WO2005011836A1 - Processus de separation - Google Patents

Processus de separation Download PDF

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Publication number
WO2005011836A1
WO2005011836A1 PCT/GB2004/003276 GB2004003276W WO2005011836A1 WO 2005011836 A1 WO2005011836 A1 WO 2005011836A1 GB 2004003276 W GB2004003276 W GB 2004003276W WO 2005011836 A1 WO2005011836 A1 WO 2005011836A1
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Prior art keywords
cellulose
starch
surface area
polysaccharide material
separation
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PCT/GB2004/003276
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English (en)
Inventor
James Hanley Clark
Jeffrey James Edwin Hardy
Krzysztof Jakub Milkowski
Francesca Maria Kerton
Andrew John Hunt
Fabien Deswarte
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University Of York
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Publication of WO2005011836A1 publication Critical patent/WO2005011836A1/fr

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    • 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
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J20/28057—Surface area, e.g. B.E.T specific surface area
    • 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
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/26—Synthetic macromolecular compounds
    • B01J20/262—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon to carbon unsaturated bonds, e.g. obtained by polycondensation
    • 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
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
    • B01J20/28004—Sorbent size or size distribution, e.g. particle size
    • 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
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J20/28069—Pore volume, e.g. total pore volume, mesopore volume, micropore volume
    • 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
    • B01J20/281—Sorbents specially adapted for preparative, analytical or investigative chromatography
    • B01J20/282—Porous sorbents
    • B01J20/285—Porous sorbents based on polymers
    • 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
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/50—Aspects relating to the use of sorbent or filter aid materials
    • B01J2220/54—Sorbents specially adapted for analytical or investigative chromatography

Definitions

  • the invention relates to a method of separating chemical compounds using high surface area polysaccharides.
  • One broad class of such methods relies on the individual compounds in a mixture having differing interactions with a separation material.
  • chromatography relies upon the differing interactions of compounds in a mixture to be separated with a stationary material or stationary phase as they are transported past that material in a stream of gas or liquid (the mobile phase).
  • Other methods of the class involve selective adsorption of particular compounds onto a separation media from a mixture, followed by release of the adsorbed compounds in response to a change in conditions, for example, to selectively remove certain gases from a mixed gas stream.
  • Silica and alumina are well known for use as stationary phases in column and thin-layer chromatography. Cellulose is also used in the chromatographic separation of certain types of compounds. Other materials are also known for use in chromatography but there remains a need for new stationary phase materials having improved properties. For example, there is a need for stationary phases which can separate with a similar efficiency as known materials such as silica but using less polar mobile phases, thereby reducing the need to use polar solvents which are often less environmentally acceptable, are more difficult to evaporate and are more expensive than solvents of lower polarity, such as the hydrocarbons.
  • Cellulose and starch are biopolymers produced by plants.
  • Cellulose is a linear polymer of D-glucose with ⁇ -linkages
  • starch is composed of a mixture of amylose and amylopectin, which have ⁇ -linkages and the latter is also branched. While the chemical composition of cellulose is largely independent of its plant source, the ratio of amylose to amylopectin in starch varies with the origin. Both polymers are non-toxic, naturally abundant and biodegradable and as such represent a vital renewable resource for sustainable development. Some polysaccharides have been used as stationary phases in chromatography.
  • cellulose has found application in chromatography for the separation of particular types of compounds and there is a range of celluloses commercially available for use in chromatography. Starches have been used to a much more limited extent and there remains a need for improved materials for use in separations.
  • the invention provides a method of separation in which compounds are separated on the basis of their interactions with a polysaccharide material having a surface area of at least 20m 2 /g.
  • polysaccharide materials having a surface area of at least 20m 2 /g referred to herein as high surface area or expanded polysaccharides
  • high surface area or expanded polysaccharides gives much improved separation efficiency as compared to some known commercially available chromatography grade celluloses.
  • the polysaccharide materials have been found to be effective at separating a variety of types of compound.
  • the method of the invention therefore permits a range of separations to be carried out using polysaccharide materials prepared from materials originally derived from natural sources.
  • the polysaccharide materials have, in general, been found to have surfaces of lower polarity than the silica commonly used in column chromatography. Accordingly, when used as stationary phases in chromatographic separations, it is often possible to use solvents of lower polarity than would be required if silica were used.
  • the compounds in the mixture may, for example, adsorb onto the surface of the polysaccharide material with differing affinities, thereby making it possible to separate the compounds, for example, by chromatography or by controlled adsorption and desorption.
  • a mixture of compounds to be separated is brought into contact with the polysaccharide material and the compounds are then separated, for example, by elution in the case of chromatography or by controlled desorption from the polysaccharide material.
  • the separated compounds may then be detected and/or collected, as desired.
  • the method of the invention is applicable to a broad range of separation and controlled absorption-release technologies.
  • the method of the invention is especially suitable for chromatography, for example, column chromatography or thin-layer chromatography, in which the polysaccharide materials are used as a stationary phase.
  • the method is a method of chromatography in which the mobile phase is a liquid.
  • the chromatographic method will include the steps of bringing a mixture of compounds to be separated into contact with the polysaccharide material, and eluting with a suitable eluent or eluents. The separated compounds by then be detected and/or collected, as desired.
  • the polysaccharide materials tend to decompose when exposed to high temperatures, for example, above 150°C, in air for prolonged periods of time and so are not suitable for use in separation techniques involving temperatures above the decomposition temperature of the polysaccharide, for example, high temperature gas chromatography.
  • Solvents which swell the polysaccharide material to a significant degree for example, water, dimethylsulfoxide and dimethylacetamide, should not be used in the separation method of the invention or should be used only in amounts that do not cause significant swelling.
  • any polysaccharide material having the required surface area may be used in the method of the invention.
  • Starch and cellulose are favoured materials due to their ready availability in a range of forms and their favourable properties.
  • Native starches and celluloses, in general, have surface areas of only several m 2 /g.
  • Starches and celluloses therefore, in general, need to be treated to increase their surface area to make them suitable for use in the invention.
  • the polysaccharide material will typically have a low water content, for example, a water content of less than 15% by weight.
  • the polysaccharide material is a starch.
  • High surface area starches have been found to be more stable upon storage for extended periods than high surface area cellulose.
  • the starch is a retrograded starch having an amylose content of at least 20%, more preferably at least 30% and most preferably at least 60% by weight. It has been found that the higher amylose starches generally give higher surface area materials after treatment than the lower amylose starches and retrograde more rapidly. Moreover, it was noted that, irrespective of the surface area, greater amounts of amylose in the starch tend to give better separation efficiency.
  • the starch is a corn starch, a potato starch, a wheat starch or a rice starch.
  • the starch may be a corn starch.
  • the starch may be a modified starch.
  • Modified starches may be readily prepared by methods known to persons skilled in the art (the word 'modified' as used herein means chemically modified to add substituent groups onto the polysaccharide polymer unless another meaning is clear from the context) and starches having a wide range of modifications are commercially available from, for example, National Starch and Chemical Corporation for use in applications such as food.
  • the starch is not modified.
  • the starch may be modified or unmodified.
  • One suitable method for preparing high surface area starches for use in the method of the invention involves the steps of i) gelatinising the starch in the presence of water to give a starch/water gel, ii) allowing the starch to retrograde; and iii) exchanging the water in the retrograded starch gel with a water-miscible non-solvent for starch which has a lower surface tension than water, such as ethanol.
  • the method may further involve exchanging the water- miscible non-solvent with one or a series of non-solvents or mixtures thereof with progressively lower surface tensions whereby the subsequent non-solvent or mixture thereof is miscible with the prior non-solvent or mixture thereof.
  • the high surface area polysaccharide is a starch obtainable by that method.
  • the method also includes the step of removing the low surface tension non-solvent, for example, by evaporation (typically under reduced pressure) or supercritical drying to leave the high surface area starch.
  • the starch is kept as a slurry in the non-solvent.
  • the polysaccharide material is a cellulose.
  • High surface area cellulose suitable for use in the method of the invention is obtainable by a method involving the steps of i) swelling the cellulose in a suitable liquid; and ii) exchanging that suitable liquid with a miscible non-solvent for cellulose which has a lower surface tension than the liquid.
  • the method may further involve exchanging the miscible non-solvent with one or a series of non-solvents or mixtures thereof.
  • the high surface area polysaccharide is a cellulose obtainable by the method.
  • the swelling liquid can be a single solvent a mixture of solvents or a solution and the conditions of step i) should be such as to swell the cellulose without dissolving it. Heating the cellulose in water, for example, at 140°C for 40 hours, has been found to swell the cellulose in a suitable way. Microwave heating has been found to give similar results in less time than conventional heating.
  • the cellulose can be swollen by sonicating the cellulose suspension in the swelling liquid with ultrasound at a room or an elevated temperature.
  • the non-solvent (or mixture thereof) for cellulose should, in general, be miscible with the swelling liquid and is advantageously volatile, so that it is easily removed from the cellulose by evaporation.
  • the method may also include the step of drying the cellulose to remove the non-solvent.
  • the cellulose may be kept as a slurry in the non-solvent.
  • the non-solvents used in the above-described methods of preparing high surface area starch and cellulose may be single liquids, mixtures of liquids or supercritical fluids.
  • the cellulose used in the treatment may be of any type but is preferably microgranular cellulose or fibrous cellulose. After treatment to increase the surface area, it has been found that the initial microgranular or fibrous structure is substantially retained.
  • the high surface area cellulose may be in the form of non-spherical particles.
  • the storage stability of cross-linked high surface area polysaccharides may be superior to that of an equivalent non-crosslinked high surface area polysaccharide and therefore methods in which the polysaccharide is cross-linked are preferred in some instances.
  • the polysaccharide material may be a modified polysaccharide but is preferably non-modified and, most preferably, has never been modified.
  • the high surface area polysaccharide material for use in the method of the invention has a surface area of at least 20m 2 /g, preferably at least 30m 2 /g, more preferably at least 50m 2 /g and most preferably at least 75m 2 /g.
  • the polysaccharide optionally has a surface area in the range of from 20m 2 /g to 500m 2 /g. All surface areas mentioned herein refer to surface area as measured by B.E.T.
  • the high surface area polysaccharide materials prepared by the methods mentioned above have been found to have surfaces of higher polarity than the original starches and celluloses.
  • the high surface area polysaccharide may have a polarity of greater than 0.55, preferably greater than 0.60.
  • the polysaccharide material has a pore volume of greater than 0.1cm 3 /g, more preferably greater than 0.2cm 3 /g and most preferably greater than 0.4cm 3 /g.
  • the pore volume distribution of the polysaccharide material also influences the efficiency of separation in a chromatographic method.
  • the polysaccharide material will have a narrow pore volume distribution, for example, in the range of from 0.05 to 1.5 ml/g.
  • Short- term exposure of the polysaccharide material to moisture present in the atmosphere can often improve the efficiency of separation by narrowing the pore volume distribution.
  • prolonged exposure or exposure to highly humid atmosphere leads to gradual decrease in porosity which progressively reduces the performance of the polysaccharide materials in chromatography and eventually leads to a complete collapse of the expanded structure and essentially total loss of separation ability.
  • the high surface area polysaccharide should therefore generally be stored in dry conditions, for example, in a dry atmosphere or vacuum sealed or under a hydrophobic liquid.
  • the inventors have found that high surface area starches are more resistant to degradation by moisture than high surface celluloses.
  • the polysaccharide material may be in any form appropriate for the particular method of separation. For column chromatography, the polysaccharide material is preferably in the form of particles having an average diameter in the range of 1 to 500 micrometers ( ⁇ m).
  • the polysaccharide materials tend to form aggregates on storage and it may therefore be advantageous to break up those aggregates, for example, by sonication for a short period of time, prior to use.
  • the polysaccharide material is a stationary phase.
  • the stationary phase consists essentially of the polysaccharide material.
  • the stationary phase may comprise at least 50% by weight, more preferably at least 90% by weight and most preferably at least 95% by weight of the polysaccharide material.
  • the invention also provides a method of chromatography in which the stationary phase comprises a polysaccharide having a surface area of at least 20m 2 /g.
  • the invention also provides the use of a polysaccharide material having a surface area of at least 20m 2 /g for the separation of chemical compounds.
  • the invention also provides a separation apparatus including a separation element which comprises a polysaccharide material having a surface area of at least 20m 2 /g.
  • a separation apparatus including a separation element which comprises a polysaccharide material having a surface area of at least 20m 2 /g.
  • the separation apparatus may be, for example, a chromatography apparatus such as a column chromatography apparatus or a HPLC apparatus.
  • the apparatus may be suitable for use in the method of the invention.
  • the invention also provides a separation element for use in the separation apparatus, the separation element comprising a polysaccharide material having a surface area of at least 20m 2 /g.
  • the separation element may be, for example, a pre-packed chromatography column or a thin-layer chromatography plate. Examples
  • Figure 1 is collection of scanning electron micrograms showing the structure of unexpanded starch (top left) and cellulose (top right) and structural changes that are the result of the expansion.
  • Figure 2 is a comparison between four charts showing GC responses in arbitrary units on the y-axis against fraction numbers on the x-axis for a column chromatography separation of ferrocene, acetylferrocene and diacetylferrocene using expanded com (upper middle chart) and rice starch (lower middle chart) as the stationary phase in comparison to an unexpanded com starch (top chart) and a silica (bottom chart).
  • Figure 3 shows the comparison in performance for the separation of ferrocenes between corn starches having different amylose contents and different surface areas (the top chart is high amylose expanded com starch, the middle chart is expanded normal com starch and the bottom chart is expanded waxy com starch).
  • Figure 4 illustrates the results of separation of natural waxes on a starch packed column (lower chart) compared to one packed with silica (upper chart).
  • Figure 6 shows the separation ability in the ferrocene system for celluloses prepared by different methods as well as native cellulose (from top to bottom the charts are for unexpanded cellulose, ethanol exchanged expanded cellulose, multisolvent hexane exchanged expanded cellulose and multisolvent supercritical CO 2 exchanged expanded cellulose).
  • waxy com starch (Sigma-Aldrich Ltd.) prepared as for example 1 are shown in table 1 and compared to the unexpanded material in table 2.
  • Table 1 Properties of starches prepared as for examples 1-5.
  • Example 6 High amylose com starch (Hylon Nib National Starch and Chemical Ltd.) was suspended in distilled water (ratio lg starch : 20mL water) and placed in a sealed vessel and heated at 130°C for 48hrs. The resultant gel was allowed to retrograde at 5°C for two days. A solvent exchange and drying was performed as for example 1 and the resultant material had the properties shown in table 3.
  • Table 3 Properties of expanded high amylose co starch compared to native high amylose corn starch.
  • Example 7 A 20 cm long and 1cm in diameter glass column was packed with the expanded starches prepared as for examples 1-6 and used to separate a 30mg (1/1/1 w/w/w) mixture of ferrocene, acetylferrocene and diacetylferrocene in 0.5mL of hexane/dichloromethane (3/2 v/v). The columns were eluted initially with hexane (6 portions of 5mL) then a 95/5%) hexane/acetone mixture (9 portions of 5mL) and finally acetone (7 portions of 5mL). 23 fractions were collected and analyzed by GC.
  • a 10cm column filled with corn starch prepared as for example 1 and packed as for example 7 was used to separate a lOOmg mixture of ethyl benzoate (EB) and diethyl phthalate (DEP) (1/1 w/w).
  • EB ethyl benzoate
  • DEP diethyl phthalate
  • the mixture was eluted with 100 % hexane, yielding five hexane fractions, of which, the first contained EB, and fractions 2-5 contained DEP. Both components were eluted with hexane with no need for an increase in the polarity of the eluent.
  • a glass column prepared as for example 7 was used to separate natural pigments extracted from spinach (Horowitz, G., J. Chem. Educ. 11, 263-4, 2000).
  • 2.5g frozen spinach J. Sainsbury Pic
  • the ethanol was removed by filtration and the dehydrated spinach added to 20mL hexane.
  • the solution was stirred for 5 minutes after which the hexane was decanted and concentrated to lmL. This extract was applied to the column.
  • Natural waxes can be obtained from plant or animal sources. Lanolin was used as a model complex mixture of waxy compounds. Chromatographic separation using expanded starch gave separations comparable to those obtained using silica. The following solvent system was used for both starch and silica: 3 times the column volume of hexane
  • a glass column prepared as for example 7 was used to separate limonene and carvone from spearmint oil. lOOmg of the spearmint essential oil (Natural by Nature Oils Ltd.) in 2 ml of hexane was applied to the column. The column was eluted with hexane (5mL portions) until limonene had ceased to elute and then carvone was eluted using ethyl acetate . Fractions were collected and analyzed by GC For starch limonene eluted in fractions 3-5 and carvone in fractions 6-9, but for silica 11 fractions were needed whereby limonene eluted in fractions 6-8 and carvone in fractions 10-11.
  • a glass column packed with the native com starch was used to separate ferrocenes as for example 7. Similar separations were carried out for the unexpanded wheat, potato, rice and com starches. The native starch materials did not separate the components in the ferrocene system.
  • a sample of expanded com starch (surface area 133.4 m 2 /g) as in example 1 was sieved and surface areas recorded by BET nitrogen absorption with the following results shown in Table 4.
  • the starch was made up principally of agglomerates of particles.
  • Table 4 Surface areas of particle size fractions of expanded com starch.
  • Corn starch expanded as for example 1 was stored in a dessicator under vacuum with silica gel desiccant for at least 10 months with no loss in surface area or change in polarity.
  • chromatographic grade cellulose Three different types of chromatographic grade cellulose were used as purchased (Sigma- Aldrich): microgranular, fibrous long and fibrous medium.
  • the cellulose is initially swollen by heating in a sealed thick glass jar in water at 140°C for a period of at least 40hrs with initial concentration of cellulose to water between 5-8 weight percent. The mixture is then allowed to cool to a minimum of 80°C and it is then equilibrated successively with 25, 50, 75 and 100% ethanol and then washed again 3 times with 100% ethanol. The cellulose is then filtered by gravity filtration until most of the solvent is removed but the solid remains as wet slurry. This slurry is then dried under vacuum at 50°C for at least 12 hrs. Material properties are summarised in Table 5. The effect of expansion on the structure of the cellulose is shown in Figure 1. Table 5: Properties of expanded cellulose
  • the ethanol from the equilibrated cellulose described in example 20 can also be removed by equilibrating with liquid carbon dioxide.
  • Such equilibrated solid can be dried by supercritical point drying with very slow release of the pressure to obtain a surface area measured by BET of up to 200m 2 /g.
  • Material properties are summarised in Table 6.
  • Table 6 Properties of cellulose exchanged with supercritical CO 2 and dried under supercritical conditions.
  • Example 20 Variation of the method - microwave heating
  • microwave heating can dramatically reduce the period of heating necessary to swell cellulose. Typically lOmin at full power (300W) is sufficient to aid swelling.
  • the material can then be solvent equilibrated and dried in any of the above-described ways.
  • the resultant materials have the same physical properties as materials heated by conventional methods and treated as in examples 17-19.
  • the cellulose as described in example 17 is swollen by suspending it in a 50% aqueous ethanol and sonicating for 3hrs at room temperature.
  • the material can then be solvent equilibrated and dried in any of the above-described ways.
  • the resulting material has a surface area of 65m /g and is structurally substantially the same as the above-described materials.
  • Example 22 Separation of ferrocene, acetylferrocene and diacetylferrocene Ferrocene, acetylferrocene and diacetylferrocene were used as purchased (Aldrich). A slurry of expanded cellulose in hexane was used to prepare a chromatographic column. 30 mg of a mixture of the three components (1/1/1 w/w/w), dissolved in 0.5 mL of hexane/dichloromethane (3/2 v/v) was loaded onto a ⁇ 16 cm by 1 cm expanded cellulose column.
  • expanded cellulose such as expanded microgranular prepared as in example 20 (SA-120 m 2 /g, 5g onto a 16 cm by 1 cm column) and expanded fibrous long (SA ⁇ 75m 2 /g, 4 g onto a 17 cm by 1 cm column), expanded fibrous medium (SA ⁇ 60m 2 /g, 4 g onto a 18 cm by 1 cm column) and expanded microgranular (SA ⁇ 65m/g, 4 g onto a 11 cm by 1 cm column) prepared as in example 19. All expanded materials gave good separation for the ferrocene system. Separations for microgranular cellulose prepared by methods described in examples 17-19 are compared to native material in Figure 6.
  • expanded cellulose behaves in a similar way to high surface area expanded starch.
  • Example 23 Separation of ethyl benzoate and diethyl phthalate
  • Ethyl benzoate and diethyl phthalate were used as purchased (Aldrich).
  • a 5 g slurry of expanded microgranular cellulose in hexane (prepared following the solvent exchange method as explained in example 20, SA ⁇ 120m 2 /g) was used to prepare a chromatographic column.
  • a lOOmg mixture of the components (1/1 w/w) was placed on top of a ⁇ 16 cm by 1cm expanded cellulose column. The mixture was eluted with 40 mL hexane/diethyl ether (95/5 v/v) and 30 mL diethyl ether successively. 12 fractions of 5 mL each were collected and analyzed by GC.
  • Ethyl benzoate is collected in fractions 4 and 5 and diethyl phthalate is eluted with diethyl ether and collected in fractions from 8 to 12 . This separation is similar to that obtained with silica as described in example 8 for starch.
  • Example 24 Separation of natural pigments
  • Example 25 Separation of limonene and carvone
  • Spearmint oil was used as purchased as a natural mixture of limonene and carvone.
  • a 5 g slurry of expanded microgranular cellulose in hexane (prepared following the solvent exchange method as explained in example 19, SA ⁇ 120m 2 /g) was used to prepare a chromatographic column.
  • 100 mg of spearmint oil was dissolved in 1 mL hexane and loaded onto a -15 cm by 1 cm column. The column was eluted with 25 mL hexane until limonene had ceased to elute and then carvone was eluted using ethyl acetate (35 mL). 11 fractions were collected .
  • Limonene came in fractions 3 and 4 and carvone eluted from fraction 5 tol 1, while for silica limonene was detected in fraction 6-8 and carvone in fractions 10-11.
  • Example 26 Degraded cellulose material
  • Expanded cellulose degrades in a humid environment.
  • a column packed with partially degraded microgranular cellulose of BET surface area of 45m 2 /g prepared according to example 19 and treated by exposure to a moist atmosphere was used for the separation of ferrocene, acetylferrocene and diacetylferrocene.
  • the separation of components works very well even at surface areas of below 50m 2 /g. Results are shown in Figure 7 and are compared with essentially collapsed material.
  • Example 27 Normal Cellulose (unexpanded)
  • Unexpanded cellulose was tested for column chromatography in order to compare it with the expanded one.
  • Three types of chromatography grade cellulose i.e. microgranular, fibrous long and fibrous medium (Sigma-Aldrich) were used in the ferrocene system. All the unexpanded materials gave poor separations.

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  • Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)

Abstract

L'invention concerne un procédé pour séparer des composés chimiques, selon lequel les composés sont séparés sur la base de leurs interactions avec une matière polysaccharide présentant une surface active d'au moins 20m2/g. Ladite matière polysaccharide peut être, par exemple, de l'amidon sur la cellulose. Ledit procédé peut être un procédé de chromatographie.
PCT/GB2004/003276 2003-07-29 2004-07-29 Processus de separation WO2005011836A1 (fr)

Applications Claiming Priority (2)

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GB0317752A GB0317752D0 (en) 2003-07-29 2003-07-29 Expanded biomaterials for adsorption and separation processes
GB0317752.4 2003-07-29

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US20080300557A1 (en) * 2005-12-09 2008-12-04 Sca Hygiene Products Ab Absorbent Product
WO2009046492A1 (fr) * 2007-10-10 2009-04-16 Lang Technologies Pty Limited Procédé de récupération de composés bioactifs
CN103331150A (zh) * 2013-07-12 2013-10-02 中国科学院地理科学与资源研究所 一种交联淀粉固相萃取柱及其制备方法和应用
US8790548B2 (en) 2006-03-15 2014-07-29 University Of York Carbonaceous materials
CN104155392A (zh) * 2014-08-15 2014-11-19 广州衡创测试技术服务有限公司 一种鞋和鞋材中邻苯二甲酸酯的检测方法
CN104897837A (zh) * 2015-06-08 2015-09-09 辽宁华润本溪三药有限公司 一种治疗气滞胃痛的药物制剂的检测方法
CN105223284A (zh) * 2014-12-29 2016-01-06 上海万香日化有限公司 留兰香油的快速气相色谱分析方法
US9457338B2 (en) 2007-09-19 2016-10-04 The University Of York Polysaccharide derived materials
GB202011442D0 (en) 2020-07-23 2020-09-09 Univ York Isolation of cannabinoids using mesoporous materials
WO2022024754A1 (fr) * 2020-07-27 2022-02-03 国立大学法人大阪大学 Procédé de préparation de particule fine

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US20080300557A1 (en) * 2005-12-09 2008-12-04 Sca Hygiene Products Ab Absorbent Product
US8790548B2 (en) 2006-03-15 2014-07-29 University Of York Carbonaceous materials
US9457338B2 (en) 2007-09-19 2016-10-04 The University Of York Polysaccharide derived materials
US8735573B2 (en) 2007-10-10 2014-05-27 Langtech International Pty Ltd. Method to recover bioactive compounds
WO2009046492A1 (fr) * 2007-10-10 2009-04-16 Lang Technologies Pty Limited Procédé de récupération de composés bioactifs
CN103331150A (zh) * 2013-07-12 2013-10-02 中国科学院地理科学与资源研究所 一种交联淀粉固相萃取柱及其制备方法和应用
CN104155392A (zh) * 2014-08-15 2014-11-19 广州衡创测试技术服务有限公司 一种鞋和鞋材中邻苯二甲酸酯的检测方法
CN105223284A (zh) * 2014-12-29 2016-01-06 上海万香日化有限公司 留兰香油的快速气相色谱分析方法
CN104897837A (zh) * 2015-06-08 2015-09-09 辽宁华润本溪三药有限公司 一种治疗气滞胃痛的药物制剂的检测方法
GB202011442D0 (en) 2020-07-23 2020-09-09 Univ York Isolation of cannabinoids using mesoporous materials
WO2022018451A1 (fr) 2020-07-23 2022-01-27 University Of York Isolement de cannabinoïdes à l'aide de matériaux mésoporeux
WO2022024754A1 (fr) * 2020-07-27 2022-02-03 国立大学法人大阪大学 Procédé de préparation de particule fine

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