low molecular compounds
WO1997037995A1 (en) * 1996-04-05 1997-10-16 Board Of Regents, The University Of Texas System Calixpyrroles, calixpyridinopyrroles and calixpyridines
WO1998028228A1 (en) * 1996-12-24 1998-07-02 Osaka Gas Company Limited Trihalomethane adsorbent and process for producing the same
WO2003095405A1 (en) * 2002-05-09 2003-11-20 Board Of Curators Self-assembled calixarene-based guest-host assemblies for guest storage by van der waals confinement
DE10226099A1 (en) * 2002-06-12 2004-01-08 Jörg Martin Dipl.-Chem. Dormann Filter material for toxins, bacteria, viruses and other physiological pollutants
WO2004056708A1 (en) * 2002-12-19 2004-07-08 University Of Surrey Material for the removal of pollutants
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KR100707163B1 (en) 2005-10-12 2007-04-13 삼성에스디아이 주식회사 Solid acid, polymer electrolyte membrane comprising the same, and fuel cell employing the same
EP1980914A1 (en) 2007-04-10 2008-10-15 Xerox Corporation Chemical toner with covalently bonded release agent
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US8101240B2 (en) 2006-06-06 2012-01-24 Rohm And Haas Company Release coating and process
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EP0710675A2 (en) 1994-10-28 1996-05-08 Rohm And Haas Company Improved method for forming polymers
WO1997031698A1 (en) * 1996-02-28 1997-09-04 Transdiffusia S.A. Process for the recovery of volatile low molecular compounds
US6136071A (en) * 1996-02-28 2000-10-24 Transdiffusia S.A. Process for the recovery of volatile low molecular compounds
US7122572B2 (en) 1996-04-05 2006-10-17 Board Of Regents, University Of Texas System Calixpyrroles
WO1997037995A1 (en) * 1996-04-05 1997-10-16 Board Of Regents, The University Of Texas System Calixpyrroles, calixpyridinopyrroles and calixpyridines
US6262257B1 (en) 1996-04-05 2001-07-17 Board Of Regents, University Of Texas System Calixpyrroles, calixpyridinopyrroles and calixpyridines
US7041819B2 (en) 1996-04-05 2006-05-09 Board Of Regents, The University Of Texas System Halogenated calixpyrroles and uses thereof
WO1998028228A1 (en) * 1996-12-24 1998-07-02 Osaka Gas Company Limited Trihalomethane adsorbent and process for producing the same
WO2003095405A1 (en) * 2002-05-09 2003-11-20 Board Of Curators Self-assembled calixarene-based guest-host assemblies for guest storage by van der waals confinement
DE10226099A1 (en) * 2002-06-12 2004-01-08 Jörg Martin Dipl.-Chem. Dormann Filter material for toxins, bacteria, viruses and other physiological pollutants
WO2004056708A1 (en) * 2002-12-19 2004-07-08 University Of Surrey Material for the removal of pollutants
KR100707163B1 (en) 2005-10-12 2007-04-13 삼성에스디아이 주식회사 Solid acid, polymer electrolyte membrane comprising the same, and fuel cell employing the same
US7619032B2 (en) 2005-12-12 2009-11-17 Rohm And Haas Company Aqueous polymer dispersions with high unsaturated flow promoter content
US8101240B2 (en) 2006-06-06 2012-01-24 Rohm And Haas Company Release coating and process
EP1980914A1 (en) 2007-04-10 2008-10-15 Xerox Corporation Chemical toner with covalently bonded release agent
WO2009144419A1 (en) 2008-05-28 2009-12-03 Centre National De La Recherche Scientifique - Cnrs Method for selectively extracting membrane proteins using calixarenes
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