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WO2017021883A1 - Système analytique à base de fibres de carbone - Google Patents

Système analytique à base de fibres de carbone Download PDF

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Publication number
WO2017021883A1
WO2017021883A1 PCT/IB2016/054644 IB2016054644W WO2017021883A1 WO 2017021883 A1 WO2017021883 A1 WO 2017021883A1 IB 2016054644 W IB2016054644 W IB 2016054644W WO 2017021883 A1 WO2017021883 A1 WO 2017021883A1
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Prior art keywords
carbon fibers
analytes
sampling
tube
tangled
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Ettore GUERRIERO
Carlo CRESCENZI
Paolo Benedetti
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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
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
    • 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
    • B01J20/28014—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 form
    • B01J20/28023—Fibres or filaments
    • 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
    • B01J20/28014—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 form
    • B01J20/28042—Shaped bodies; Monolithic structures
    • 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
    • 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
    • B01J20/286—Phases chemically bonded to a substrate, e.g. to silica or to 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
    • B01J20/3242—Layers with a functional group, e.g. an affinity material, a ligand, a reactant or a complexing group
    • B01J20/3244—Non-macromolecular compounds
    • B01J20/3246—Non-macromolecular compounds having a well defined chemical structure
    • 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
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
    • B01J20/3242—Layers with a functional group, e.g. an affinity material, a ligand, a reactant or a complexing group
    • B01J20/3244—Non-macromolecular compounds
    • B01J20/3246—Non-macromolecular compounds having a well defined chemical structure
    • B01J20/3248—Non-macromolecular compounds having a well defined chemical structure the functional group or the linking, spacer or anchoring group as a whole comprising at least one type of heteroatom selected from a nitrogen, oxygen or sulfur, these atoms not being part of the carrier as such
    • 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
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
    • B01J20/3242—Layers with a functional group, e.g. an affinity material, a ligand, a reactant or a complexing group
    • B01J20/3268—Macromolecular compounds
    • B01J20/3272—Polymers obtained by reactions otherwise than involving only carbon to carbon unsaturated bonds
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N1/00—Sampling; Preparing specimens for investigation
    • G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
    • G01N1/40—Concentrating samples
    • G01N1/405—Concentrating samples by adsorption or absorption

Definitions

  • the present invention refers to the field of analytic chromatography and more in particular to a stationary phase made of a bundle of carbon fibers to be used in analysis of samples and/or analytes in vapor and/or gaseous phase, making use of sampling devices packed with said solid phase.
  • the stationary phase of the present invention trapping and concentrating samples and/or analytes in gaseous and/or vapor phase can be used for analytic applications because the analytes/samples can be easily removed to undergo to further separation and analysis.
  • Volatile organic compounds are compounds present in the vapor phase at room temperature, defined as vapor pressure greater than 0.1 (0.0133 kPa) at 25°C (T.J. Kelly, R. Mukund, S.M. Gordon, M.J. Hays, W.A. Mc Clenny, Ambient Measurement Methods and Properties of the 189 Title III Hazardous Air Pollutants, Final Report, Contract No. 68-D0-0007, US Environmental Protection Agency, Research Triangle Park, NC, March 1994) .
  • Compounds less volatile are defined as semi- volatile organic compounds (SVOCs) which may be present in the atmosphere in the vapor phase, but are more normally associated with aerosol, either as dusts or liquid droplets.
  • VOCs are trapped from the air, for example to clean the air, for the recovery of waste anesthetic gases in found in many hospital surgeries.
  • measurement of VOCs and SVOCs in air is necessary for many reasons, for example for determining the sources and transport mechanisms of pollution, for health effects studies, and to determine compliance with regulated limits (M. Harper, Methods of characterizing sorbents for air sampling purposes, in: M. Suzuki (Ed. ) , Fundamentals of Adsorption: Proc. IVth Int. Conf. on Fundamentals of Measure Adsorption, Kyoto, 17-22 May 1992, Kodansha Press Com Japan, 1993, p. 267) .
  • Measurement of analytes requires three main steps: trapping, recovery and analysis.
  • Analytes are extracted from air by absorption or reaction with a sorbent surface (Standard Test Method for Flow Rate of Personal Sampling Pumps, American Society for Testing and Materials, Standard D 5337-97, ASTM, West Conshohocken, PA, 1997) .
  • the process of trapping can be carry out assisted by a pumping system which force the fluids through a sorbent material (active sampling) or driven by the diffusion of the analytes in a specific device (passive sampling) (Gorecki T, Namiesnik J (2002) TrAC - Trends Anal. Chem. 21:276-291) .
  • sorbents are classified as to their method of trapping: physical adsorption and chemical adsorption. Sorbents may also be classified as to the mechanism of recovering analytes: solvent desorption or thermal desorption.
  • the analyte trapped on the sorbent in order to be further analyzed should be desorbed from the sorbent.
  • a liquid solvent being suitable for injection into chromatography is used (L.D. White, D.G. Taylor, P.A. Mauer, R.E. Kupel, Am. Ind. Hyg. Assoc. J. 31 (1970) 225) .
  • Solvent should not interfere with the detection of analytes and at the same time must be capable of stripping the analytes from the sorbent with high degree of efficiency and reproducibility (E.R. Kennedy, T.J. Fischbach, R. Song, P.M. Eller, S.A. Shulman, Guidelines for Air Sampling and Analytical Method Development and Evaluation, DHHS (NIOSH) Publication No. 95-117, 1995) .
  • Carbon disulfide is used for non-polar compounds and hydrocarbons (F.H. Reid, W.R. Halpin, Am. Ind. Hyg. Assoc. J.
  • Polar compounds are desorbed by using polar solvents, water or polar co-solvents added to carbon disulfide
  • polar solvents, water or polar co-solvents added to carbon disulfide are also known isopropanol, butanol, amyl and hexyl alcohols, dimethylformamide either alone or in combination with carbon disulfide, mixture of methylene chloride-methanol , mixture of dimethyl sulfoxide (DMSO) and carbon disulfide (P.V. Langvardt, R.G. Melcher, Am. Ind. Hyg. Assoc. J. 40 (1979) 1006; Q. Gong, K.L. Demerjian, J. Air Waste Manage. Assoc. 45 (1995) 490; J. Kenny, G. Stratton, Am.
  • Porous charcoal from plants is the commonest sorbent: nut shell charcoals are used because they are hard and non- friable, and possess an original porosity very suitable for activation; coconut shells and olive pits are also used. Their drawbacks are existence of a residual inorganic ash content, enhanced water uptake.
  • charcoals based on petroleum or by-products of the petroleum industry are used because contain less inorganic material and can be fashioned into a charcoal with reproducible properties.
  • charcoals made from coal there are less used (L.D. White, D.G. Taylor, P.A. Mauer, R.E. Kupel, Am. Ind. Hyg. Assoc. J. 31 (1970) 225; F.H. Reid, W.R. Halpin, Am. Ind. Hyg. Assoc. J. 29 (1968) 390; F.X. Mueller, J.A. Miller, Am. Ind. Hyg. Assoc. J. 40 (1979) 380; E.J. Otterson, C.U.
  • Carboxens are sorbents manufactured from the partial to full carbonization of porous polymers, they are not inert at the high temperatures used in thermal desorption (W.R. Betz, S.G. Maroldo, G.D. Wachob, M.C. Firth, Am. Ind. Hyg. Assoc. J. 50
  • sorbents made of micro-porous poly-styrenes , which absorb no significant water and exhibit inert surfaces to reactive molecules.
  • carbon molecular sieves that have very high capacity for small, volatile molecules but unfortunately retain also water.
  • the adsorbed molecules are held very tightly a solvent with a high heat of adsorption is required for displacement and recovery (M.Harper, J. Chromatography A, 885 (2000) 129-151.)
  • Thermal desorption allows the release of analytes from sorbents by heating and is used for pre-concentration of low- concentration analytes before detection and analysis, especially ex-situ detection in GC columns.
  • sorbents used for solvent desorption are not suitable for thermal desorption because have high surface activity leading to sample degradation at high temperature.
  • examples of sorbents for thermal desorption are semi-crystalline polymer manufactured from diphenyl-p-phenylene oxide (DPPO) and polystyrene cross-linked polymers, graphitized carbons, carbon molecular sieves and multi-beads thereof. It is well-known in the art that sampling of semi volatile organic compounds can be complex and may need more than one sampling device because, due to their nature and molecular weight, they are distributed between the particulate matter
  • PM and the vapor phase and this distribution is not constant and depends on several factors.
  • double sampling device are usually used, made of filters to sample the particulate matter followed by sorbents for the vapor phase.
  • PM filters are usually made of quartz, Teflon or paper while the vapor phase is sampled for example on polyurethane foam
  • PAF polymers such as styrene/divinylbenzene (XAD) or 2,6- diphenylene oxide (tenax) .
  • Sampled volume, sampling flow and sampling time depend on the class of the analytes and on the sampling site, as for example an open area, a remote one or an indoor place.
  • the filter and the vapor phase sorbent are suitable for solvent desorption by elution of extraction in order to remove the analytes for further analytical steps (Compendium of Methods for the Determination of Toxic Organic Compounds in Ambient Air Second Edition.
  • the analysis is generally conducted by chromatography, preferably Gas chromatography and HPLC.
  • sorbents In case of sampling of inorganic gases and vapor, specific sorbents are used.
  • a mixture copper/manganese oxide is used for collecting mercury vapor, high-purity silica gel for collecting acid gases such as HC1, H 2 SO 4 ; acid-coated sorbents, (e.g., silica gel, charcoal, firebrick) for ammonia, phosphine and hydrazine, alkali-treated charcoal for collecting sulfur dioxide, triethanolamine coated on an inert sorbent for nitrogen oxides and sulfur dioxide (M.Harper, J. Chromatography A, 885 (2000) 129-151.)
  • Inorganic Mercury vapor are usually analyzed by Atomic Fluorescence Spectroscopy (AFS) or by Inductively Coupled Plasma (ICP) /Atomic Absorption (AA) .
  • AFS Atomic Fluorescence Spectroscopy
  • ICP Inductively Coupled Plasma
  • AA Atomic Absorption
  • two types of sorbent tubes are used: tubes packed with gold beads of silica beads covered with gold for sampling of vapor mercury when an AFS instrument is used, since Hg is well adsorbed on gold materials and it can be released heating up the cartridges at about 500°C under a stream of an inert gas; while, when ICP or AA systems are employed, sampling tubes are usually packed with iodinated acid washed carbons, wherein mercury vapors are oxidized and trapped by the sorbent for further solvent extraction and analysis in laboratory (Compendium of Methods for the Determination of Inorganic Compounds in Ambient Air Chapter 10-5 SAMPLING AND ANALYSIS FOR ATMOSPHERIC
  • Granular activated carbons are widely used for filtration and respiratory protection.
  • Activated carbon has been historically used in the adsorption of gases and vapours (Cheremisinoff, P.N. and Ellerbusch, F. (1978) Carbon Adsorption Handbook, Ann Harbor Science Publishers, Inc., Ann Harbor, MI, U.S.A.; Hall, C.R. and King, K.S.W. (1988) Chem. Br. 24, 670) .
  • Its various important applications include the separation of mixtures, purification of liquids, recovery of gaseous components and catalysis (Bansal, R.C., Donnet, J.B. and Stoeckli, F.S. (1988) Active Carbon, CRC Press, New York) .
  • Carbon nanotubes are attractive for their use in in water treatment, because due to their hydrophobic nature, show strong adsorption affinities to a wide range of organic environmental contaminants. They are also used for the removal of microorganisms, natural organic matter, and toxins from drinking water due to their large external surface area and well developed meso-pores. CNTs have high adsorption capacities than traditional activated carbons (ACs) for dioxin (Long, R. Q . ; Yang, R. T. J. Am. Chem. Soc. 2001, 123, 2058- 2059), chloroform (Lu, C. S . ; Chung, Y.-L.; Chang, K.-F. Water Res.
  • ACs activated carbons
  • Activated carbon fibers are fibrous carbonaceous adsorbents obtained by the carbonization and activation of polymeric fibers that can be prepared from various precursors, such as, phenol-aldehyde, poly ( acrylonitrile ) (PAN), pitch and rayon fibers.
  • PAN poly ( acrylonitrile )
  • the small fiber diameter allows the homogeneous activation of the fibers, thus yielding a material with a narrow pore-size distribution composed mainly of micro-pores (Feng W, Kwon S, Borguet E et al.
  • Micropores in ACFs are straight and uniform in size, and are directly accessible from the external surface of the fiber, therefore the adsorption sites in ACFs can be accessed more easily than in other forms of activated carbon, and the adsorption kinetics are faster than that of granular activated carbon (GAC) (Liu Q-S, Zheng T, Wang P, Jiang J-P, Li N (2010) Chem. Eng. J. 157:348-356) .
  • GAC granular activated carbon
  • Activated carbon fibers have larger surface areas (1000-2400 m2/g) , larger adsorption capacities (as high as 250% of that of GAC) and faster heat and mass transfer properties (Petkovska, M., Tondeur, D., Grevillot, G., Granger, J. and Mitrovic, M. (1991) Sep. Sci . Technol. 26, 425) .
  • ACFs can be manufactured in various forms, such as woven cloth and unwoven felt (Huang et al . 2002) .
  • Activated carbon fibers (ACFs) are used in air pollution control devices (Takeuchi, Y., Shigeta, A. and Iwamoto, H. (1993) Sep. Technol.
  • Filters composed of a mat of ACFs have also been used in the capture of toxic gases emanating from industrial processes and gasoline vapors from automobile tanks.
  • Other applications of ACFs include environmental cleaning, the recovery of Sulphur dioxide and nitric oxide in flue gas, energy saving and storage such as methane storage, carbon dioxide (CO 2 ) capture, and air separation (Kisamori, S., Kurod, K., Kawano, S., Mochida, I., Matsumura, Y. and Yoshikawa, M.
  • Activated carbon fibers are used as stationary phase in analytical system such as HPLC columns, liquid samples concentrating tools or solid phase micro-extraction techniques (SPME) . Activated carbon fibers are suitable for filtering for removing a wide range of organic compounds since they are used for air cleaning and in personal protective equipment.
  • the analysis of organic and inorganic compounds in air is usually carried out by a three-step process wherein the first step is the enrichment of the analytes on a proper sampling media, the second one is the removal of the analytes from the media for further analytical steps and the last one is the identification and quantification of the compounds.
  • a different volume of air has to be sampled. For high volumes of sample it is necessary to use pumps to force the air to pass through a solid or liquid sorbent. For lower volumes or longer sampling periods it is possible to use passive sampling devices in which the driving force is the diffusion of the compounds through a specific layer onto a sorbent as stated by the law of Fick.
  • micro-extraction techniques SPME the adsorption of the compounds is driven by the equilibrium between their concentration in the fluid and in the sorbent that is influenced by several factors, such as temperature, humidity, flows, ionic strength and gradients, micro-extraction techniques SPME is used for the analysis of compounds in water or in their headspace but it is not a correct approach for the direct analysis of the air components. Active and passive sampling are suitable for every situation, meanwhile SPME technique is not so reliable and efficient .
  • the elution of the analytes from the sampling media depends to the type of analytes and to the matrix sampled.
  • the best technique is the thermal desorption, wherein the sampled tube, packed with a proper sorbent, is heated up to a specific temperature suitable for the removal of the analytes from the solid support.
  • a flow of inert gas helps this removal and transports the compounds in a secondary cooled trap packed with a weaker sorbent. This trap is then rapidly heated up to have a punctual desorption of the analytes into a gas- chromatographic system.
  • the thermal desorption technique provides high sensitivity, lower limits of detection and it is suitable for thermostable compounds.
  • the removal of the analytes from the sorbent is caused by a thermal shock in the Gas Chromatography injector: the more labile adsorption onto the fiber and the minor sorbent area allow a quicker desorption that is not possible with the common thermal desorption tubes.
  • the SPME fibers are directly inserted in the injector, passing through the septa, as an usual GC microsyringe needle.
  • the SPME injection is more similar to a classic Gas Chromatography injection than to a temperature assisted desorption of analytes from a solid support (Pawliszyn, J. Handbook of solid phase microextraction . (Elsevier, 2011) ) .
  • US patent N. 7291263 discloses a stationary phase for chromatography, in particular HPLC, comprising a fiber rod wherein fibers may be engaged to create a self-sustaining, rod-like structure; fibers are of thermoplastic or resin material .
  • US patent N. 5897782 discloses the absorbing of antimicrobial agents in biological fluids by means of a fibrous material made of activated carbon fibers, the device is in the form of a stick or a needle which is dipped in the liquid sample.
  • Chinese patent N.104359996 discloses a column for solid phase extraction from liquids packed with a bundle of activated carbon fibers and followed by solvent desorption.
  • Japanese patent application discloses an adsorbent made of active carbon fibers for the concentration of compound in liquid samples followed by solvent desorption.
  • US patent application N. 2005/276727 discloses a device for in vivo study of chemical concentrations in liquid biological samples comprising fibers partially coated with an extraction phase for absorbing components of interest followed by a solvent desorption step or direct matrix assisted laser desorption (MALDI) .
  • Chinese patent application N. CN1405560 discloses a solid phase made of carbon fibers for solid-phase micro extraction SPME .
  • Granular carbons are widely used in analytical systems for different purpose. They present several drawbacks. For instance granular carbons are fragile, suffer mechanical stress even during transportation and packing, and are not suitable for relatively high pressure, thus limiting their use in several conditions such as high flow rate chromatography and high pressure liquid chromatography. Moreover, granular carbons require frits and careful handling during column packaging; packaging conditions may also influence permeability and proper functioning of the column. Granular carbons have poor compatibility with high humidity samples, because their ability in catching water turn out as drawback since traps or column quickly clogs in the attempt of sampling high humidity air sample, thus limiting the sample volumes in these cases. Systems suggested to overstep this limitation dramatically affect the efficiency of the trap, especially for polar compounds.
  • sampling in situ sampling may be necessary, and in this case, may be not always easy to set up a complete filtering equipment on site, for example in some outdoor area due to the meteorological conditions.
  • sampling standard mixture should be added to the sampling media, before the sampling procedure, to evaluate, at the end of the analysis, the quality of the sampling step and provide a reliable and accurate result.
  • the sampling standard is usually dropped on the filter, in the site of the sampling, and this operation maybe altered by possible adverse atmospheric conditions. It is not appropriate to spike the filter in laboratory before going in the site of the sampling, since lacks of analytes is possible during the storage and transport due to volatility of the compounds or to contamination of the filter itself.
  • activated carbon fibers are not commonly used as sorbents in analytical application because suspected to present the same drawbacks of granular carbons, for example, too high theoretical retain rate and possible crumbling and pulverization of ACFs (Kawata K, Minagawa M, Fujieda Y, Yasuhara A (1993) Sampling method of organotin compounds in air using a quartz-fibre filter and an activated carbon-fibre filter for gas chromatographic determination. Journal of Chromatography A 653:369-373.
  • carbon fibers have the ability of trapping a much wider range of analytes compared to granular carbons and quantitatively desorb them under suitable conditions.
  • the stationary phase of the present invention can be used in thermal and/or solvent assisted desorption, and it is particularly suitable for thermal desorption because it does not burn and it is fireproof at the high temperature. Moreover it is stable at high pressures and does not pulverized. In addition it is inert and does not react with analytes or other chemicals.
  • Activated carbon fibers ACFs have a high specific surface area which improves the performances in sampling VOCs with a small amount of sorbent, even in unfavorable conditions such as high humidity.
  • the arrangement of the bundle of carbon fibers within the trap allows contemporary sampling and trapping of several types of analytes in gaseous and/or vapor phase, which can be then easily desorbed, by thermal and/or solvent assisted desorption and further analyzed.
  • the stationary phase of the present invention can be considered as "self-confining" because does not need any kind of frits in column preparation and can be configured in setup which are not possible using granular carbons, such as self- confined cylinder, disks, tube/sleeve shape and wires. Those configurations further decrease the fluid (gas) impedance thus allowing the easy and efficient use of carbon fibers in application such as exhaled breath analysis or as denuders type samplers.
  • traps of the present invention are able to sample at the same time both SVOCs phase, the one on the particulate matter and the other in the vapor phase. Furthermore, the quantitative extraction of the analytes from the trap can be carried out with less solvent than double device sampling systems known in the art, with a high efficiency. It is also possible to add sampling standards in laboratory, thanks to the high sorptive properties of the trap that don't allow an easy release of the analytes. Also, the inertness of the trap to wet vapor samples avoids a too high pressure drop during the sampling that can cause the arrest of the sampling. Therefore, a less expensive, more rapid, simple but reliable system has been developed and optimized.
  • the present invention overcomes all the major drawback of the prior art.
  • the technical problem is solved by providing a trap made of a bundle of carbon fibers, activated and not-activated, optionally graphitized or grafted or coated, to be used as a stationary phase for analytic applications, in particular of samples and/or analytes in gaseous and/or vapor phase.
  • object of the present invention is a a trap made of a bundle of carbon fibers, activated and not-activated, being optionally graphitized or grafted or coated, wherein said bundle of carbon fibers is suitably arranged as tangled, woven, fabric, wires, in parallel, fabric woven, fabric woven into a tube or disk shape and tangled into a tube or disk shape. It is also object of the present invention the use of said trap as stationary phase for analytic use.
  • a further object of the present invention is the use of said stationary phase for retaining analytes being organic and inorganic compounds, in gaseous and/or vapor phase.
  • a further object of the present invention is a process for analyzing analytes being organic and inorganic compounds, in gaseous and/or vapor phase comprising the following steps: a) Trapping the analytes (active or passive mode) on a stationary phase being a trap made of a bundle of carbon fibers, activated and not-activated, optionally graphitized or grafted or coated, wherein said bundle of carbon fibers is suitably arranged as tangled, woven, fabric, wires, in parallel, fabric woven, fabric woven into a tube or disk shape and tangled into a tube or disk shape;
  • a further object of the present invention is a system for analyzing analytes being organic and inorganic compounds, in gaseous and/or vapor phase comprising: i. At least one sampling device filled in with the stationary phase being a trap made of a bundle of carbon fibers, activated and not-activated, optionally graphitized or grafted or coated, , wherein said bundle of carbon fibers is suitably arranged as tangled, woven, fabric, wires, in parallel, fabric woven, fabric woven into a tube or disk shape and tangled into a tube or disk shape;
  • Figure 1 shows a comparison between prior art and the present invention wherein: panel A is a schematic representation of the prior art as a common thermal desorption tubes prepared using granular carbons according to Brancaleoni E, Scovaventi M, Frattoni M, Mabilia R, Ciccioli P (1999) Journal of Chromatography A 845:317-328.
  • Panel B is a schematic representation of three different arrangements of carbon fibers according to the present invention into a thermal desorption tube 6mm x 160mm (internal diameter 4mm), wherein in panel B, type 1 represents the bundle of carbon fibers arranged as tangled; type 2 represent the bundle of carbon fibers arranged as tangled into a tube shape; type 3 represent the bundle of carbon fibers arranged in a fabric woven in a tube shape.
  • Figure 2 is a schematic representation of two frit-less fabric woven disk shape or tangled disk shape passive samplers having different capacity (type 4b has double capacity) .
  • Figure 3 is a schematic representation of the embodiments being high volume sampler filters suitable for SVOCs sampling followed by solvent desorption being disks of 60 mm or 102 mm diameter and 0,25 mm thickness made of activated carbon fibers in the form of a bundle of carbon fibers arranged as tangled.
  • Figure 4 presents two chromatograms resulting from sampling emission from a Biomass boiler (wet vapor) by means of prior art (lower) and type 1 (upper), showing differences in collected compounds
  • Figure 5 presents chromatograms resulting from sampling emission from a Biomass boiler (wet vapor) by means of prior art (lower) and type 1 (upper), showing collection of NO 2 and S0 2 ;
  • Figure 6 presents chromatograms resulting from sampling emission from a Biomass boiler (wet vapor) by means of and type 1 showing peaks of low concentration analytes.
  • Figure 7 presents chromatograms resulting from sampling exhaled breath (wet vapor conditions) by means of prior art
  • Figure 8 presents chromatograms resulting from sampling exhaled breath (wet vapor conditions) by means of prior art
  • Figures 9 presents mass spectra resulting from sampling of Mercury vapors in air.
  • Figure 10 presents mass spectra resulting from sampling of Mercury vapors in artificially contaminated atmosphere.
  • Figure 11 present mass spectra resulting from sampling of Mercury vapors in real indoor air. Description of the invention
  • carbon fibers means a material consisting of fibers about 1-10 ⁇ in diameter and composed mostly of carbon atoms.
  • activated carbon fibers are fibrous carbonaceous adsorbents obtained by the carbonization and activation of polymeric fibers preferably phenol-aldehyde or poly ( acrylonitrile ) (PAN) type.
  • PAN poly ( acrylonitrile )
  • the sampling can be carried out in active or passive mode.
  • stationary phase means a solid or liquid adsorbed on solid coherent material used in contact with gases, vapor and fluids in order to retain and concentrate analytes to be later released and subjected to further analysis preferably by means selective quantitate methods such as of chromatographic techniques.
  • analytical use means analytical procedures, excluding procedures limited to filtration, purification and retaining only, therefore including trapping analytes during sampling step, releasing analytes by desorption or extraction and quantifying analytes with analytical means (e.g. gas chromatography) .
  • arrangement of the bundle of non-activated carbon fibers or activated carbon fibers arranged as tangled means nonwoven carbon fibers homogenously matted together at specific density using different systems such as heat, pressure humidity in order to obtain consistent suitable shapes.
  • arrangement of the bundle of non-activated carbon fibers or activated carbon fibers arranged as fabric means that carbon fibers are woven or knitted in order to obtain clothes.
  • arrangement of the bundle of non-activated carbon fibers or activated carbon fibers arranged in parallel means that all fibers are aligned parallel to the long axis each other.
  • suitable coating for preparing coated non-activated carbon fibers or activated carbon fibers are selected from the group consisting of: Squalene, Methyl-silicone, Methyl-phenyl-silicone,
  • FFAP Nitroterephtalic ester of PEG
  • DEGS Diethyleneglycol succinate
  • alkali metal silicates alkali metal silicates
  • grafted means, chemically modification to introduce suitable exposed group R on the surface of the non activated and activated carbon fibers, wherein R, equal or different, is selected from the group consisting of: hydrogen, linear, branched, cyclic and polycyclic alkanes, cumulative conjugated and unconjugated alkenes , cumulative conjugated and unconjugated polyenes, conjugated and unconjugated alkynes, conjugated and unconjugated polyalkynes, aromatic rings, polyaromatic rings, alkyl vinyl alkynyl aryl acyl halides, moieties containing a bond between a carbon atom and a halogen, moieties containing a bond between a halogen and an oxygen or nitrogen or sulfur or phosphorus atom, primary secondary tertiary and cyclic non-cyclic aromatic non-aromatic amines and their salts, alkylammonium salts, haloamines (i.e.
  • moieties wherein phosphorus forms a double bond with an oxygen or nitrogen or selenium or tellurium atom and three bonds with the same number of atoms of oxygen or nitrogen or sulfur or halogens or silicon phosphonates (i.e. moieties wherein phosphorus forms a double bond with an oxygen or nitrogen atom, or selenium or tellurium, a bond with a carbon atom, and two bonds with the same number of atoms of oxygen or nitrogen or sulfur or halogens or silicon), phosphinates (i.e.
  • moieties wherein phosphorus forms a double bond with an oxygen or nitrogen or selenium or tellurium atom, two bonds with the same number of carbon atoms, and a bond with an oxygen atom or nitrogen or sulfur or halogens or silicon moieties wherein phosphorus forms a double bond with an oxygen or nitrogen or selenium or tellurium atom and three bonds with the same number of carbon atoms (phosphine oxides), phosphonium salts (i.e. moieties wherein phosphorus forms four bonds with the same number of atoms of carbon or oxygen or nitrogen or sulfur or halogens or silicon, and has a positive charge balanced by a halogen or by another anion), phosphoranes (i.e.
  • moieties wherein phosphorus forms five bonds with the same number of atoms of carbon or oxygen or nitrogen or sulfur or halogens or silicon phosphites (i.e. moieties wherein phosphorus forms three bonds with the same number atoms of oxygen or nitrogen or sulfur or halogens or silicon), phosphonites (i.e. moieties wherein phosphorus forms two bonds the same number of atoms of oxygen or nitrogen or sulfur or halogens or silicon and a bond with a carbon atom), phosphinites (i.e.
  • moieties wherein phosphorus forms two bonds with the same number of carbon atoms and a bond with an atom of oxygen or nitrogen or sulfur or halogens or silicon phosphines (also known as phosphanes, i.e. moieties wherein the phosphorus form three bonds with the same number of carbon atoms), phosphalkenes (i.e. compounds wherein the phosphorus forms a double bond with a carbon atom), phosphalkynes (i.e. compounds wherein the phosphorus form a triple bond with a carbon atom), diphosphenes (i.e.
  • graphitized means chemically modification coat or impregnate with graphite of the non activated and activated carbon fibers obtained by heat treatment.
  • Known process to are performed above 2800°C in an inert atmosphere.
  • trap means a filter made of a bundle of non activated and activated carbon fibers which aims to complete retention of the analytes wherein said filter is not in the form of a needle or stick such as the one used in the so called solid phase micro- extraction techniques (SPME) which is a sampling technique where the quantity of analyte extracted by the fiber is proportional to a constant specific for each compound and to its concentration in the sample, as long as equilibrium is reached.
  • SPME solid phase micro- extraction techniques
  • solvent desorption means that a specific solvent is used in order to desorb the analytes form the stationary phase for further analysis.
  • thermal desorption means the use of heat to increase volatility of analytes such that they can be removed (separated) from the stationary phase.
  • Volatile organic compounds are chemical compounds, present in the vapor phase at room temperature, defined as vapor pressure greater than 0.1 (0.0133 kPa) at 25°C.
  • semi-volatile organic compounds are organic compound which has a boiling point higher than water and which may vaporize when exposed to temperatures above room temperature, such as phenols and polynuclear aromatic hydrocarbons (PAH) , poly- halogenated dioxins and furans, dioxin-like compounds (DLCs), polychlorinated biphenyls (PCBs), polychlorinated benzenes (CBs) .
  • quantification mean to be used in the quantification step are selected from the group consisting of: liquid chromatography, gas chromatography, optical spectrometry, mass spectrometry, gas chromatography-mass spectrometry (GC-MS) .
  • the object of the present invention is a trap made of a bundle of carbon fibers, activated and not-activated, optionally graphitized grafted or coated, wherein said bundle of carbon fibers is suitably arranged as tangled, woven, fabric, wires, in parallel, fabric woven, fabric woven into a tube or disk shape and tangled into a tube or disk shape.
  • the activated carbon fibers are obtained by activation of polymeric phenol-aldehyde fibers.
  • the bundle of carbon fibers is arranged as tangled, fabric woven into a tube or disk shape, tangled into a tube or disk shape.
  • the carbon fibers may be coated with Squalene, Methyl- silicone, Methyl-phenyl-silicone, Cyanopropyl-methyl-phenyl- silicone, Polyethylenglycol , Nitroterephtalic ester of PEG (FFAP), Diethyleneglycol succinate (DEGS), alkali metal silicates, epoxy resins.
  • Squalene Methyl- silicone, Methyl-phenyl-silicone, Cyanopropyl-methyl-phenyl- silicone, Polyethylenglycol , Nitroterephtalic ester of PEG (FFAP), Diethyleneglycol succinate (DEGS), alkali metal silicates, epoxy resins.
  • FFAP Nitroterephtalic ester of PEG
  • DEGS Diethyleneglycol succinate
  • alkali metal silicates epoxy resins.
  • the trap is made of a bundle of carbon fibers is arranged as tangled and it is in the form of a disk of 60 mm diameter and 0,25 mm thickness made suitable for SVOCs vapor phase sampling.
  • the trap is made of a bundle of carbon fibers is arranged as tangled and it is in the form of a disk of 102 mm diameter and 0,25 mm thickness made suitable for both PM and vapor phase sampling.
  • the trap is included in a thermal desorption tube.
  • the thermal desorption tube include a trap made of a bundle of carbon fibers is arranged as tangled.
  • the trap is used as stationary phase for analytic use.
  • Said stationary phase is used for retaining analytes being organic and inorganic compounds in gaseous and/or vapor phase, preferably volatile organic compounds (VOCs), semi-volatile organic compounds (SVOCs) and inorganic compounds, mercury vapor.
  • VOCs volatile organic compounds
  • SVOCs semi-volatile organic compounds
  • mercury vapor mercury vapor.
  • the stationary phase is positioned in a conventional thermal desorption tube.
  • the process for analyzing analytes being organic and inorganic compounds in gaseous and/or vapor phase preferably volatile organic compounds (VOCs), semi-volatile organic compounds (SVOCs) and mercury vapor comprises the following steps: a) Trapping the analytes (active or passive mode) on a stationary phase being a trap made of a bundle of carbon fibers, activated and not-activated, optionally graphitized or grafted or coated, wherein said bundle of carbon fibers is suitably arranged as tangled, woven, fabric, wires, in parallel, fabric woven, fabric woven into a tube or disk shape tangled into a tube or disk shape ;
  • step b) thermal desorption is performed at a temperature between 250°C and 350°C, more preferably at 300°C.
  • step b) thermal desorption is performed at a flow rate of 20 mL/min to 40 mL/min, more preferably at 20 mL/min
  • step b) thermal desorption is performed for a time of 4 to 10 minutes more preferably 5 minutes.
  • step c) quantification is performed by Gas chromatography-mass spectrometry (GC-MS) .
  • GC-MS Gas chromatography-mass spectrometry
  • a further object of the present invention is a system for analyzing being organic and inorganic compounds in gaseous and/or vapor phase preferably volatile organic compounds (VOCs), semi-volatile organic compounds (SVOCs) and mercury vapor comprising: i. At least one sampling device filled in with the stationary phase being being a trap made of a bundle of carbon fibers, activated and not-activated, optionally graphitized or grafted or coated, wherein said bundle of carbon fibers is suitably arranged as tangled, woven, fabric, wires, in parallel, fabric woven, fabric woven into a tube or disk shape, tangled into a tube or disk shape;
  • the desorption mean ii is a thermal desorption tube or a Soxhlet extractor.
  • the quantification mean iii is chromatography-mass spectrometry (GC-MS) .
  • Analytes desorption was obtained by increasing the temperature according to conventional thermal desorption procedure.
  • figure 1 In embodiments of figure 1 (type 1-3) a much smaller amount (mass) of carbon fiber is necessary in comparison with granular carbon sorbent.
  • the carbon fiber stationary phases are more efficient and generate lower impedance to sample flow. Even collecting water in more the amount of approximately twice its weight due to morphological structure of carbon fiber arrangements the impedance is not substantially increased thus limiting the use in humid sample or even in presence of liquid water (wet vapors) .
  • the large amount of water collected does not negatively influence the trapping ability of stationary phase.
  • the drop of pressure of a prior art thermal desorption tube is more than 80 mm 3 ⁇ 40.
  • the drop of pressure was 20 mm of 3 ⁇ 40.
  • Further decrease of the drop of pressure can be obtained using carbon fiber based tube type 2 and 3.
  • type 2 the drop of pressure was just 2 mm 3 ⁇ 40 and using type 3 was lower than 1 mm 3 ⁇ 40.
  • Such trapping devices are especially useful in applications such as exhaled breath analysis for non-invasive diagnostic of several diseases were exhaled breath can be collected even from patients with no special effort or complex devices.
  • figure 2 can be used as passive sampler in order to effectively estimate the exposure to VOCs .
  • Using a disk geometry of suitably tangled carbon fiber is also possible to collect large volume sample and use solvent desorption (or soxhlet extraction) in order to recover SVOCs and non-volatile compound, then quantified using both gas and liquid chromatographic systems.
  • solvent desorption or soxhlet extraction
  • Example 2 Wet gas, flue gas emissions
  • a carbon fibres based thermal desorption trap was used for sampling emissions from a Biomass boiler with mobile grid burning poplar wood for production of 450Kcal/h.
  • the gas emission was sampled at the mean temperature of 145°C.
  • the emission composition was O 2 12%, CO 2 6,5%, 3 ⁇ 40 12% (absolute humidity) .
  • 450 mL samples were collected at the flow rate of 45 mL/min using a pump. Larger samples, namely 1 and 2 litres where collected using a syringe.
  • the drop of pressure at the beginning of the sampling was ⁇ 0,33 bar for the ACF 30 mg Type 1 trap and ⁇ 1,23 bar for conventional MCT GACs .
  • Major evidence of the superior sampling efficiency of the ACF Type 1 toward conventional TD tubes are: the larger sample potentially collectable (up to 2 litre without any consistent drawback due to the presence of wet vapour) thus consistently decreasing the limits of detection; the larger r number of compounds collected; the collection of gases such as N 2 O and SO 2 ; collection of acids such as Acetic and Propionic acid; collection very polar compounds such as Paraformaldehyde and Guaiacol; Much lower limits of detections for analytes present at lower concentration by collecting larger samples.
  • Type 1 and 2 thermal desorption tubes were compared with conventional GAC TD tubes in the following conditions:
  • Sampled volume 1 L; the sampling flow rate was 10-15 mL/min when using ACF Type 1 and, because the intrinsic higher impedance was just 3-4 mL/min when sampling with the conventional MCT GACs based TD tubes.
  • Sampling type direct deep expiration (of a healthy non-smoker 28 years old) in the trap after deep inspirations.
  • ACF TD tubes Major advantages of ACF TD tubes observed in these experiments were: higher permeability even in presence of wet vapor samples; possibility of sampling large volume (1 liter) in just two expirations. In the case of GACs TD tubes in order to collect 1 liter samples eight deep expirations were necessary toward a very high impedance. Such sampling conditions are not suitable for sampling on patients; ability of trapping more volatile metabolites and gases; lower contamination of food and stomach emissions due to due the shorter persistence time of the exhaled breath in the oropharynx.
  • Example 4 Mercury vapors
  • the traps based on carbon fibers were evaluated for their ability in analysing metals vapours in the conditions used for the analysis of VOCs .
  • the breakthrough volume was evaluated using a second trap in series. After 20 liters mercury was efficiently adsorbed and desorbed in the conditions previously describes on the first traps there was no evidence of breakthrough occurring during the sampling.
  • figures 9 and 10 the mass spectra of mercury and its chromatographic peak are reported.
  • figure 11 the results obtained on a real sample of indoor air are reported.
  • Example 5 - SVOCs sampling using a high volume sampler based on ACF filtering device The potential use of a carbon fibers based filtering disk such device type 5 for sampling SVOCs was evaluated by using it inserted after the filter and prior the polyurethane foam
  • Experiment A has been performed to test the ACF filter as a vapor phase sampler.
  • Experiment B has been performed to sample both PM and vapor phase (experiment B) .
  • experiment A in the high volume sampler, a glass fiber 102 mm disk was used to sample the particulate (PM10) .
  • Vapor phase SVOCs were sampled using a 60 mm diameter ACF filter/disk 2.5 mm thick.
  • a second ACF filter/disk was put in series in order to evaluate breakthrough.
  • a 3 inch long PUF was then put after the ACF disks.
  • the glass fiber filter was replaced by an ACF filter and a parallel sampling was performed in the same place (2 m of distance) and at the same time with a conventional glass filter/PUF sampling system.
  • the sampling flow rate was 200 Liters/minute up to final volume of about 540 m 3 . Samples were collected in a recent fire polluted area.
  • recoveries and quantifications are reported in the following tables 2-6.
  • Ratios % glass filter A ACF disk A PUF/felt A
  • PCB 118 0.7 1.0 0.2
  • PCB 114 0.6 1.0 -
  • experiment B demonstrates that the total SVOC amount in the glass filter/PUF system is comparable to the one in the sampling with the only ACF filter.
  • the differences between the sampling are in the range of the RSD% stated by the EPA methods.
  • Pentachlorobenzene (PeCB) and Hexachlorobenzene (HCB) that are more volatile than the other classes of compounds analyzed, it was not possible to provide such comparison due to the differences between the recoveries.
  • the recoveries of the sampling standard for PeCB and HCB was always higher of at least one order of magnitude than the one obtained with the glass filter/PUF sampling system.
  • ACF filter can be used as a single device for sampling the total SVOC fraction in the air and requires also less solvent for the pre-cleaning and extraction than the PUF.

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Abstract

La présente invention concerne un piège constitué d'un faisceau de fibres de carbone, activées et non activées, dans lequel le faisceau est agencé sous forme enchevêtrée, tissée, de tissu, de fils, en parallèle, de tissu tissé, de tissu tissé sous forme de tube ou de disque, et echnevêtrée sous forme de tube ou de disque pour être utilisé en tant que phase stationnaire pour une application analytique sur des composés organiques et inorganiques en phase gazeuse et/ou vapeur et un procédé associé.
PCT/IB2016/054644 2015-08-04 2016-08-02 Système analytique à base de fibres de carbone Ceased WO2017021883A1 (fr)

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