DOI: 10.1007/s11814-014-0115-2 eISSN: 1975-7220 INVITED REVIEW PAPER INVITED REVIEW PAPER
Solvent screening for the separation of ethylbenzene and p-xylene by extractive distillation Yukwon Jeon*, Sung Wook Row*,**, Gichun Lee*, Sang Sun Park*, Young-Jong Seo***, Young Hwan Chu****,†, and Yong-Gun Shul*,†
*Department of Chemical and Biomolecular Engineering, Yonsei University,
50 Yonsei-ro, Seodaemun-gu, Seoul 120-749, Korea **GS Engineering & Construction, 33 Jong-ro, Jongro-gu, Seoul 110-130, Korea ***The 4th Research Team, Daedeck Research Institute, Lotte Chemical Corp., Jang-dong #24-1, Yuseong-gu, Daejeon 305-726, Korea ****Department of New Energy · Resource Engineering, College of Science & Engineering, Sangji University, 124, Sangjidae-gil, Wonju-si, Gangwon-do 220-702, Korea (Received 8 March 2014 • accepted 16 April 2014)
Abstract−Extractive distillation is one of the most effective processes for the separation of ethylbenzene and p-xylene. The goal was to find single solvents or combinations of multi-solvents with good properties while minimizing the ratio of solvent to feed. The distillations were performed at equilibrium to determine the relative volatility of ethylbenzene to p-xylene with the extractive solvents under isothermal condition. For a single extraction solvent, 1,2,4-trichlo- robenzene had the highest relative volatility at 1.123. In some cases, combinations of two or three solvents were used as well as different ratios of solvent to feed to investigate the synergy effect of the mixture solvents. The binary solvent mixture of 1,2,4-trichlorobenzene and maleic anhydride (2 : 1) had the best performance with a relative volatility of 1.228 at the solvent/feed ratio of 1 : 1. Some of the solvents were further studied at different solvent/feed (S/F) ratios. Selected solvents generally tended to have higher relative volatilities at high S/F ratios, but the operation cost will in- crease. Therefore, it is important to find the proper conditions to optimize the S/F ratio for extractive distillation from the industrial point of view. Keywords: Ethylbenzene, p-Xylene, Extractive Distillation, Solvent Screening, Relative Volatility
INTRODUCTION Table 1. Chemical structures, physical properties, and uses of eth-
ylbenzene and p-xylene Ethylbenzene (EB) and p-Xylene (PX) have a great importance Ethylbenzene p-Xylene in petrochemical industries for their use as a main base for the syn- thesis of many organic compounds. For example, ethylbenzene is a major precursor for styrene, which is principally used in the manu- Structure facture of plastics. p-Xylene is used on a large scale to manufac- ture terephthalic acid, which is a basic feedstock of the polyester industry. Thus, pure ethylbenzene and p-xylene are in great demand. Normal boiling point [K] 409 411 In the industrial field, these two feed stocks can come from mixed Normal melting point [K] 178 221 xylene, which comes as a mixture of o-xylene, m-xylene, p-xylene and ethylbenzene [1-4]. Recuperation and purification of each iso- Use Styrene Ester production mer are essential processes for high value products. The purity of ethylbenzene and p-xylene for the subsequent process is required volatility of ethylbenzene to p-xylene is 1.06; thus, the separation with a high grade. For the dehydrogenation of ethylbenzene to sty- of ethylbenzene and p-xylene by distillation is impractical and uneco- rene, greater than 99.5% of the ethylbenzene purity is demanded. nomical because of their close boiling points and vapor pressures. The presence of impurities affects the catalytic reaction of produc- This conventional rectification of ethylbenzene and p-xylene needs ing styrene and may promote a side effect which prevents to adjust the use of fractional columns containing more than 200 plates and the desired purity of the product. However, this is technically a dif- high reflux ratio to assure effective separation thereof [7]. Since ficult process due to the large similarity of their physical properties, ethylbenzene and p-xylene are C8 aromatic isomers, the separa- which makes the relative volatility low (Table 1) [5,6]. The relative tions by chemical means are not quite attractive for the industrial applications [8,9]. Therefore, the distillation characteristics are of † To whom correspondence should be addressed. considerable practical importance. The effective separation of these E-mail: [email protected], [email protected] two components by the addition of the solvent to increase the selec- ‡ This article is dedicated to Prof. Hwayong Kim on the occasion of his tivity is a challenge to realize the industrial process. retirement from Seoul National Univerisity. Extractive distillation is one of the most effective processes for Copyright by The Korean Institute of Chemical Engineers. separating compounds with close boiling points. The Krupp-Kop- 1824 Solvent screening for the separation of ethylbenzene and p-xylene by extractive distillation 1825
pers (KK) extractive distillation method is used with different non- gate the effect of combined mixtures. The ratio of solvent to feed volatile components as solvents. With extractive distillation as opposed (S/F) was also varied for selected solvents to monitor solvents with to azeotropic distillation, the extractive agent boils at a much higher high separation ability at low quantity. temperature than any of other the mixture components. The solvent should be easily separable from the bottom product, and should not EXPERIMENTAL SECTION react chemically with the components or the mixture, or cause cor- rosion in the equipment. This prevents the formation of low-boiling 1. Materials and Solvent Selection azeotropes, thus rendering pure distillates after a single extractive The feed materials were ethylbenzene (Sigma-Aldrich, anhydrous, distillation [10,12]. Although extractive distillation has a wide accep- 99.8%) and p-xylene (Yakuri Pure Chemicals, ≥99%). In general, tance in some hydrocarbons--for example, toluene from nonaromatic commercial simulator PRO/II provides a high-level and field-proven hydrocarbons, this separation method has not been recently inves- degree of detail in simulating processes. It may be reliable for con- tigated in separating ethylbenzene and p-xylene. The advantage of ventional hydrocarbons when the ionic liquids may have some devi- using extractive agents for this separation is the possibility of increas- ations from the experiments. In our case, however, we observed the ing the relative volatility (EB/PX), which leads to a reduction of the trend in the separation of EB and PX by different solvents. There- theoretical plates when the ethylbenzene separates from the p-xylene fore, a commercial simulator PRO/II was used to calculate the infinite with a purity of 99%. From the literature, the relative volatility of dilution activity coefficient for the estimation of the ehtylbenzene 1.11 requires 87 plates and the relative volatility of 1.20 will even selectivity for the solvent pre-selection. Estimated solvents included reduce the plate requirement to less than 50 plates. Therefore, some aromatics, chlorinated aromatics, carbonyls, straight chains, alcohols, researchers tried some extractive agents to increase the relative vola- cyclics, sulfoxides and phosphates. Some solvents and the three other tility to more than 1.20 before, but these were either ineffective or ionic liquids were selected from other research of aromatics extrac- unstable. Possible candidates with a large potential are the ionic liq- uids which have a high chemical and thermal stability, broad liquid range and high capacity for the extractive distillation of ethylben- zene and p-xylene. They have been studied for the extractive sol- vents as single compounds to increase the relative volatility for EB and PX separation, such as aromatics, chlorinated aromatics, car- bonyls, straight chains, alcohols, cyclics, sulfoxides and phosphates. For example, 1,2,4-trichlorobenzene increases the relative volatility from 1.06 to 1.11, which shows an enhancement in the performance of EB and PX separation [12-15]. For the mixture of the agents, Berg found that the mixtures with two or three components are more effective than the single com- pounds. However, the mechanism of separating ethylbenzene and p-xylene by extractive distillation was not clearly proved of their complex phenomena when the solvent was applied [12-14]. Gen- erally, the effectiveness of an extraction solvent is related to the ways that it interacts on a molecular level with the feeds to be distilled. The extraction solvent’s ability to effect a separation of the two com- ponents depends on its molecular size, shape, and charge distribu- tion. In general, non-ideal behavior of solvent with the ethylbenzene and p-xylene mixture is hard to estimate by the current knowledge. A good assay requires that many solvents of different structures, electronic configurations, and polarities be tested. From a practical point of view, the solvent must alter the relative volatility by a wide enough margin for a successful result. Toxicity, quantity, cost and availability of the solvent should be considered for practical uses [13-15]. Sometimes, the engineering bottleneck is the ratio of sol- vent to feed (mixture to separate) because of the solvent cost and the separation energy of the solvent. Therefore, a wide variety of different solvents at different conditions need to be tested to cover the possible process evaluation. We examined different extractive agents, referred to herein as Fig. 1. Experimental setup. “solvents,” for their abilities to separate ethylbenzene and p-xylene. ① Condenser TE. Thermocouple type K Under consistent experimental conditions, various ionic liquids and ② Reflux drum (250 mL) TR. Temperature recorder several solvents were evaluated for their abilities if they could adjust ③ Boiling pot (500 mL) AP. Sampling point the relative volatilities of a 1 : 1 mixture of p-xylene and ethylben- ④ Heating mantle with zene. Specific binary and ternary solvents were tested to investi- ④ magnetic stirrer Korean J. Chem. Eng.(Vol. 31, No. 10)
