Professional Documents
Culture Documents
1Introduction
At the petrochemical enterprises, aromatic streams obtained from catalytic reforming and cracking processes always contain undesirable trace olefins[1] which are harmful to the downstream technological processes and the applications of aromatics[2]. Hence, the impurities must be removed before aromatic streams are routed to the petrochemical processes provided with the suitable treatment technologies[3]. Two processes have been proposed for removing trace olefins from aromatics[4] (i.e., activated clay treating and catalytic hydrogenation treating) and currently most refineries in China are still using the clay treatment technologies to remove olefins. However, the commercial clay material has a very limited lifetime and should usually be land-filled when it is discarded, which will definitely cause pollution to the environment. Through the efforts of our research team, several new catalysts with longer lifetime have been developed and compared with the commercial clay through side-stream tests [5]. In order to achieve better performance of the scale-up product, a novel type of additive, which can alleviate the catalyst deactivation effectively, is expected to
be envisaged. The present paper is a continuation of our research on removing trace olefins from aromatics[6]. In this work, the effect of different additives that would be modifying our synthesized catalyst was studied. Then, the optimum conditions for commercial manufacture of the proven catalyst were selected. Under the strict supervision by means of the available techniques, over 100 tons of the ROC catalyst for removal of trace olefins from aromatics had been produced at Kairui Chemical Co., Ltd. of Hebei province, China.
2Experimental
2.1Materials
The aromatic hydrocarbons were obtained from the bottom of the naphtha reforming column at the Sinopec Zhenhai Refining and Chemical Company (SZRCC), the CNOOC Huizhou Refining and Chemical Company (CHRCC) and the Sinopec Guangzhou Refining
Corresponding Author: Professor Shi Li, E-mail: yyshi@ecust. edu.cn; Telephone: +86-21-64252274.
44
Pu Xin, et al. Industrial Production of Catalyst for Removing Trace Olefins from Aromatics
and Chemical Company (SGRCC). The bromine index of three aromatics samples was equal to about 1 200 mgBr/100g, 650 mgBr/100g, and 400 mgBr/100g, respectively. Three feedstock samples mainly contained paraxylene, m-xylene, o-xylene, C9 aromatics, and C9+ aromatics with their compositions presented in Table 1. The density of three aromatic samples was around 0.87 g/mL. The active clay used as solid support in the laboratory and the factory was collected from Anhui province, China. The components of the active clay are shown in Table 2.
Table 1Composition of aromatic hydrocarbons
Component Non-aromatics Benzene Toluene Ethylbenzene p-Xylene m-Xylene o-Xylene C9 aromatics C9+ aromatics Mass fraction, % SZRCC 1.77 0.09 0.01 6.39 7.54 16.89 10.94 37.29 19.09 CHRCC 0.52 0.02 0 5.78 9.50 19.52 11.32 36.54 16.80 SGRCC 0.28 <0.01 0 6.42 10.43 21.44 11.98 35.58 13.87
clay with different additives and a proper amount of the transition metal ions for 0.5 h prior to being extruded to form the extrudate. The catalyst was dried at 393 K for 2 h to remove the solvent and moisture, baked in a muffle furnace at 423 K for 2 h., and then crushed and screened to 2040 mesh before use. The industrial procedures for manufacture of the ROC catalyst were as follows. Firstly, the clay and the metal halide were mixed completely in a mixing kneader, and then a suitable amount of transition metal solution was added. Secondly, the raw materials which had been mixed through stirring for 0.5 h were sent to a twin-screw extruder by the conveying system; thirdly, the moisture of the extrudate was removed in a belt drier at 393 K in a two-hour drying process; and finally, the extrudate was baked in another belt drier at 433 K for 2 h.
2.4Catalyst characterization
X-ray diffraction (XRD) analyses of the representative catalyst samples were carried out on a Rigaku-3014 diffractometer with a monochromator using Cu K (=0.154 nm) radiation. The diffractograms were recorded in the 2 range of 1080 in steps of 0.04 with a scanning rate of 2 ()/min. The surface acidity was investigated through adsorption of pyridine on the solid surface of catalyst samples. Prior to pyridine adsorption, sample wafers were evacuated at 753 K under high vacuum, followed by pyridine adsorption at room temperature. Finally, the wafers were desorbed at 473 K and 733 K, respectively. The Fourier
The catalyst A was the clay modified via incorporating the transition metal ions without any additive; and the catalyst B was prepared from the catalyst A through kneading with a metal halide additive; the catalyst C was prepared from the catalyst A through kneading with a zeolite; and the catalyst D was prepared from the catalyst A through kneading with the activated carbon.
2.2Catalysts preparation
The catalyst samples were prepared through kneading the
45
2012,14(2): 44-49
transform infrared (FTIR) spectra of sample wafers were recorded using a FT-IR6700 spectrometer.
4 h of reaction. It should be noted that the catalyst B maintained a higher activity than other catalysts during the whole reaction process. At the end of eight-hour reaction, catalysts A, B, C and D maintained an olefin conversion of more than 55% over a reaction duration of 5 h, 8 h, 5 h and 4.5 h, respectively. The activity of the catalyst B increased by 60% in comparison with the catalyst A used as a reference. In addition, it can be found from Figure 2 that the commercial clay maintained a conversion rate of above 55% for 2.5 h. The catalyst B was about 3.2 times more active in comparison with that of the commercial clay. Because of its superior performance, the processing parameters of the catalyst B were selected for the commercial application at Kairui Chemical CO., Ltd.
It can be seen obviously from Figure 2 that the catalyst B had demonstrated a long lifetime. The ROC catalyst used for removing olefins from aromatics stream was produced by keeping the same processing parameters as those of the catalyst B. In order to verify whether the ROC catalyst could replace the commercial clay, a series of studies had been carried out and the results are showed in Figure 3. Figure 3a shows that a higher catalytic activity could be achieved by the ROC catalyst used for removing olefins from aromatics stream that was obtained from SZRCC than did the commercial clay that was used at the Sinopec Zhenhai Refining and Chemical Company. Above 55% of the olefins conversion can be attained for 8 h of reaction upon application of the ROC catalyst, while the olefins conversion of the commercial clay had fallen to 55%
46
Pu Xin, et al. Industrial Production of Catalyst for Removing Trace Olefins from Aromatics
after only 2.5 h of reaction. This result has revealed that the lifetime of the ROC catalyst had greatly improved. In Figure 3b, the ROC catalyst was applied to treat different aromatics streams which were obtained from SZRCC, CHRCC and SGRCC. After 8 hours of reaction, the olefin conversions of three samples reached 55.66%, 78.29% and 66.61%, respectively. It can be concluded that the ROC catalyst was able to treat different aromatics streams with high catalytic activity as evidenced by Figure 3b.
tained a higher concentration of para-xylene, m-xylene, o-xylene and C10 aromatics than did the commercial clay along with a lower content of C9 aromatics. This comparison implied that the distribution of the aromatics after being hydrotreated by the ROC catalyst tended to increase the amount of xylene, which was in accord with the aim of the PX combination units. The test result confirmed the expectation that the ROC catalyst could take the place of the commercial clay thanks to its high catalytic activity and better product distribution.
Figure 4Comparison of the products refined by the commercial clay and the ROC catalyst
raw oil; product treated by commercial clay; product treated by ROC catalyst
47
2012,14(2): 44-49
and the ROC catalyst had higher content of weak L acids as compared to other samples, and especially the ROC catalyst contained 2.756 510-4 mol/g of weak L acids which were the highest value among all samples. This fact was in accordance with the catalytic activity data and can be concluded that the increase in activity of the catalyst was attributed to the increase in the amount of the weak L acids. The amount of the weak L acids in the commercial clay was only 0.186 510-4 mol/g, which could explain why the commercial clay activity was much poorer than the ROC catalyst as evidenced by Figure 3a. Since the commercial clay had large surface area and relatively high pore volume, this commercial clay upon reaching its adsorption equilibrium would be deactivated quickly. The catalyst D had a large amount of strong L acids and these strong L acids could enhance the polymerization of olefins[12]. This was why the catalyst D had a high conversion at the beginning of the reaction. When the polymers occupied the mesopores provided by the active clay, the catalyst D would decay quickly. The catalyst C could not change much in the amount of the weak L acids and its activity data were close to those of the catalyst A.
Figure 5FTIR spectra of pyridine adsorbed on different samples at 473 K and 723 K
Ano additive; Bmetal halide used as additive; Czeolite used as additive; and Dactivated carbon used as additive
4Conclusions
(1) The XRD analyses indicated that the structure of the catalyst sample after addition of metal halide had not been changed and the metal halide was dispersed amorphously on the surface of the support. (2) The catalytic activity tests showed that the activity and capacity of catalysts for removing trace olefins from the aromatics stream after addition of metal halide to the catalyst samples had greatly improved by 60% under laboratory conditions as compared to the catalyst consisting of clay kneaded with the transition metal without any additive. (3) The ROC catalyst performance demonstrated a great superiority over the commercial clay and it could be applied to treat different aromatics streams. The GC-FID analyses confirmed the increase in the target product (xylene) content after reaction. Because of its excellent performance, the ROC catalyst had got the permit for using this catalyst at the Sinopec Zhenhai Refining and Chemical Company.
It can be seen from Table 3 that the amount of total L acids existed in all three samples (B, C and D) and increased after adding the metal halide, the zeolite and the activated carbons, respectively. However, the amount of the weak L acids showed an enormous difference among these catalyst samples. It is obvious that the catalyst B
48
Pu Xin, et al. Industrial Production of Catalyst for Removing Trace Olefins from Aromatics
(4) The acidity of the four catalyst samples was evaluated, indicating that the amount of the weak L acid sites increased after incorporation of metal halide to the catalyst A, and the enhancement of the efficiency on removing olefins in aromatics streams through catalytic reaction was attributed to the increase in the amount of the weak L acid in the catalyst composition.
Acknowledgments: We thank the Sinopec Zhenhai Refining and Chemical Company for their help in the experiments.
2011, 50 (12): 7150-7154 Li [6] G L, Luan J N, Zeng X S, et al. Removal of trace olefins from aromatics over metal-halides-modified clay and its industrial test[J]. Ind Eng Chem Res, 2011, 50 (11): 66466649 Guerra S R, Merat L M O C, Gil R A S S, et al. Alkyla[7] tion of benzene with olefins in the presence of zirconiumpillared clays[J]. Catal Today, 2008 133: 223-230 Kasztelan S, Moffat J B. The oxidation of methane on het[8] eropolyoxometalates: III. Effect of the addition of cesium on silica-supported 12-molybdo-phosphoric acid, molybdena, vanadia, and iron oxide[J]. J Catal, 1988, 112(1): 54-65 Kawi S, Yao Y Z. Silica bonded K10 montmorillonite [9] (SBM): A high surface area catalytic clay material[J]. Microporous Mesoporous Mater, 1999, 28: 25-34 [10] Hoang V T, Qing I H, Adrian U, et al. Effect of the acid
References
[1] Brown S H, Waldecker J R, Lourvanij M. Process for reducing bromine index of hydrocarbon feedstocks: The United States, US 7744750[P]. 2005 Chen C W, Wu W J, Zeng X S, et al. Study on several mes[2] oporous materials catalysts applied to the removal of trace olefins from aromatics and commercial sidestream tests[J]. Ind Eng Chem Res, 2009, 48 (23): 10359-10363 Stephen H B, Terry E H, Arthur P W. Decreasing BI-reac[3] tive contaminants: The United States, US 6368496B1[P]. 2002 [4] Brown S H, Helton T E, Werner A P. Decreasing Br-reactive
properties on the diffusion of C 7 hydrocarbons in ULZSM-5 materials[J]. Microporous Mesoporous Mater, 2006, 92: 117-128 [11] Pranjal K, Narendra M G, Rajiv K. Synergistic role of acid
sites in the Ce-enhanced activity of mesoporous Ce-AlMCM-41 catalysts in alkylation reactions: FTIR and TPDammonia studies[J]. J Catal, 2007, 245: 338-347 [12] Awate S V, Waghmode S B, Agashe M S. Synthesis, char
contaminants in aromatic streams: The United States, US 6781023[P]. 2004 [5] Luan J N, Li G L, Shi L. Study of modified clay and its in
acterization and catalytic evaluation of zirconia-pillared montmorillonite for linear alkylation of benzene[J]. Catal Commun, 2004, 5: 407-411
49