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Nikolaos C. Kokkinos, Anastasia Lazaridou, Christos E. Papadopoulos, Nikolaos Nikolaou

Department of Petroleum & Natural Gas Technology Faculty of Engineering Kavala Institute of Technology (KIT) Kavala, Greece

Abstract- Fuel-ethers (MTBE, ETBE, TAME) took the place of TEL (Tetra-Ethyl Lead) as suitable octane boosters in the refinery blended gasoline pool and not as environmentally benign compounds. An environmentally friendly two-step synthesis of an upgraded light-light cracked naphtha (LLCN) could overcome the known toxic effects from the use of gasoline ether oxygenates and even more, it could successfully replace them. In the present research study, we accomplish the second and final step of the LLCN upgrade process through in situ Ru/TPPTS biphasic hydrogenation of the aldehyde content of a hydroformylated refinery (real) LLCN in aqueous media to the corresponding alcohols. The influence of the reaction pressure (50-75 bar), temperature (60-120 oC) and time (1-6 h) were examined. The highest conversion of 98.9% of the aldehydes was observed at 120 oC, 75 bar, during 2 h of reaction. Keywords- Naphtha; Refinery process; Hydrogenation; Ruthenium/TPPTS; Aqueous organometallic catalysis;

I. INTRODUCTION The ban on TEL in the early of 1970s and also the installation of the two-way and then three-way catalytic converters in automobile exhaust since 1975, which were intolerant of lead, led the refinery industry to the use of highoctane oxygenated components, called oxygenates, in order to meet the standards of US CAA Amendments of 1977 and 1990 as well as the demands of the EU Fuel Quality Directive (98/70/EC) [1] and its updates (till the update of Directive 2009/30/EC [2]). According to the ASTM D 4814, branched alkyl tertiary alkyl ethers, like methyl tert-butyl ether (MTBE), ethyl tert-butyl ether (ETBE) and methyl tert-amyl ether (TAME), belong to oxygenates. The first term of alkyl tert-alkyl ethers, MTBE, was produced in industrial quantities by ANIC in Italy in 1973 and by Chemische Werke Hls in Germany in 1976 [3]. Hitherto, ether oxygenates are added to certain gasoline (petrol) formulations to improve combustion efficiency and to increase the octane rating, known as gasoline ether oxygenates (GEOs) or fuel-ethers. Greece, as well as Germany, Italy, Finland and France, produces and uses TAME as GEO. The production capacity in TAME of the Aspropyrgos refinery in Greece is approximately

This research work was financially supported by the Kavala Institute of Technology, the Epeaek II Programme of the Greek Ministry of Education and the European Union (50/37/13).

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Aqueous biphasic Hydrogenation of the Aldehyde Content of a Hydroformylated real Naphtha cut to valuable oxygenated Products
Nikolas Psaroudakis, Konstantinos Mertis
Department of Inorganic Chemistry Faculty of Chemistry University of Athens Athens, Greece

128,000 tpa, while the European production capacity in TAME for 2011 was ca. 586,000 tonnes [4]. However, despite the fact that TEL was replaced by GEOs, due to the environmental consequences and the severe human health effects of the former, it is worthy of remark that the GEOs took the place of TEL as suitable octane boosters in the refinery blended gasoline pool and not as environmentally benign compounds. According to Bonventre et al. [5], even though MTBE, ETBE and TAME elicit some of the same vascular lesions, the additional methyl group in ETBE and TAME resulted in more toxic compounds disrupting the development of different target organ systems including the heart, skeletal, and water regulation systems. Furthermore, Ahmeds review [6] showed that TAME is more toxic in comparison with MTBE and ETBE. The most common sources of TAME environmental pollution seem to be leakages from underground gasoline storage tanks into groundwater and from discharges of refineries, too [7]. Thus, TAME disperses rapidly polluting the environment, being also highly persistent, due to its high water solubility (11 g/l at 20 oC), its high volatility (vapour pressure 9 kPa at 20 oC), its low biodegradability in the aerobic aquatic environment and its growing scale of use in the refinery industry [8]. Aspropyrgos refinery and several other contemporary European refineries produce TAME according to the process flow diagram of Figure 1. As it is illustrated in Figure 1, the feedstock of TAME production is light light cracked naphtha (LLCN) which stems from the debutanisation and depentanisation of an unsweetened light cracked naphtha (LCN) of the FCC (Fluid Catalytic Cracking) unit. The catalytic synthesis of TAME starts primarily with the addition of methanol to LLCN (specifically, to the two reactive isoamylenes, 2-methyl-2-butene and 2-methyl-1butene) [9, 10] into boiling point reactor, and then the reaction is completed with the simultaneous separation of the product from the reactants in the catalytic distillation. Therefore, it is unavoidable the production of TAME to be combined indestructibly with the loss of the octane contribution of two high-octane reactive isoamylenes.

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Figure 1. Process flow diagram of TAME production in the European refineries.

On the other hand, an environmentally friendly two-step synthesis of an upgraded LLCN that could replace the harmful TAME from the refinery blended gasoline pool is being investigated by our research group (Figure 2). Recently, we comprehensively studied the first step (Part 1) of the upgrade process of a real LLCN from the Aspropyrgos refinery in Greece [10, 11]. The olefin content of the specific refinery LLCN was successfully hydroformylated by Rh/TPPTS complex in aqueous media to the corresponding aldehydes. In the present research study, we accomplish the second (Part 2) and final step of the LLCN upgrade process through in situ hydrogenation of the produced aldehydes of the hydroformylated LLCN to the corresponding alcohols catalysed by Ru/TPPTS complex in aqueous media. After the end of the catalytic reaction, the upper organic phase holds the substrate and the products and the lower aqueous phase contains the catalyst ready for recovering. In the past, Ru/TPPTS complexes have been reported as effective catalytic systems for the biphasic hydrogenation of individual aldehydes [12-18] and of a mixture of specific aldehydes [19], too. To the best of our knowledge, this is the first report on biphasic hydrogenation of aldehydes present in a real hydroformylated naphtha cut.

Figure 2.

A. Materials and Instrumentation The hydroformylated LLCN was produced according to Kokkinos et al. [10] from a real LLCN from Aspropyrgos refinery (Hellenic Petroleum S.A.). RuCl3xH2O was purchased from Aldrich and used as catalyst precursor. TPPTS was purchased from Alfa Aesar and used as ligand. Toluene extra pure was obtained from Merck. Hydrogen 5.0 N, 2, r, Zero Air, and He 5.0 N were purchased from Axarlis (Kavala, Greece). Hydrogen 5.0 N was used in the hydrogenation reactions without further purification. Na2SO4 was used for drying and was obtained from Panreac.

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All the reactions were performed in 100 ml Autoclave Engineers batch reactor which was equipped with a low carbon stainless steel vessel (316 LSS), an electromagnetic agitation system, a cooling-heating system, a central control unit (URC) and a sampling valve [10]. The substrate and the products were analysed using a Perkin Elmer 8700 gas chromatograph (GC) with a flame ionization detector (FID) and an Agilent 6890 N/5973 N GC/MS system both of them employing a Petrocol DH 150 capillary column (150 m length, 0.25 mm diameter, 1.0 m film). Column temperature was kept initially constant at 40 oC for 5 min, then it was raised at 200 oC at a rate of 2 oC min-1 and remained there for 45 min. Helium (99.999%) was used as a carrier gas with a flow rate 20 cm/sec at 175 oC and 65 psig. In order to clean the column from various remaining redundant compounds the oven temperature was kept at 230 o C for 180 min (the temperature of both the injector and detector was 280 oC) prior to the analysis. B. Analytical Method The methods of gas chromatography with FID and mass spectroscopy were used for qualitative analysis of the hydroformylated LLCN and of the hydrogenated products. In the qualitative analysis of the substrate and of the products we used standard compounds to identify the reported peaks from the GC. Moreover, mass spectral library NIST 05 was used for component MS search and final identification. In the quantitative analysis of the hydroformylated LLCN and the hydrogenated products, it was essential to correct the areas of the reported peaks of the GC, due to the existence of organic compounds in various homologous series. In addition, the detector of a GC/FID does not count the amount of oxygen in the oxygenated compounds (e.g. aldehydes and alcohols) during the burning, because oxygen already exists in the zero air which is necessary for the combustion inside the GC/FID device. This means that the aldehydes of the substrate and the produced alcohols are underestimated. Therefore, we approximated the response factors of the reported components in order to correct for their quantities. Owing to the complexity of the substrate and the lack of literature as far as it concerns the characterisation of complicated organic mixtures, we estimated the response factors (fi) by applying the equations of Ongkiehong [20, 21] and taking into consideration the theoretical approaches of the response in a FID [22-25] for both the reactants and the products of the hydrogenation reaction (Figure 3).
Equation applying to aldehydes: = 1 + 0.3 12 Equation applying to alcohols: = 1 + 0.5 12

An environmentally friendly two-step synthesis of an upgraded LLCN.

II.

EXPERIMENTAL

Figure 3. The equations which were used to estimate the response factors (fi) for aldehydes and alcohols, respectively based upon Ongkiehongs results. Mi: Molecular weight of a compound i, ni: the amount of carbon atoms of a compound i.

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C. Hydrogenation Procedure The hydrogenation reactions as well as the analysis of the products were carried out in the Chemical Process Simulations and the Petroleum & Natural Gas Chemistry & Technology Labs of the Department of Petroleum & Natural Gas Technology, of Kavala Institute of Technology. All manipulations and reactions were performed under argon or nitrogen atmosphere using standard Schlenk techniques [26]. In the beginning of the experimental procedure, deoxygenation of distilled demineralised water was carried out via an ultrasonic cleaning bath under high vacuum for 3 h prior to use. Furthermore, a pot with the substrate of the hydroformylated LLCN was stirred in ambient temperature in order to achieve better homogenization of the mixture. The Ru-TPPTS catalyst used was prepared in situ by direct addition of RuCl3 to TPPTS in aqueous solutions. Thus, in a typical experiment, an aqueous solution of the RuCl3xH2O catalyst precursor (10 mg; 0.04 mmol) and TPPTS ligand (110.5 mg; 0.15 mmol) in water (15 ml) together with hydroformylated LLCN (7.5 ml; 37.99 mmol aldehydes) in toluene (7.5 ml) were fed in the stainless steel autoclave reactor. The reactor was then purged with hydrogen at room temperature. Afterwards, hydrogen pressurization and heating were taken place according to the desired reaction pressure and temperature. The temperature set points, the dwell time and the agitation speed were monitored and controlled by the indicators and controllers of the central control unit. Zero time of the reaction was taken when the temperature inside the autoclave reached the preferred value. At the end of the run the autoclave vessel was rapidly cooled in ice and salt, the stirring was stopped and the reactor was vented before opening it. A separation funnel was used to divide the withdrawn reaction mixture into two phases. Immediately then, the organic layer was analysed by gas chromatography. III. RESULTS AND DISCUSSION

A. Hydroformylated LLCN characterisation According to the above mentioned analytical method, a hydroformylated light-light cracked naphtha characterisation was performed by using a Perkin Elmer 8700 GC/FID and an Agilent 6890N/5973N GC/MS (MS library NIST 05) both employing a Petrocol DH 150 capillary column. The hydroformylated LLCN (Table 1) was constituted by parafins (6%), isoparafins (26%), olefins (11%), naphthens (1%), aldehydes (55%) and alcohols (1%). There were few more peaks in the GC report (indentified as C4-C5 alkanes and C5 alcohols) that were rejected, due to their total negligible amount being less than 0.03 mol%. B. Aqueous biphasic catalytic hydrogenation of aldehydes from a hydroformylated refinery LLCN A series of experiments was carried out with temperatures in the range of 60-120 oC, pressures between 50bar and 75bar and reaction times between 1 h and 6 h. Conversion is given as the mole% ratio of the initial aldehydes of the substrate minus the final aldehydes after the hydrogenation to the initial aldehydes of the substrate, yield

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as the mole% ratio of produced alcohols to the total aldehydes of the substrate, TON as the mole of alcohols per mole of Ru and TOF as the mole of alcohols per mole of Ru per hour. At the end of all the hydrogenation reactions, the reaction mixture was strictly biphasic. The upper organic layer was colourless and it contained the produced alcohols, while the catalyst remained in the yellowish lower aqueous layer.
TABLE I. CHEMICAL ANALYSIS OF THE HYDROFORMYLATED LLCN

Hydroformylated LLCN Components Molar allocation (%) PARAFINS 5.80 n-Butane 0.07 n-Pentane 5.73 ISOPARAFINS 26.14 Isopentane 26.03 2,2-Dimethyl-Butane 0.11 OLEFINS 10.57 trans-2-Butene 0.25 3-Methyl-1-Butene 0.05 1-Pentene 0.12 2- Methyl-1-Butene 1.07 trans-2-Pentene 1.61 cis-2-Pentene 0.54 2- Methyl-2-Butene 6.82 Cyclopentene 0.11 NAPHTHENS 1.01 Cyclopentane 1.01 AROMATICS 0 ALDEHYDES 55.40 3-Methyl-Butanal 3.20 2-Methyl-Butanal 0.50 Pentanal 0.34 2,3-Dimethyl-Butanal 10.07 4-Methyl-Pentanal 0.10 2-Methyl-Pentanal 13.88 2-Ethyl-Butanal 4.57 3-Methyl-Pentanal 15.53 Hexanal 4.91 2,2-Dimethyl-Butanal 0.19 Cyclopentyl-Methanal 2.11 ALCOHOLS 1.08 3-Methyl-Butanol 0.09 2-Methyl-Butanol 0.25 2,3-Dimethyl-Butanol 0.03 4-Methyl-Pentanol 0.04 2-Methyl-Pentanol 0.12 3-Methyl-Pentanol 0.16 Hexanol 0.22 2,2-Dimethyl-Butanol 0.04 Cyclopentyl-Methanol 0.13

1) Influence of reaction pressure and temperature Table II shows that a higher conversion was observed by increasing hydrogen pressure. A sensible explanation is that the rise of hydrogen pressure in the solution increases H2 dissolution in the liquid phase and thus, H2 concentration at the water-organic interface favouring so the creation and further stabilization of RuH(CO)(TPPTS)3 active catalytic complex. It must also be noted that the conversion of the aldehydes and the yield of the alcohols performed an almost parallel change with the increase of pressure, meaning that any parallel reaction that also took place preserved a steady yield.

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Moreover, a series of experiments was carried out at temperatures in the range of 60-120 oC. A higher yield was observed by increasing the reaction temperature up to 120 C (Table II). The increase in conversion was more profound above 90 C, but it was also increased, although at a lower rate, below 90 C.
TABLE II. INFLUENCE OF REACTION PRESSURE AND TEMPERATURE

Entry P1 P2 T1 T2 T3 Substrate HLLCN HLLCN HLLCN HLLCN HLLCN Catalyst Ru/TPPTS Ru/TPPTS Ru/TPPTS Ru/TPPTS Ru/TPPTS Pressure (bar) 50 75 75 75 75 Temperature (oC) 90 90 60 90 120 Total aldehydes (mol%) 91.70 75.87 93.85 74.30 1.08 Aldehydes (n/iso) 0.10 0.11 0.11 0.11 0.42 Total alcohols (mol%) 7.15 22.41 5.26 23.98 94.41 Alcohols (n/iso) 0.23 0.14 0.20 0.13 0.14 Isomerisation (mol%) 1.01 1.58 0.74 1.58 4.36 Conversion (mol%) 6.4 22.5 4.2 24.1 98.9 Yield (mol%) 5 21 3 23 94 -1 TOF (h ) 27 104 17 122 470 TON 53 208 34 224 936

2) Effect of reaction time Figure 4 illustrates the influence of reaction time in the aqueous biphasic catalytic hydrogenation of the hydroformylated LLCN assuming that the zero time (start-up time) of the reaction is the time moment where the system reaches the preset temperature (set point) and the end of the reaction is the moment that the heating was stopped. It is worthy of remark that 70% of the aldehydes were hydrogenated within the first 4h of the experiments. For reaction times more than 4h, both conversion and yield continued to increase with small and steady steps. It is also notable that the difference between conversion and yield seems to be retained stable with the increase of time; this means that the side-products of any parallel reaction preserved a constant yield.

Figure 4. Hydrogenation of a hydroformylated LLCN at different reaction times. P= 75 bar, T= 90 C, agitation= 650 rpm.

IV. CONCLUSION According to Jo [27], the interest of the chemical industry lies on the potential of catalyst recycling, on the

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simplified required technology and nowadays, on the use of less environmental hazardous chemicals, due to the stringent environmental standards and legislations. Aqueous biphasic catalytic hydrogenation of a hydroformylated LLCN is an industrially attractive approach, because: It is a green procedure, it offers an easy and efficient recovering of the catalyst by using simplified techniques, it can increase the concentration of molecular oxygen on the fuel improving its combustion properties, the new composition of the final fuel will contain less harmful and water-soluble compounds than TAME, the FON (Front Octane Number) and the RON (Research Octane Number) of the ultimate fuel will be raised [28, 29], the produced long-chain alcohols should achieve a better solubility in the fuel and probably, it should positively take off the solubility of low-chain alcohols in the fuel and finally, it will improve the storage stability of the ultimate fuel by reducing the conciseness of olefins, diolefins [10] and aldehydes. Taking everything into consideration, aqueous biphasic hydrogenation of aldehydes from a hydroformylated LLCN as an in situ and an environmentally friendly catalytic process for producing favorable oxygenated compounds could overwhelm the disadvantages from the use of the harmful and water-soluble TAME. ACKNOWLEDGMENT This research work was financially supported by the Kavala Institute of Technology, the Epeaek II Programme of the Greek Ministry of Education and the European Union (50/37/13), which are gratefully acknowledged. Special thanks are also due to Dr. A. Chatzigakis (Head of Aspropyrgos Refinery Chemical Laboratory, Hellenic Petroleum S.A.) for his support and granting of LLCN samples and to Prof. S. Mitkidou for her valuable support in GC-MS analysis. REFERENCES
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