Journal of Industrial and Engineering Chemistry 17 (2011) 788793

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Journal of Industrial and Engineering Chemistry

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Decarboxylation of naphthenic acid using alkaline earth metal oxide

Hyun-Young Oh a, Jong-Ho Park a,*, Young-Woo Rhee b, Jong-Nam Kim a
a b

Green House Gas Research Center, Korea Institute of Energy Research, 71-2 Jang-Dong, Youseong-Gu, Daejeon 305-343, Republic of Korea Department of Chemical Engineering, Chungnam National University, Daejeon 305-764, Republic of Korea

A R T I C L E I N F O

A B S T R A C T

Article history: Received 20 August 2010 Accepted 15 December 2010 Available online 14 May 2011 Keywords: Naphthenic acid Decarboxylation Base catalyst

Removal of naphthenic acid in model acid solution by the catalytic decarboxylation using alkaline earth metal oxide catalysts such as MgO, CaO, BaO and SrO was investigated. Among the alkaline earth metal oxides, MgO and CaO showed better activity than BaO and SrO. The surface properties of MgO have been modied by calcination or hydration followed by dehydration under vacuum and the effects of those treatments on the catalytic activities were investigated. Although the calcination at higher temperature reduced the BET surface area and number of basic sites, it gave the highest decarboxylation activity. The CPMgO which was made by hydrationdehydration under vacuum gave the highest BET surface area and number of basic sites. But, the catalytic activity of CPMgO was inferior to the catalyst calcined at 800 8C. This fact implies that both pyrolytic and catalytic reactions play important roles in decarboxylation of naphthenic acid. FT-IR spectra of the catalysts before and after reaction gave the evidence for the formation of bulk magnesium naphthenate, which is the reaction intermediate of the pyrolytic decarboxylation. 2011 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights reserved.

1. Introduction Naphthenic acids in crude oil are responsible for corrosion of pipeline and distillation unit during the rening of acidic crudes. In addition, the naphthenic acids can react with other metal salts to form sludge and gum during the transportation to reneries, which makes scales on the surface of process unit and stabilizes crude oil emulsion. Even though the naphthenic acid causes many problems in the renery process, the interest to acidic crude has been recently increased because of its lower price than conventional oil. Naphthenic acid represents a group of organic acids, which has a carboxylic functional group attached to a cyclopentane or a cyclohexane ring through a CH2-group or a chain containing up to ve or more CH2-groups. Since the acidic compounds in oil are very complicated, the content of acid in oil is usually dened by total acid number (TAN), the number of milligrams of KOH required neutralizing the acidity of 1 g oil. And the crude oil with a TAN greater than 0.5 is considered as acidic crude. Since the naphthenic acid in crude oil makes so many problems that the removal of naphthenic acid before it enters main renery has become an important unit process for fully utilizing the economic benet of acidic crude.

* Corresponding author. E-mail address: jongho@kier.re.kr (J.-H. Park).

Renery uses metallurgy upgrading or dilution with a low TAN crude oil to reduce the problems related to the processing the high TAN crude. But, those methods are not entirely satisfactory because those methods require high investment cost or diminish the value of the low TAN crude. There are several efforts to minimize the acidity based on extraction. Wang et al. used ammonia solution of ethylene glycol to remove the naphthenic acids from a second vacuum fraction [1]. On the other hand, Wu used an isopropyl alcohol-ammonia-water solvent to extract naphthenic acids [2]. The extraction can substantially remove the naphthenic acid, but the process generates large amount of wastewater and emulsions that are problematic to treat. Catalytic removal of naphthenic acids has been studied for a many years. It has been revealed that transition metal catalyst could reduce the acidity of crude oil under the hydrogen atmosphere because it consumes large amount of hydrogen [3]. But, it has not been commercialized yet. Recently, it has been reported that alkaline earth metal oxides decompose the naphthenic acids in crude oil and substantially reduce the acidity of crude oil through the decarboxylation reaction [4]. The advantage of the catalytic decarboxylation is that it does not consume any hydrogen and shows higher activity than hydrotreating process. Catalytic decarboxylation is a well-established chemical reaction in organic processes and it has been widely applied in organic synthesis. For example, ZrO2 promotes the catalytic decarboxylation of acetic acid in supercritical water (673 K, 2540 MPa) [5]. Zeolite has also been investigated for the

1226-086X/$ see front matter 2011 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights reserved. doi:10.1016/j.jiec.2011.05.024

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catalytic decarboxylation of benzoic acid, but its reaction occurred at around 400 8C [6]. It is well-known that the catalytic activity of alkali earth metal oxide is greatly affected by the pre-treatment conditions like calcination at high temperature and the precursor used to make the nal catalyst [7]. And, it has been reported that hydration and dehydration of MgO can change the surface properties such as surface basicity and BET surface area [8,9]. But, the roles of these pre-treatments have not been thoroughly studied by Zhang et al. [4]. In this study, the catalytic activity of various alkali earth metal oxides has been compared in a wide range of catalyst to acid weight ratio to screen the best catalyst for decarboxylation of the naphthenic acid. The effects of calcination conditions and hydration-dehydration treatment on the catalytic activity of MgO have been investigated. 2. Experimental 2.1. Model acid solution The model acid solution includes ve different acids such as CPCA (Cyclo Pentane Carboxylic Acid), CHCA (Cyclo Hexane Carboxylic Acid), CHPA (Cyclo Hexane Propionic Acid), BA (Benzoic Acid) and TP-CHCA (Trans-4-Pentyl Cyclo Hexane Carboxylic Acid). Each acid was dissolved in dodecane solvent about 0.5 wt%, respectively. So, the total amount of acids was 2.5 wt% in dodecane. Used carboxylic acids have RCOOH functional group with 5 or 6 member carbon rings and heavy molecular weight.

2.2. Catalyst preparation Three types of alkali earth metal oxides were used in this study, CMMeO, CMeO, and CPMeO (Me = Mg. Ca, Sr, Ba). The prex CM, C, and CP represent commercially available metal oxides, calcined metal oxides, and conventionally prepared metal oxide, respectively. CMMeO was purchased from Junsei Chemical Co, which was used without pre-treatment. CMeO was prepared by calcining the corresponding CMMeO at three different temperatures, 400 8C, 600 8C, 800 8C for 10 h with ramping rate of 1 8C/min. For the preparation of CPMeO, the same procedure used by Stark et al. [9] was adapted in this study. The CPMgO was prepared by subjecting the CMMgO to hydration for 24 h and dehydration under vacuum at 350 8C. 2.3. Catalyst characterization The surface basicity and base strength distribution of the catalysts were determined by the temperature-programmed desorption of CO2 (CO2-TPD). The measurement was carried out using a gravimetric apparatus (TGA-Q50). Before the measurement, the catalysts were pre-treated at 400 8C under helium and then CO2 gas was introduced for 30 min at the room temperature. And then, physically adsorbed CO2 was desorbed at room temperature in a ow of helium for 30 min. Finally, the catalysts were heated up to 400 8C with a ramping rate of 5 8C/min. The BET surface areas of the catalysts were obtained with an ASAP 2010 (Micrometrics). The catalysts were pretreated at 200 8C prior to N2 adsorption. XRD was also performed on a MAX-Ultima plus.

Fig. 1. Schematic diagram of ow reactor.

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H.-Y. Oh et al. / Journal of Industrial and Engineering Chemistry 17 (2011) 788793 Table 1 Physical properties of CM, C, CPMgO. CMMgO BET suface area (m /g) Micropore area (m2/g) Average pore diameter (A)
2

2.4. Catalytic activity The sealed VCR tube was used as a batch reactor. The model acid solution of about 4 ml has been lled in tube reactor and then predetermined amount of catalyst was added to the solution. The batch reactors were placed in a furnace to start the reaction under 250 8C for 3.5 h. After the reaction, the reactors were quenched by immersing the reactors to cold water bath to prevent any further reaction. In addition to the batch experiments, a ow reaction was also performed to investigate the stability of the catalysts in a 3/8inch stainless steel tube reactor. Fig. 1 shows the schematic diagram of the ow reactor used in this study. A HPLC pump was used to feed the model acid solution or dodecane solution to the reactor at a constant ow rate. The reaction temperature was controlled by the mufe furnace surrounding the reactor and the reaction pressure was xed by a back pressure regulator installed on the top of the reactor. The reaction efuent was collected every 30 min after the reaction started. The concentrations of acidic compounds were analyzed by a GC-FID equipped with an Allteck ECTM WAX column. 3. Results and discussion 3.1. Catalytic decarboxylation with alkali earth metal oxides In order to compare the catalytic activity of different alkali earth metal oxides, a series of batch reaction experiment was performed varying the weight ratio of catalyst to NA (naphthenic acid). Fig. 2 shows the total acid conversion at 250 8C when various alkali earth metal oxides were used for the naphthenic acid removal. It is seen in Fig. 2 that MgO and CaO show better catalytic activity compared to BaO and SrO, especially at lower catalyst/NA weight ratio. The order of catalytic activity was BaO < SrO < MgO < CaO at lower catalyst/NA weight ratio, which is the same as the order Zhang et al. [4] reported. The reactivity order gradually changed to BaO < SrO < CaO < MgO when the catalyst/NA weight ratio increased above 10 wt%. The reason why the order of catalytic

CMgO 30.73 4.668 129.47

CPMgO 210.42 29.38 69.67

47.24 36.75 67.87

activity between CMMgO and CMCaO is reversed with the increase of the catalyst/NA weight ratio is unclear up to now. More than 95% of acids in the model acid solution were removed at 20 wt% of catalyst/NA weight ratio when the CMMgO was used. The total acid conversion of CMCaO, CMBaO, CMSrO at the same catalyst/NA weight ratio was 80%, 55%, 62%, respectively. Since the catalytic activity of MgO was the highest at high catalyst/ NA weight ratio and the activity was maintained for longer reaction time compared to the other catalysts, MgO was chosen as a catalyst for the decarboxylation of naphthenic acid. 3.2. Catalytic decarboxylation with CM, C, CPMgO It is well known that the surface properties of MgO are greatly affected by various pretreatments such as calcination at high temperature [7]. In this section, the effects of those pretreatments on the catalytic activity of MgO are investigated. CMgO represents a catalyst calcined at 800 8C with heating rate of 5 8C/min. The BET surface area and average pore diameters of the catalysts are summarized at Table 1. As expected, CMgO showed lowest BET surface area (30.7 m2/g) due to excessive sintering. As reported by Lee and Park [10], hydration followed by dehydration under vacuum greatly increased the BET surface area. The BET surface area of CPMgO has increased to 210.4 m2/g from 47.2 m2/ g. It can be noted from the Table 1 that the hydrationdehydration treatment is helpful to generate micro and meso pores. Surface basicity and the number of basic sites on the catalysts have been affected by the pre-treatment. Fig. 3 shows the temperature programmed desorption pattern of CO2 from the three catalysts. Regardless of the pretreatment, the highest desorption peaks of the CMMgO, CMgO, and CPMgO were observed at around 64 8C. Different from CMMgO, the CPMgO

Fig. 2. Catalytic decarboxylation of naphthenic acids in dodecane with alkali earth metal oxides at 250 8C batch test.

Fig. 3. Basic sites and its strength of CM, C, CPMgO on CO2 TPD.

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shows wide distribution of basic strength, which is characterized by the desorption temperature. In case of CMMgO, most of the basic sites are located within the range between 30 8C and 175 8C. The number of basic sites stronger than peak desorption temperature gradually decreased with temperature. But, CP MgO has the basic sites where carbon dioxide is desorbed above 250 8C and the number of basic sites between 100 8C and 240 8C is almost constant. The total number of basic sites which can be obtained by integrating the peak area above the baseline was the highest for CPMgO. This observation matches to the fact that CPMgO has the highest BET surface area. The total number of basic sites followed the order of CMgO < CMMgO < CPMgO. XRD analysis was carried out to identify the crystal structure of MgO catalysts. It is seen in the Fig. 4 that the CMMgO and CPMgO consist of both MgO and Mg(OH)2, but the peak of Mg(OH)2 is not observed on the CMgO. This means that the Mg(OH)2 phase was completely removed during the calcination at 800 8C. Moreover, the peak intensity at 2u = 438 and 628 has increased by the calcination temperature of MgO catalyst. This indicates that the crystallinity of MgO has been enhanced after calcination. Also, it is considered that the presence of Mg(OH)2 structure is due to the adsorption of H2O in the air. 3.3. Catalytic activity of CM, C, CPMgO Fig. 5 shows the catalytic activities of three catalysts, CMMgO, CMgO, and CPMgO with the weight ratio of catalyst to NA at 250 8C. The catalytic activity of CMgO was slightly higher than other catalysts at lower MgO/NA ratio. For example, at 7 wt% MgO/ NA ratio, the total acid conversion of CMMgO, CMgO and CP MgO was 38%, 45% and 27% respectively. Regardless of the catalysts used, the total acid conversion increased almost linearly with the increase of the catalyst loading, especially below 10 wt% and it reached 98% conversion at 40 wt% catalyst loading. This means that the decarboxylation reaction is not inhibited by the product produced during the reaction. The total number of basic sites follows the order of C MgO < CMMgO < CPMgO as mentioned above. But, the activity of the catalysts does not follow the above order. It is completely reverse of the order especially at low catalyst loading, below 4 wt%. Although the CMgO has the lowest BET surface area and the total number of basic sites, the catalytic activity was better than other MgOs. It seems that the BET surface area and total number of basic sites do not play an important role in the decarboxylation of

Fig. 5. Catalytic activity of CM, C, CPMgO in 250 8C batch test.

naphthenic acid. The reason for this will be discussed in later section. 3.4. Effects of calcination temperature Among the various pretreatment conditions, calcination at high temperature gave the best resultshighest decarboxylation activity. It has been reported that the catalytic activity of a base catalyst varies with the calcinations temperature and the best calcination temperature depends on the type of the reaction. In this section, the effects of calcinations temperature will be discussed. The BET surface areas of the calcined MgO at three different temperatures were listed in Table 2. It should be noted that the heating rate for these preparation was 1 8C/min. Because of sintering, the BET surface areas of the catalysts have decreased with the increase of the calcination temperature. The BET surface areas of C400, C600, C800MgO were 41.1, 32.1, and 8.1 m2/g, respectively. The BET surface of MgO calcined at 400 8C was close to its original one, CMMgO. This implies that the MgO can maintain its original structure without much sintering below 400 8C calcination. Fig. 6 shows the CO2 TPD patterns of three catalysts prepared at different calcination temperature. The total number of basic sites of the catalysts followed the order of C400MgO > C600 MgO > C800MgO. For all three catalysts, the peak desorption temperature of the catalysts was observed at around 68 8C. This is very similar to the peak desorption temperature of the commercial MgO. It was 66 8C. Both the catalysts showed wide distribution of basic strength compared to other catalysts calcined at 600 8C and 800 8C. It is seen from Fig. 6 that all the basic sites of MgO calcined at 400 8C lose its basicity above 250 8C similar to the CMMgO. This again conrms that the calcination at 400 8C does not cause any severe change in surface property as shown in the BET surface measurement.
Table 2 Physical properties of C400, C600, C800MgO. C400MgO BET surface area (m2/g) Micropore area (m2/g) Average pore diameter (A) 41.12 18.26 72.159 C600MgO 32.06 3.90 109.95 C800MgO 8.14 0.72 137.61

Fig. 4. XRD peaks of CM, C, CPMgO.

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Fig. 6. Basic sites and its strength of calcined-MgO on CO2 TPD.

Fig. 8. Catalytic activity of C400, C600, C800MgO in 250 8C batch test.

With the increase of calcination temperature, the total number of basic sites on the catalysts gradually decreased. As the calcination temperature increases from 400 8C to 600 8C, strong basic site corresponding to the desorption temperature of 250 8C disappears more drastically than that corresponding to 150 8C. This means that the stronger basic sites are more unstable than the weaker ones. Fig. 7 shows the XRD pattern of the MgO calcined at different temperatures. It is seen from Fig. 7 that peak for Mg(OH)2 crystal completely disappears by calcinating above 400 8C. The peaks around 388, 528 and 588 corresponds to the Mg(OH)2 crystal and it was observed only on the CMMgO. This implies that calcination above 400 8C is enough for complete dehydration of MgO. The peak intensity of MgO structure has grown as the calcination temperature increased. This fact means that the crystallinity of calcined MgO has been improved by calcination at high temperature.

3.5. Catalytic activity of calcined catalysts The catalytic activity of MgO calcined at three different temperatures was compared by batch reaction using model acid solution. The results were shown in Fig. 8. As expected, the activity has been increased as the MgO/NA ratio has increased. More than 75% removal of acidic compound was achieved with all three catalysts at 10% MgO/NA ratio. It was found that the C800MgO showed the highest activity. The total acid conversions of C400MgO, C600MgO and C800 MgO at 10 wt% of MgO/NA were 75%, 85%, 90%, respectively. The BET surface area, number of basic sites and strength of catalysts were not directly related to the catalytic activity. As shown above, C400MgO has large number of basic sites and surface area. But the activity of the catalyst was the lowest among the catalyst. The same phenomena were observed for CMMgO, CMgO, and CP MgO. This means that the decarboxylation reaction occurs both through pyrolysis and surface catalytic routes. Pestman et al. has studied about the ketonization of acetic acid on MgO catalyst [11]. They found that ketonization of acetic acid took place via two different mechanisms, that is, pyrolytic and catalytic routes. In pyrolytic reaction pathway, acetic acid and MgO

Fig. 7. XRD peaks of C400, C600, C800MgO.

Fig. 9. IR spectra of CM, C, CPMgO.

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adsorption of carbon dioxide evolved during the reaction. Also, there is CH group at 2856 cm1 and 2923 cm1. The appearance of the characteristic absorption peak of magnesium naphthenate implies that MgO forms complex with naphthenic acids during the reaction. This is the reaction intermediate of the pyrolytic reaction pathway. Other catalysts also show similar IR spectra after they are used. Metallic salts of naphthenic acid (metal naphthenates) like a (RCOO)2Mg are soluble in hydrocarbon solvents [14]. This may cause problems in renery like plugging the pipelines so that the formation of metal naphthenates should be minimized to be applied as commercial catalysts. Fig. 11 shows the ow reaction experiment results with the calcined catalysts. All the catalysts showed 100% removal efciency of naphthenic acids for 10 h. The photos in the gures shows the reaction products collected during the reaction. For all catalysts, a white suspension of a solid particle was observed. This may be the cluster of metal naphthenates formed during the reaction. To minimize the formation of this white solid suspension would be the next topic of our research.
Fig. 10. IR spectra of C400, C600, C800MgO.

4. Conclusion Catalytic decarboxylation of naphthenic acid in model acid solution was investigated using alkaline earth metal oxide catalysts such as MgO, CaO, BaO and SrO. Among the alkaline earth metal oxides, MgO and CaO showed better activity than BaO and SrO. The effects of surface modication by calcination and hydration of MgO on the catalytic activities were investigated. Although the calcination at higher temperature reduced the BET surface area and number of basic sites, it gave highest decarboxylation activity. The CPMgO which made by hydrationdehydration treatment under vacuum gave the highest BET surface area and number of basic sites, as expected. But, the catalytic activity of the catalyst of CPMgO was inferior to the catalyst calcined at 800 8C. This implies that both pyrolytic and catalytic reaction play an important roles in decarboxylation of naphthenic acid. FT-IR spectra of the catalysts before and after reaction gave the evidence for the formation of bulk magnesium naphthenate, which is the reaction intermediate to decompose to carbon dioxide and water at elevated temperature. Since the metal naphthenates formed during the reaction can be dissolved in hydrocarbon and plug the pipelines, it can be a problem in commercializing the catalysts. The ow reaction experiment with the calcined MgO catalysts veried that almost 100% of acidic compound can be removed with the catalysts, but a white solid suspension eluted during the reaction which can block the pipeline after long time of operation. It is necessary to develop an acid resistance base catalyst for the commercialization of decarboxylation process and this would be the next topic of our research. References
[1] [2] [3] [4] [5] [6] [7] [8] [9] [10] [11] [12] [13] [14] Y. Wang, Z. Chu, B. Qiu, C. Liu, Y. Zhang, Fuel 85 (2006) 2489. J.H. Wu, Lubricant (Chinese) 14 (3) (1999) 8. D.K. Lee, I.C. Lee, S.I. Woo, Appl. Catal. A: Gen. 109 (1994) 195. A. Zhang, Q. Ma, K. Wang, X. Liu, P. Shuler, Y. Tang, Appl. Catal. A: Gen. 303 (2006) 103. M. Watanabe, H. Inomata, R.L. Smith, K. Arai, Appl. Catal. A: Gen. 219 (2001) 149. Y. Takemura, A. Nakamura, H. Taguchi, K. uchi, Ind. Eng. Chem. 242 (1985) 312. H. Hattori, Mater. Chem. Phys. 18 (1998) 533. T. Ushikubo, H. Hattori, K. Tanabe, Chem. Lett. (1984) 649. J.V. Stark, D.G. Park, I. Lagadic, K.J. Klabunde, Chem. Master 8 (1996) 1904. M.H. Lee, D.G. Park, Bull. Korean Chem. Soc. 24 (2003) 10. R. Pestman, R.M. Koster, A. duijne, J. Pieterse, V. Ponec, J. Catal. 168 (1997) 265. G. Zou, R. Liu, W. Chen, Z. Xu, Mater. Res. Bull. 42 (2007) 1153. N.A. Nechitailo, M.V. Hishkina, V.F. Trapeznikova, M.A. Dzyubina, S.P. Brusentseva, A.N. Niyazov, Pet. Chem. U.S.S.R. 20 (1980) 115. L.F. Fieser, M. Fieser, Advanced Organic Chemistry, Reinhold, New York, 1961.

Fig. 11. Catalytic stability of C400, C600, C800MgO in 250 8C ow test.

rst forms bulk magnesium acetate, Mg(CH3COO)2, releasing water at low temperature and then it decomposes to CO2 and acetone at elevated temperature. Another reaction pathway, acetic acid is rst adsorbed dissociatively on catalytic surface and then transformed to acetone, CO2 and water. The same reasoning may be applied for the decarboxylation of naphthenic acid. In case of pyrolytic reaction pathway, surface properties like basic strength of active site and the number of base sites are not important. This is why the catalytic activities of MgO catalysts do not directly related to the BET surface area and the number of base sites. To verify that pyrolytic reaction is one of the possible reaction routes during the base-catalyzed removal of naphthenic acid, the FT-IR spectra of the fresh and used catalysts were measured. Figs. 9 and 10 show the IR spectra of CM, C, CPMgO and C400, C600, C800MgO catalysts respectively before and after batch reaction test. A fresh CMMgO has absorption band around 445 cm1 and 3700 cm1, which correspond to MgO stretching and isolated OH group [12]. IR-spectrum of used CMMgO shows the absorption band at 1430 cm1 and 1573 cm1, which corresponds to the stretching of carbonyl group in Magnesium naphthenate [13]. A small absorption peak appearing at 2345 cm1 Resulted from the