Method of detecting carbon dioxide in a gaseous sample, an apparatus, and use of an anion exchange resin

Abstract

According to an example aspect of the present invention, there is provided a method of detecting carbon dioxide in a gaseous sample, the method comprising: flowing the gaseous sample through an anion exchange resin that is capable of selectively adsorbing CO.sub.2 present in the gaseous sample; releasing the adsorbed CO.sub.2 from the resin by heating the resin to a temperature in the range 80 to 250° C. to obtain a concentrated gaseous sample; determining the amount of an isotopic form of CO.sub.2 in the concentrated gaseous sample by infrared absorption spectroscopy.

Claims

1. A method of detecting carbon dioxide in a gaseous sample, the method comprising: flowing the gaseous sample through an anion exchange resin that is capable of selectively adsorbing CO.sub.2 present in the gaseous sample; releasing the adsorbed CO.sub.2 from the resin by heating the resin to a temperature in the range 80 to 250° C. to obtain a concentrated gaseous sample; and determining the amount of an isotopic form of CO.sub.2 in the concentrated gaseous sample by infrared absorption spectroscopy.

2. The method according to claim 1, wherein the isotopic form is .sup.12CO.sub.2 or .sup.13CO.sub.2 or .sup.14CO.sub.2 or any combination of them.

3. The method according to claim 1, wherein the isotopic form of CO.sub.2 is any isotopologue of CO.sub.2 containing any isotope(s) of oxygen and any isotope of carbon.

4. The method according to claim 1, wherein the anion exchange resin features primary, secondary, and/or tertiary amino groups.

5. The method according to claim 1, wherein the anion exchange resin comprises crosslinked polymeric material.

6. The method according to claim 1, wherein the resin is heated to a temperature in the range 100 to 200° C.

7. The method according to claim 1, wherein the resin is heated for a time period of 1 to 15 minutes.

8. The method according to claim 1, wherein the determining step comprises measuring an infrared absorption spectrum of the concentrated gaseous sample by using a cavity down-ring laser spectroscopy.

9. The method according to claim 1, wherein: the isotopic form is .sup.14CO.sub.2; the gaseous sample further comprises .sup.14CH.sub.4, and the method further comprises, before the determination step: catalytically oxidizing the .sup.14CH.sub.4 to .sup.14CO.sub.2 by a catalyst, wherein the .sup.14CO.sub.2 to be determined in the determination step also comprises .sup.14CO.sub.2 converted from the .sup.14CH.sub.4 present in the gaseous sample.

10. The method according to claim 9, wherein the catalyst is a Pd catalyst, and the step of catalytically oxidizing the .sup.14CH.sub.4 to .sup.14CO.sub.2 comprises: heating the Pd catalyst to a temperature of at least 300° C.; bringing the gaseous sample into contact with the heated Pd catalyst; wherein the heated Pd catalyst catalyses oxidation of the .sup.14CH.sub.4 present in the gaseous sample to .sup.14CO.sub.2.

11. The method according to claim 1, wherein the isotopic form is .sup.14CO.sub.2 and the gaseous sample originates from a nuclear power plant.

12. The method according to claim 1, wherein the gaseous sample is an atmospheric sample.

13. The method according to claim 1, wherein the gaseous sample is/originates from a biofuel.

14. The method according to claim 1, wherein the gaseous sample is/originates from a biological sample.

15. An apparatus comprising in a cascade: first means for concentrating CO.sub.2 present in a gaseous sample to obtain a concentrated gaseous sample; and second means for determining the amount of an isotopic form of CO.sub.2 present in the concentrated gaseous sample by infrared absorption spectroscopy, wherein the first means comprises an anion exchange resin that is capable of selectively adsorbing CO.sub.2 present in the gaseous sample.

16. The apparatus according to claim 15, wherein the anion exchange resin features primary, secondary, and/or tertiary amino groups.

17. The apparatus according to claim 15, wherein the isotopic form is .sup.12CO.sub.2 or .sup.13CO.sub.2 or .sup.14CO.sub.2 or any combination of them.

18. The apparatus according to claim 15, wherein the isotopic form of CO.sub.2 is any isotopologue of CO.sub.2 containing any isotope(s) of oxygen and any isotope of carbon.

19. The apparatus according to claim 15, wherein: the isotopic form is .sup.14CO.sub.2; and the apparatus further comprises: upstream of said first means, further means for catalytically oxidizing .sup.14CH.sub.4 present in the gaseous sample, wherein said second means is adapted for determining the combined amount of .sup.14CO.sub.2 present in the gaseous sample and .sup.14CO.sub.2 converted from the .sup.14CH.sub.4 present in the gaseous sample by infrared absorption spectroscopy.

20. The apparatus according to claim 19, wherein the further means for catalytically oxidizing .sup.14CH.sub.4 present in the gaseous sample comprises a catalyst bed comprising a catalyst.

21. The apparatus according to claim 15, wherein the second means comprises a cavity down-ring laser spectrometer comprising a quantum cascade laser as an IR light source.

22. (canceled)

23. A method of detecting carbon dioxide in a gaseous sample, the method comprising: flowing the gaseous sample through an anion exchange resin that is capable of selectively adsorbing CO.sub.2 present in the gaseous sample; releasing the adsorbed CO.sub.2 from the resin by heating the resin to obtain a concentrated gaseous sample; and determining the amount of an isotopic form of CO.sub.2 in the concentrated gaseous sample.

24. The method according to claim 23, comprising: determining the amount of an isotopic form of CO.sub.2 in the concentrated gaseous sample by infrared absorption spectroscopy

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0062] FIG. 1 illustrates schematically a laser spectroscopy apparatus, more specifically a cavity ring-down spectroscopy setup, in accordance with at least some embodiments of the present invention;

[0063] FIG. 2 shows results from an experiment that studies desorption of CO.sub.2 from a resin in accordance with an embodiment of the present invention;

[0064] FIG. 3 shows results from an experiment that studies eventual adsorption of N.sub.2O by an anion exchange resin in accordance with an embodiment of the present invention;

[0065] FIG. 4A shows an absorption spectrum measured in a method according to an embodiment of the present invention, using an anion exchange resin for extracting CO.sub.2;

[0066] FIG. 4B shows a comparative absorption spectrum measured in a method that uses cryogenic trapping for extracting CO.sub.2; and

[0067] FIG. 5 illustrates an experimental set-up for fast sampling in accordance with an embodiment of the present invention.

EMBODIMENTS

[0068] The present method uses an anion exchange resin to trap CO.sub.2. Only a small amount of CO.sub.2 is required for a spectroscopic analysis, and accordingly a small amount of the resin is sufficient. Further, the trapping time is short. This type of resin allows efficient trapping and fast release of the trapped CO.sub.2.

[0069] We have surprisingly observed that the resin does not adsorb N.sub.2O, which is a critical condition for carrying out a spectroscopic analysis of carbon dioxide isotopes, particularly .sup.14CO.sub.2.

[0070] In the present context, “isotopologues” are molecules that differ only in their isotopic composition. The isotopologue of a chemical species has at least one atom with a different number of neutrons than the parent.

[0071] In the present context, the term “radiocarbon” refers to .sup.14C, the radioactive isotope of carbon.

[0072] In the present context, the term “weakly basic” anion exchange resin refers to for example a resin that does not contain exchangeable ionic sites and functions as acid adsorber. The different types of ion-exchange resins differ mainly in their functional groups. Weakly basic resins typically feature primary, secondary, and/or tertiary amino groups, for example polyethylene amine.

[0073] Air samples usually contain trace amounts of N.sub.2O, which has strong absorption lines close to the CO.sub.2 absorption line in the mid-infrared wavelength range. In the case of detecting .sup.12CO.sub.2, such trace amounts would not pose any problem, because the levels of .sup.12CO.sub.2 in the air are in the range 400 ppm to a few %. For the purpose of monitoring ppt levels of .sup.14CO.sub.2, the interference from N.sub.2O significantly decreases sensitivity.

[0074] The inventors have surprisingly observed that the interference arising from N.sub.2O in laser spectroscopic radiocarbon detection methods can be successfully eliminated by using an anion-exchange resin for concentrating CO.sub.2.

[0075] According to some embodiments of the present invention, any isotopologue of carbon dioxide can be detected, preferably selected from the unstable isotopologues of carbon dioxide, such as the unstable isotopologues containing at least one of the following: C-13, C-14, O-17, O-18.

[0076] According to some embodiments of the present invention, several isotopologues of carbon dioxide can be detected, preferably the stable carbon dioxide CO.sub.2 in combination with any of the unstable isotopologues of carbon dioxide.

[0077] According to an embodiment, the isotopologue is .sup.14C.sup.16O.sup.16O.

[0078] According to an embodiment, the isotopologue is .sup.13C.sup.16O.sup.16O.

[0079] According to an embodiment, the isotopologue is .sup.12C.sup.16O.sup.18O.

[0080] According to an embodiment, the isotopologue is .sup.12C.sup.16O.sup.17O.

[0081] According to an embodiment, the isotopologue is .sup.13C.sup.16O.sup.18O.

[0082] According to an embodiment, the isotopologue is .sup.13C.sup.16O.sup.17O.

[0083] According to an embodiment, the isotopologue is formed by an unstable isotope of carbon (.sup.14C or .sup.13C) and any isotope(s) of oxygen as any combination.

[0084] According to an embodiment, the isotopologue is formed by the stable isotope of carbon (.sup.12C) and any isotope(s) of oxygen as any combination.

[0085] In some embodiments of the present invention, the concentration of .sup.14CO.sub.2 in the sample can be increased from ppq or ppb levels to ppt or ppm levels.

[0086] While traditional radiation detectors rely on the detection of emitted radiation, the method presented here detects the molecules containing the radioisotope C-14 itself. The present method is based on optical methods for the detection of molecules containing radiocarbon.

[0087] Radiocarbon is a beta emitter. In the present invention, it is not necessary to chemically separate other beta emitters, such as tritium, beforehand, which is an advantage over traditional radiochemistry methods, such as liquid scintillation counting.

[0088] In some embodiments of the present invention, radiocarbon originally present in different molecular forms is detected in the form of carbon dioxide (.sup.14CO.sub.2).

[0089] The invention provides several advantages in terms of size, price, and on-site measurement capabilities. The system presented here enables automated onsite and online monitoring of fugitive radiocarbon emissions in nuclear facilities.

[0090] In one embodiment, before trapping .sup.14CO.sub.2, .sup.14CH.sub.4 present in the sample is catalytically oxidized to CO.sub.2 by a catalyst according to the following reaction:

CH.sub.4+O.sub.2.fwdarw.CO.sub.2

[0091] The catalyst is preferably a Pd catalyst, for example an alumina supported Pd catalyst.

[0092] In one embodiment, the catalyst is a Pd catalyst comprising 2 to 3 wt-% Pd.

[0093] In some embodiments, the Pd catalyst is prepared by the method described in Fouladvand et al., “Methane Oxidation Over Pd Supported on Ceria-Alumina Under Rich/Lean Cycling Conditions”, Topics in Catal. (2013) 56:410-415.

[0094] Other possible catalysts for catalysing oxidation of .sup.14CH.sub.4 are precious metals, such as platinum or palladium or rhodium.

[0095] During the catalytic oxidation of .sup.14CH.sub.4 by the catalyst, the temperature is preferably at least 285° C., more preferably in the range 300 to 500° C., most preferably in the range 300 to 350° C.

[0096] Anion Exchange Separation

[0097] In one embodiment, the anion exchange resin is an amine-based resin.

[0098] Preferably the resin is an anion exchange resin functionalized with amino groups.

[0099] In one embodiment, the anion exchange resin features primary, secondary, and/or tertiary amino groups, e.g. polyethylene amine.

[0100] In one embodiment, the anion exchange resin is a crosslinked polystyrene based resin, preferably functionalized with amino groups.

[0101] In one embodiment, the anion exchange resin is a polystyrene polymer based resin, which is crosslinked via the use of divinylbenze, and is functionalized with primary amine groups, such as benzylamine. Such a resin can be produced by a phthalimide process, for example by a process that is commercially available from LANXESS Deutschland GmbH under the brand name LEWATIT® VP 001065.

[0102] In one embodiment, LEWATIT® VP OC 001065 resin is used. According to literature (Alesi & Kitchin, Ind. Eng. Chem. Res. 2012, 51, 6907-6915) the capture capacity of LEWATIT VP OC 001065 resin is remarkably high; 1.85 to 1.15 mol CO.sub.2/kg in a packed bed reactor exposed to 10 vol-% of CO.sub.2 at adsorption temperatures ranging from 30 to 70° C.

[0103] In one embodiment, the anion exchange resin is a weakly basic purely gel-type resin.

[0104] The thermal stability of the resin must be high enough to facilitate fast regeneration. Therefore, the resin preferably comprises crosslinked polymeric material.

[0105] In one embodiment, the gaseous sample is flown through a column containing the resin, whereby the CO.sub.2 present in the sample becomes adsorbed.

[0106] In preferred embodiments, to release the adsorbed CO.sub.2, the resin is heated, preferably to a temperature in the range 100 to 250° C., for example 150 to 200° C. It is advantageous to keep the temperature below 250° C., for example below 170° C., so that nitrogen-containing functional groups in the resin do not decompose or react and produce interfering N.sub.2O.

[0107] The duration of the heating step is preferably 1 to 15 minutes, more preferably 10 minutes at maximum. A short and fast heating is preferred so that nitrogen-containing functional groups in the resin do not decompose or react and produce interfering N.sub.2O.

[0108] In some embodiments, multiple columns, at least two columns, can be arranged in parallel to enable continuous or at least faster sampling. One cycle of trapping a sample, heating the resin, cooling the resin and regenerating the resin typically takes about 30 minutes. By using parallel columns, sampling for example at 5-minute intervals becomes possible.

[0109] Optical Measurement

[0110] In some embodiments, the optical detection is based on measuring infrared absorbance of the sample. The preferred wavenumber range is 2200 to 2250 cm.sup.−1. The preferred absorption line of CO.sub.2 for determining the amount of radiocarbon in the form of .sup.14CO.sub.2 is situated at 2209.1 cm.sup.−1.

[0111] Preferably, the light source is a tunable laser, for example a quantum cascade laser, or an optical parametric oscillator.

[0112] In one embodiment, the optical detection method is a cavity ring-down spectroscopic method, and light is detected by an infrared photovoltaic detector at the output of the cavity.

[0113] FIG. 1 illustrates schematically a laser spectroscopy apparatus in accordance with at least some embodiments of the present invention. The apparatus comprises a tunable light source 11, a gas cell 12 in form of a cavity, and a detector 13 at the output of the gas cell. The length L of the gas cell is for example 40 cm. Absorption is measured as a function of wavenumber.

[0114] In some embodiments, the spectroscopic set-up described in the publication G. Genoud et al., “Radiocarbon dioxide detection based on cavity ring-down spectroscopy and a quantum cascade laser”, Optics Letters 40 (2015) 1342-1345, and comprising a cavity down-ring spectrometer, a quantum cascade laser and an infrared photovoltaic detector is used.

EXAMPLES

Example 1: Adsorption and Release of CO.SUB.2

[0115] Air samples are flown through the resin at room temperature. The CO.sub.2 present in the sample becomes trapped. Then the resin is heated to a temperature in the range 150 to 200° C., whereby pure CO.sub.2 is released and can be lead to spectroscopic analysis. A sufficient amount of CO.sub.2 can be trapped in about 5 to 10 minutes. The trapped CO.sub.2 is almost instantly released when the resin reaches the required temperature, for example 150° C.

[0116] FIG. 2 shows results from an experiment in which we studied desorption of CO.sub.2 from a resin. 0.5 g of Lewatit VP OC 1065 resin was placed in a quartz tube. The resin was heated up to 200° C. in a He flow to clean its surface and then cooled down to 25° C. The effluent gas was analyzed using a quadrupole mass spectrometer (QMS). Carbon dioxide pulses of 1 ml were added to helium flow until the resin was saturated with CO.sub.2. The size of the peak following each pulse in the QMS remained constant. The resin was heated in helium flow ramping the temperature at a rate of 30° C./min while monitoring the desorption by means of QMS (ion current vs. temperature). The graph shows ion current (arbitrary unit) of mass number 44 as a function of temperature (° C.).

Example 2: Testing of N.SUB.2.O Adsorption

[0117] FIG. 3 shows results from an experiment in which we tested to what extent N.sub.2O is adsorbed by the anion exchange resin in accordance of an embodiment of the present invention.

[0118] The setup and procedure was the same as in the case of FIG. 2 except that the resin was pulsed with a gas mixture containing 100 ppm of N.sub.2O in nitrogen. The size of the peaks remained constant from the first pulse and no adsorption of N.sub.2O could be detected. Also the desorption curve did not show any desorbing N.sub.2O. The graph shows ion current (arbitrary unit) of mass number 44 as a function of temperature (° C.).

Example 3: Comparative Experiments by Using Either an Anion Exchange Resin or a Cryogenic Trap for the Extraction of CO.SUB.2

[0119] FIG. 4A shows an absorption spectrum measured in a method according to an embodiment of the present invention, using an anion exchange resin for extracting CO.sub.2. FIG. 4B shows a comparative absorption spectrum measured in a method that uses cryogenic trapping for extracting CO.sub.2. In both graphs, absorption coefficient is shown as a function of wavenumber. It was observed that the resin selectively adsorbs carbon dioxide without adsorbing N.sub.2O. A small amount of N.sub.2O may be released when the resin is heated to a high temperature; this phenomenon can be further reduced by minimizing the heating time. When the cryogenic trap was used, peaks originating from N.sub.2O have a high intensity in relation to CO.sub.2 peaks, which decreases the accuracy of CO.sub.2 determination.

Example 4: Parallel Columns

[0120] FIG. 5 illustrates an experimental set-up for fast sampling in accordance with an embodiment of the present invention. The sample is filtrated by a particle filter 21 before leading the sample into anion exchange columns. Three parallel columns 23 are used to enable faster sampling. Multiport valves 22 are controlled so that the filtered air sample gas flow is directed to only one of the three columns at a time. Heaters 24 are placed around the columns for carrying out release of a concentrated CO.sub.2 sample. In this embodiment, after extraction, any remaining N.sub.2O is removed from the concentrated sample by catalytic conversion 25 by using a NiO/NaOH catalyst, to further improve the accuracy of the CO.sub.2 determination. Cryogenic trapping is not needed. Thereafter, the sample is lead to a photometric measurement cell 27 comprising high-reflectivity mirrors 26a, 26b at both ends and a pressure sensor 28, and a laser spectroscopic measurement is carried out. The measurement set-up comprises a quantum cascade laser 30 as the light source, mode matching optics 29, and a photovoltaic detector 31. Section “c.” shows the result of the measurement.

[0121] It is to be understood that the embodiments of the invention disclosed are not limited to the particular structures, process steps, or materials disclosed herein, but are extended to equivalents thereof as would be recognized by those ordinarily skilled in the relevant arts. It should also be understood that terminology employed herein is used for the purpose of describing particular embodiments only and is not intended to be limiting.

[0122] Reference throughout this specification to “one embodiment” or “an embodiment” means that a particular feature, structure, or characteristic described in connection with the embodiment is included in at least one embodiment of the present invention. Thus, appearances of the phrases “in one embodiment” or “in an embodiment” in various places throughout this specification are not necessarily all referring to the same embodiment.

[0123] As used herein, a plurality of items, structural elements, compositional elements, and/or materials may be presented in a common list for convenience. However, these lists should be construed as though each member of the list is individually identified as a separate and unique member. Thus, no individual member of such list should be construed as a de facto equivalent of any other member of the same list solely based on their presentation in a common group without indications to the contrary. In addition, various embodiments and example of the present invention may be referred to herein along with alternatives for the various components thereof. It is understood that such embodiments, examples, and alternatives are not to be construed as de facto equivalents of one another, but are to be considered as separate and autonomous representations of the present invention.

[0124] Furthermore, the described features, structures, or characteristics may be combined in any suitable manner in one or more embodiments. In the following description, numerous specific details are provided, such as examples of lengths, widths, shapes, etc., to provide a thorough understanding of embodiments of the invention. One skilled in the relevant art will recognize, however, that the invention can be practiced without one or more of the specific details, or with other methods, components, materials, etc. In other instances, well-known structures, materials, or operations are not shown or described in detail to avoid obscuring aspects of the invention.

[0125] While the forgoing examples are illustrative of the principles of the present invention in one or more particular applications, it will be apparent to those of ordinary skill in the art that numerous modifications in form, usage and details of implementation can be made without the exercise of inventive faculty, and without departing from the principles and concepts of the invention. Accordingly, it is not intended that the invention be limited, except as by the claims set forth below.

[0126] The verbs “to comprise” and “to include” are used in this document as open limitations that neither exclude nor require the existence of also un-recited features. The features recited in depending claims are mutually freely combinable unless otherwise explicitly stated. Furthermore, it is to be understood that the use of “a” or “an”, i.e. a singular form, throughout this document does not exclude a plurality.

INDUSTRIAL APPLICABILITY

[0127] The present invention is industrially applicable at least in the monitoring of radiocarbon gaseous emissions in the form of carbon dioxide and methane from atmospheric samples, typically emitted from nuclear power plants or radioactive waste repositories.

REFERENCE SIGNS LIST

[0128] 11 tunable light source [0129] 12 gas cell [0130] 13 detector [0131] 21 particle filter [0132] 22 multiport valves [0133] 23 resin [0134] 24 heater [0135] 25 catalytic conversion; N.sub.2O removal [0136] 26a, 26b high-reflectivity mirrors [0137] 27 measurement cell [0138] 28 pressure sensor [0139] 29 mode matching optics [0140] 30 quantum cascade laser [0141] 31 photovoltaic detector

CITATION LIST

Patent Literature

[0142] US 2007/0217982 A1

Non Patent Literature

[0143] A. Yoshida et al., “Adsorption of CO.sub.2 on composites of strong and weak basic anion exchange resin and chitosan”, J. Chem. Eng. of Japan 35 (2002) 32-39. [0144] Fouladvand et al., “Methane Oxidation Over Pd Supported on Ceria-Alumina Under Rich/Lean Cycling Conditions”, Topics in Catal. (2013) 56:410-415. [0145] G. Genoud et al., “Radiocarbon dioxide detection based on cavity ring-down spectroscopy and a quantum cascade laser”, Optics Letters 40 (2015) 1342-1345. [0146] W. R. Alesi et al., “Evaluation of a Primary Amine-Functionalized Ion-Exchange Resin for CO.sub.2 Capture”, Ind. Eng. Chem. Res. 51 (2012) 6907-6915. [0147] I. Galli et al., “Spectroscopic detection of radiocarbon dioxide at parts-per-quadrillion sensitivity”, Optica 3 (2016) 385-388. [0148] A. J. Fleisher, D. A. Long, Q. Liu, L. Gameson, and J. T. Hodges, “Optical measurement of radiocarbon below unity fraction modern by linear absorption spectroscopy”, The Journal of Physical Chemistry Letters 0, PMID: 28880564, 4550 (2017). [0149] A. D. McCartt, T. Ognibene, G. Bench, and K. Turteltaub, “Measurements of carbon-14 with cavity ring-down spectroscopy”, Nucl. Instr. Meth. Phys. Res. B 361,277 (2015).