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Catalytic Oxidation and Reduction ofPolycyclic Aromatic Hydrocarbons (PAHs)Present as Mixtures in HydrothermalMediaMARIAN ASANTEWAH NKANSAH a , ALFRED A. CHRISTY a & TANJABARTH ba Department of Science, University of Agder, Kristiansand, Norwayb Department of Chemistry, University of Bergen, Bergen, NorwayPublished online: 24 Jul 2012.
To cite this article: MARIAN ASANTEWAH NKANSAH , ALFRED A. CHRISTY & TANJA BARTH (2012):Catalytic Oxidation and Reduction of Polycyclic Aromatic Hydrocarbons (PAHs) Present as Mixtures inHydrothermal Media, Polycyclic Aromatic Compounds, 32:3, 408-422
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Polycyclic Aromatic Compounds, 32:408–422, 2012Copyright C© Taylor & Francis Group, LLCISSN: 1040-6638 print / 1563-5333 onlineDOI: 10.1080/10406638.2012.663451
Catalytic Oxidation andReduction of PolycyclicAromatic Hydrocarbons(PAHs) Present as Mixturesin Hydrothermal Media
Marian Asantewah Nkansah,1 Alfred A. Christy,1
and Tanja Barth2
1Department of Science, University of Agder, Kristiansand, Norway2Department of Chemistry, University of Bergen, Bergen, Norway
The reactivity of fluorene, anthracene, and fluoranthene under oxidation and reduc-tion conditions were investigated in this study. This project looks at catalytic andgreen approaches of converting PAHs to less toxic and/or less stable derivatives thatare amenable to further degradation. Hydrothermal reactions have been performed at300◦C with pure H2O and Nafion-SiO2 catalyst for oxidation, and pure H2O, HCOOH,Pd-C, and Nafion-SiO2 catalysts for reductive hydrogenation. Time series has been per-formed for both the oxidation and hydrogenation systems. The products of the reactionwere identified and quantified by the use of Gas Chromatography-Mass Spectrometryand the NIST Library. The reaction products include oxidized products of anthraceneand fluorene; and hydrogenated derivatives of anthracene and fluoranthene. Fluoran-thene did not undergo oxidation, and fluorene did not undergo hydrogenation under theconditions of this research.
Key Words: anthracene, fluorene, fluoranthene, hydrothermal, oxidation, reduction
Received 6 November 2011; accepted 31 January 2012.The authors are grateful to the Agder Fund and the University of Agder, Kristiansand(UiA) for financing this research and to the Department of Chemistry of the Universityof Bergen (UiB) for the use of their facilities for this work. The authors are also grate-ful to Prof. George W. Francis, Bjarte Holmelid, and Lucia Liguori Bjørsvik all of theDepartment of Chemistry, UiB for their varied contributions towards the success of thisproject.Address correspondence to Marian Asantewah Nkansah, Department of Science,Faculty of Engineering and Science, University of Agder, Service Box 422, NO - 4604,Kristiansand, Norway. E-mail: [email protected]
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Catalytic Hydrothermal Reactions of PAH Mixtures 409
INTRODUCTION
Polycyclic aromatic hydrocarbons (PAHs) such as fluorene, anthracene, andfluoranthene are known hazardous by-products of combustion in the coal,petroleum, and metal smelting industry. They are naturally generated fromvolcanos and forest fires (1–3).
PAHs belong to the group of persistent organic pollutants (POPs). Theseare organic contaminants that are resistant to degradation and can remain inthe environment for long periods (4). The notion that PAHs are inert entitieseven at high temperatures has been rarely questioned by chemists (5).
PAHs are known to pollute air, soil, and water resources at even lowconcentrations, exhibiting high thermal stability and persistence in soil andgroundwater (6).
The widespread release of PAHs is associated with health and environ-mental hazards (7) and a global treaty, whose main purpose is the total elim-ination of 12 POPs on a global scale, was signed in May 2001 in the Stock-holm Convention for the regulation of POPs (8). The European Union as wellas the USEPA have classified 16 PAHs as priority compounds with specifiedpermissible limits and the list includes fluorene, anthracene and fluoranthene(9, 10). Due to the ever increasing enforcement of regulations on the emis-sion levels of PAHs in the environment, remediation technologies have evolvedover the years to prevent increased environmental levels of these pollutants.These include landfilling (11), the use of microbes in biodegradation (12–14),incineration, chemical, and or catalytic oxidation (15–18) to gaseous productspredominantly CO2 and CxHy, ozone degradation to various oxidised products(19, 20), ultraviolet (UV) degradation (21, 22), or combination of such meth-ods. Improvements and refinements of these techniques and technologies arecontinuing. New catalysts and methods have been tried for oxidation and/orreduction of PAHs in order to produce less toxic and environmental friendlyreaction products.
In this context, Nafion catalyst has successfully been used in the oxidationas well as reduction of a mixture of PAHs. Nafion is a perfluorosulfonic acidresin, which is a copolymer of tetrafluoroethene and a perfluorosulfonyletherderivative. It is a strong Brønsted acid (23). The silicate supported Nafion cata-lyst; Nafion-SiO2 has the acid catalyst properties of Nafion resin with the highsurface area characteristic of silica as a porous support (24). Nafion catalysthas been used in the hydrodeoxygenation of bio-derived phenols to hydrocar-bons (25). A previous article from our research reports the successful oxidationand reduction of anthracene with the Nafion catalytic system (26).
In this article, the use of Nafion-SiO2 catalyst in oxidative (with H20) andreductive hydrogenation (with H2O + HCOOH + Pd-C) reaction systems fordegradation of a mixture of polycyclic aromatic hydrocarbons (PAHs) as a re-mediation measure has been explored.
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EXPERIMENTAL
Hydrothermal treatment of a mixture of flourene, anthracene, and flouran-thene under oxidative and reductive conditions has been studied using highpressure reactors. The Nafion-SiO2 catalyst which is polymeric and environ-mentally benign has been used to enhance the rate of degradation of PAHsunder both oxidative and reductive processes.
Gas Chromatography-Mass Spectrometry (GC-MS) was used for analysisof the reaction products. The reactor was tested by filling with 10 ml of waterand heating for 24 h. The volume of water remained constant.
Standards, Solvents, and ReagentsFormic Acid of 99% purity was obtained from Riedel-de Haen R©, Seelze-
Germany.Anthracene, fluorene, and fluoranthene of 98% purity, ethyl acetate,
Nafion-SiO2 and Pd-C catalysts were obtained from Sigma Aldrich, St. Louis,MO, USA.
Procedure A: Oxidation Reaction SystemAccurate aliquots of 5.0 mg each of anthracene, fluorene, and fluoranthene
were transferred into a 20 ml capacity cylindrical stainless steel (SS316) re-actor. Nafion-SiO2 of mass 5.0 mg was added. An aliquot of 5.0 ml of doublydistilled water was added and air was retained as the headspace gas. Theweight of the assembled reactor was determined before and after heating toensure that there was no leakage. The reactor was sealed and tightened withscrews. The reactor was then transferred into a pre-heated oven set at 300◦Cand heated for a predetermined period. The reactor was then removed fromthe oven and cooled in an air stream. The weight after opening the reactor toexpel any gaseous products was also determined. Batch processes of the aboveprocedure were repeated for different durations of one-hour increments untilthe rate of conversion reached a maximum.
Procedure B: Hydrogenation Reaction SystemAccurate aliquots of 5.0 mg each of anthracene, fluorene, and fluoranthene
were transferred into a 20 ml capacity cylindrical stainless steel (SS316) reac-tor. Nafion-SiO2 of mass 5.0 mg and Pd-C of mass 1.0 mg were added. Aliquotsof 5.0 ml of doubly distilled water and 0.2 ml formic acid were added. The re-actor was sealed and tightened with screws. The reactor was then transferredinto a pre-heated oven set at 300◦C. The weight of the assembled reactor wasdetermined before and after heating to ensure that there was no leakage. The
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Catalytic Hydrothermal Reactions of PAH Mixtures 411
weight after opening the reactor to expel any gaseous products was also de-termined. Batch processes of the above procedure were repeated for differentdurations of one-hour increments until the rate of conversion reached a maxi-mum.
Extraction of ResidueAfter each reaction process, the reactor was cooled to room temperature
and its content transferred into a separating funnel. The product was extractedwith 10 ml (3, 3, 4 ml) of analytical grade ethyl acetate. The organic phase wascollected into a vial and stored in a refrigerator prior to analysis.
GC-MS ConditionsGC-MS analysis was performed with the use of Thermo Scientific Trace GC
Ultra equipped with (25 m × 0.2 mm, 0.33 µm) Ultra - 2 HP WCOT fused silicacolumn by Agilent Technologies from J&W Scientific, USA. The GC is coupledwith Thermo Scientific DSQ II quadrupole Mass Spectrometer. Samples wereinjected at a rate of 1 µl min−1 by splitless injection mode and helium was usedas the carrier gas at a constant flow rate of 1 ml min−1. The oven program wasstarted at 50◦C and held for 1 min, increased at a rate of 8◦C min−1 up to 220◦Cand held for 1 min, and then increased at a rate of 10◦C min−1 up to 300◦C andheld for 1 min. Mass detection was operated in a full scan mode (m/z ratio ofrange 50–400) at 3.86 scans s−1 for product identification. Ionisation was byelectron impact at 70 eV. Ion source temperature was 250◦C.
Quality AssuranceHigh purity analytical grade chemicals were used in all cases. All glass-
ware were soaked overnight in detergent and thoroughly washed with ace-tone and dried before use. Doubly distilled water was used for all reactions.Replicate values are reported. Semi-quantification of reaction products wasconducted by determining relative percentage of peaks. Reliability of quan-tification was established by preparation of a calibration curve of solutions ofknown concentrations.
RESULTS AND DISCUSSION
The rate of decay of individual PAHs in the mixture are presented in Figures 1and 2. In Figure 1, the oxidative decay of anthracene and fluorene seems tofollow a first-order reaction law. The oxidized products are 9 H-fluorene-9-oneand 9, 10 anthracenedione. Fluoranthene did not undergo oxidation under theexperimental conditions though it was present in the mixture. Figure 2 showsthat hydrogenation of anthracene and fluoranthene increased with time butdoes not fit a linear pseudo first-order reaction. Fluorene, however, remained
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Figure 1: Degradation curves of (Ant: anthracene and Fle: fluorene): (a) In ([Ant]t/[Ant]oversus duration of hydrothermal oxidation; (b) In ([Fle]t/[Fle]o versus time of hydrothermaloxidation.
stable in the mixture throughout the reaction process. A number of hydro-genated forms of anthracene and fluoranthene were formed and these havebeen presented in Figures 3 and 4. Suggested mechanisms for oxidation andhydrogenation were presented in Figure 5. Figure 6 shows the chemical struc-tures of the reaction products and Table 1 shows some properties of the purePAHs considered in the study.
Figure 2: Degradation curves of: (a) Anthracene (%) vs. duration of hydrothermalhydrogenation; (b) Fluoranthene (%) vs. duration of hydrothermal hydrogenation.
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Catalytic Hydrothermal Reactions of PAH Mixtures 413
0
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80
1 2 3 4 5 6 7 8 9 10 11 12
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Figure 3: Relative percent composition of hydrogenated products of anthracene versustime (DHA: 9, 10 - dihydroanthracene, THA: 1, 2, 3, 4-tetrahydroanthracene, OHA: 1, 2, 3, 4, 5,6, 7, 8 - Octahydroanthracene, ISO - OHA: 1, 2, 3, 4, 4a, 9, 9a, 10 - octahydroanthracene).
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Figure 4: Relative percent composition of hydrogenated products of fluoranthene versustime (THF: 1, 2, 3, 10b -Tetrahydrofluoranthene, HHF: 6b, 7, 8, 9, 10,10a-Hexahydrofluoranthene).
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Oxidation Reaction of Fluorene, Anthracene, and FluorantheneThere was complete oxidation of anthracene and fluorene to 9, 10 -
anthracene-dione and 9H-fluorene-9-one, respectively, while fluoranthene re-mained un-reactive after 7 h (Figure 1). In the oxidation process, it is assumedthat oxygen from air in the reactor head acts as an oxidant.
AnthraceneAnthracene showed 73.82% degradation within the first 1 hour to 100.00%
degradation in 7 hours (Figure 1a) at 300◦C. Anthraquinone was the only prod-uct formed from anthracene oxidation at all durations of oxidation reaction. Ina previous part of this study where hydrothermal treatment was done withanthracene without other PAHs, there was complete oxidation of anthracenein 6 h in the presence of Nafion but oxidation started in the second hour andincreased steadily until completion. Although anthracene was proven to un-dergo a slow oxidation in the presence of water without Nafion-SiO2 catalyst,a yield of only 48.4% degradation was observed for 96 h at 400◦C, a clear in-dication that the Nafion-SiO2 catalyst enhanced the rate of conversion in thisinstance. It was also observed that though the same ratio of reactants wasused in both cases, the initial rate of degradation of anthracene was enhancedin the mixture relative to experiments with only anthracene. Rate constants Kof 0.3504 and 0.4514 were obtained for reactions involving anthracene onlyand anthracene in a mixture, respectively (26). From the results, it seemsthe mechanism of oxidation is a straightforward oxidation of anthracene, asshown in Figure 5. The first step oxidation leads to anthrone. Further oxida-tion of anthrone leads to anthraquinone. It appears that anthrone functionedas an intermediate in this reaction since it was not detected in any of the re-action products. Oxidation of anthracene to 9,10-anthracene-dione and or withother products has been extensively studied by other authors with differentreaction systems such as metachloroperbenzoic acid (m-CPBA) as oxidant inthe presence of iron and manganese porphyrins (FeF20TPPCl, MnF20TPPCl,FeCl8TPPCl and MnCl8TPPCl) as catalysts yielding anthrone, oxanthrone,and anthraquinone (27). Also, anthracene oxidation with cerium (IV) ammo-nium nitrate in the presence of air yielded 99.6% anthraquinone precipitate(28)].
FluoreneComplete oxidation of fluorene to 9H-fluorene-9-one was observed in 7 h
but the rate was faster than that of anthracene with 67.43% degradation in 1 hto 100.00% in 7 h (Figure 1b). This could be attributed to the fact that fluorenehas a lower molecular weight (166 g/mol) as compared to that of anthracene(178 g/mol) and therefore molecules have a high kinetic energy which leadsto more effective collisions and fast formation of products. The mechanism of
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Catalytic Hydrothermal Reactions of PAH Mixtures 415
Figure 5: Suggested mechanisms for oxidation and hydrogenation processes. (i)Anthracene oxidation; (ii) fluorene oxidation; (iii) anthracene hydrogenation; (iv)fluoranthene hydrogenation.
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Figure 6: Chemical structures of the identified product compounds in this study (i)–(vi).
oxidation is again straight forward as in the case of anthracene (Figure 5). Suc-cessful production of 9H-fluorene-one has been reported by other authors forreaction of fluorene by alkaline hexacyanoferrate (III) (29) and vanadium (V)in aqueous acetic acid containing 1.0 M sulfuric acid at 50◦C (30), an indicationthat the oxidation of fluorene can be performed at relatively low temperaturesin strong acidic medium.
FluorantheneFluoranthene remained stable and did not undergo oxidation through-
out the reaction durations of 1–7 h. The use of a stronger oxidising agentother than O2 from air probably will give a satisfactory result since successfuldegradation of fluoranthene in soil has been achieved with the use of Fenton’sReagent (H2O2 + FeSO4) (31). Air oxidation of fluoranthene in the presence
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Catalytic Hydrothermal Reactions of PAH Mixtures 417
Table 1: Chemical properties of parent PAH in this study.
Chemical Molecular Molecular Boiling point Water solubilityname formular weight (◦C) 25◦C (mg/l) Structure
Fluorene C13H10 166.22 298.0 1.690
Anthracene C14H10 178.23 339.9 0.045
Fluoranthene C16H10 202.25 375.0 0.265
of minerals such as calcite, clay, and silica at 100◦C also resulted in decom-position to CO2 and other CXHY gaseous products (32). Most of the researchon oxidation of fluoranthene are bacteria induced and includes Mycobacteriumsp. strain PYR-1 and P.ostreatus mycelium degradation to 9-fluorene-9-one andother products (10, 33), an indication that flouranthene is susceptible to bacte-ria oxidation than chemical oxidation.
Reductive Hydrogenation of Fluorene, Anthracene,and FluorantheneThe experimental results indicate that there was 100%, 55%, and 0.0%
hydrogenation of anthracene, fluoranthene, and fluorene, respectively. Formicacid, HCOOH acts as hydrogen precursor for the hydrogenation processes (34).The hydrogenation processes are predicted to proceed by a mechanism similarto the Birch reduction of aromatic hydrocarbons. However, the reduction is notselective (35).
AnthraceneComplete degradation of anthracene by hydrogenation was observed in
12 h starting with 81.14% degradation in the first hour (Figure 2a). The hy-drogenated products were identified as 9,10 - dihydroanthracene (DHA), 1,2, 3, 10b - tetrahydroanthracene (THA), 1, 2, 3, 4, 5, 6, 7, 8 - octahydroan-thracene (OHA), and 1, 2, 3, 4, 4a, 9, 9a, 10-octahydroanthracene (Iso-OHA).These products were observed in a previous study when hydrothermal oxida-tion of anthracene alone resulted in complete conversion in 8 h. However, itshould be noted that the mass of anthracene in the previous study was 1.0 mgas compared to 5.0 mg of individual PAHs in this study. Considering durationof 8 h for 1.0 g anthracene to 12 h for a mixture of 5.0 g each of anthracene,
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fluorene, and phenanthrene, it could be said that the individual PAHs have asynergetic effect on the individual reaction rates (26). It was observed that al-though anthracene content decreased with time of reaction, the same cannot besaid about the hydrogenated products of anthracene. For reaction time of 1 h,the distribution was 48.47% - DHA, 31.10% - THA, and 1.57% - OHA, howeverthe distribution trend did not have a correlation with time of reaction. In thefinal product, however, the percentage of THA was highest at 67.35% with thatof the rest being 15.61% - DHA, 67.35% - THA, 15.68% - OHA, and 1.36% of Iso-OHA a new product (Figure 3). This trend could be attributed to isomerisationand continous hydrogenation. However, combination of the Pd-C and Nafion-SiO2 catalysts together with HCOOH enhances degradation. This is observedwhen compared to results of anthracene hydrogenation with only HCOOH at400◦C in the presence of water which yielded only 47.2% of hydrogenated prod-ucts in 96 h (26). The mechanism follows the Birch type reduction but does notstop after the formation of 9, 10-dihydroanthracene (34). This is similar to re-sults reported by Nelkenbaum et al. (6), where hydrogenation was achieved bythe use of TMPyP-Ni catalyst and nano-ZVI as an electron donor. Nelkenbaumet al. achieved complete hydrogenation in 168 h at ambient temperature andpressure (6).
FluoreneThe fluorene used in this experiment had <1.0% I, 4-dihydroflourene as
impurity. This figure remained constant throughout all the batch reactions upto 12 h. Fluorene was un-reactive to the hydrogenation system employed inthis work. Thus, hydrothermal reaction at 300◦C was not suitable for fluorenereactivity. Research done by scientists in the Department of Chemical Engi-neering, University of Delaware indicates that catalytic hydrogenation andhydrocracking reaction for fluorene is possible at 335–380◦C and 153-atm to-tal pressure when presulfided NiW/A12O3 catalyst is used for isomerizationand hydrogenation to yield 1, 2, 3, 4, 4a, 9a-hexahydrofluorene and ultimatelyperhydrofluorene (36).
Reaction of a mixture of anthracene, phenanthrene, and fluoreneNiMo/Al2O and H2 at 573 K by Koltai et al. (37) indicated that the order of hy-drogenation of fluorene was several orders of magnitude lower than the othercomponents of the mixture. This confirms that fluorene has a high chemicaland thermal stability with regards to reduction (37).
FluorantheneThe hydrogenation of fluoranthene started at 5.71% in the first hour of the
reaction and increased steadily to 55.0% in 12 h. The hydrogenated product
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Catalytic Hydrothermal Reactions of PAH Mixtures 419
was mainly 1, 2, 3, 10b - tetrahydrofluoranthene (THF), throughout the reac-tion until 12 h when 2.26% of 1, 2, 3, 6b, 7, 8, 9, 10, 10a-Hexahydrofluoranthene(HHF) was formed (Figure 4). A time series on the catalytic reaction for fluo-ranthene hydrogenation and further hydrocracking was perfomed by Lapinaset al. (38) in the temperature range of 310–380◦C and 153 atm.
Fluoranthene hydrogenation was catalyzed by a presulfided NiW /A1203
catalyst, whereas its hydrogenation and subsequent hydrocracking were cat-alyzed by a presulfided NiMo/zeolite-Y catalyst to yield tetrahydrofluoran-thene and finally to perfluoranthene (38). The temperature range used by Lap-inas et al. (38) is high when compared to the current study at 300◦C.
CONCLUSION
The degradation of PAHs remains a global challenge to the quest to limit pollu-tion from these hazardous chemicals. The experimental results from this studyconfirm that it is possible to use Nafion-SiO2 and H2O reaction systems at300◦C to obtain 100% oxidisation of anthracene to anthraquinone. It also indi-cates that fluorene can undergo 100% conversion to 9 H-fluorene-9-one underthe same chemical conditions. However, fluoranthene is stable and not reactiveunder these conditions. On the other, reductive hydrogenation in the presenceof Nafion-SiO2, H2O, HCOOH and Pd-C at 300◦C for 12 h resulted in 100% and55.0% conversion of anthracene and fluoranthene, respectively, while fluoreneremained un-reactive.The presence of other PAHs enhanced the conversion of anthracene.The order of the extent of the individual PAHs to oxidation is as follows:
fluorene > anthracene > fluoranthene
The order of the extent of the individual PAHs to hydrogenation is as follows:
�Decreasing oxidation
Products like anthaquinone and 9-H-fluorene-9-one have industrial and medi-cal applications if isolated.
�anthracene > fluoranthene > fluorene
Decreasing hydrogenation
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