You are on page 1of 6

China Petroleum Processing and Petrochemical Technology Catalyst Research 2012,Vol. 14, No.

2, pp 44-49 June 30, 2012

Industrial Production of Catalyst for Removing Trace Olefins from Aromatics
Pu Xin; Shi Li
(The State Key Laboratory of Chemical Engineering, East China University of Science and Technology, Shanghai 200237)
Abstract: A novel additive incorporated into the catalyst for removing trace olefins from aromatics was proposed, and under the laboratory conditions the lifetime of the catalyst was increased from 5 h to 8 h upon specifying the conversion of the olefins equating to more than 55% as a criterion. Catalyst production, which was named ROC, has been successfully scaled up from laboratory formulations to commercial scale manufacture and over 100 tons of catalyst had been produced. The superiority in catalytic activity was identified by the evaluation tests of the ROC catalyst based on whatever kind of feedstocks (with their bromine index ranging from 400 mgBr/100g to 1 200 mgBr/100g) being used as the feedstock. The X-ray diffraction patterns had verified that the additive was highly dispersed on the surface of catalyst; the GC-FID analysis results showed that the ROC catalyst could increase the xylene content; the pyridine-FTIR spectroscopic analyses suggested that the additive could increase the amount of the weak L acids, which was the main cause leading to enhancement of the catalyst activity. Key words: olefins; aromatics; industrial production; catalyst

1 Introduction
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.

2 Experimental
2.1 Materials
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 1 Composition 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 20—40 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.

2.3 Catalytic tests in laboratory
The catalytic activity tests were carried out in a fixedbed tubular micro-reactor, equipped with a constant-flow pump to control the flow rate and a controllable heating system to maintain the required temperature. Two milliliters of the catalyst were loaded in the middle of the reactor, with the spare space filled with quartz sand (40—60 mesh). The experiments were carried out at a reaction temperature of 448 K, a reaction pressure of 1 MPa, and a WHSV of 30 h-1. The inlet and effluent liquids to and from the reactor were analyzed by a bromine index analyzer. The olefins conversion rate was: X=[(no–ni)/no]×100%, where no was the initial content of olefins, and ni was the final content of olefins.

Table 2 Analysis of active clay
Component SiO2 Al2O3 Fe2O3 CaO MgO K2O Na2O Others Mass fraction, % 72.6 12.2 3.8 1.4 2.3 0.9 1.9 4.9

2.4 Catalyst characterization
X-ray diffraction (XRD) analyses of the representative catalyst samples were carried out on a Rigaku-3014 diffractometer with a monochromator using Cu Kα (λ=0.154 nm) radiation. The diffractograms were recorded in the 2θ range of 10°—80° 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.

2.2 Catalysts preparation
The catalyst samples were prepared through kneading the

45 ·

China Petroleum Processing and Petrochemical Technology

2012,14(2): 44-49

transform infrared (FTIR) spectra of sample wafers were recorded using a FT-IR6700 spectrometer.

3 Results and Discussion
3.1 Mineralogical structure of catalysts
X-ray diffraction analysis of catalyst samples (as shown in Figure 1) was carried out in order to identify the mineralogical structure of four catalysts (A, B, C and D). The diffractograms of catalyst samples were very similar, which suggested that theses additives (metal halide, zeolite and activated carbon) as amorphous materials loaded on the surface of catalyst A had retained the original crystal structure of the catalyst A[7]. Furthermore, another reason was that these additives were present in small quantity and were highly dispersed on the large surface area of the catalyst[8]. The XRD patterns of four catalysts showed characteristic deflections at 2θ=20.86°, 26.64°, and 59.88°, respectively, that corresponded with the planes (100), (101) and (211) of silica[9] existing in the active clay as evidenced by the analytical data of Table 2.

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.

Figure 2 The influence of different additive
A—no additive; B—metal halide used as additive; C—zeolite used as additive; and D—activated carbon used as additive

3.3  valuation of the ROC catalytic perforE mance
Figure 1 XRD patterns of four catalysts (A, B, C and D)
A—no additive; B—metal halide used as additive; C—zeolite used as additive; and D—activated carbon used as additive

3.2 nfluence of different additives on cataI lytic activity
A correlation between the conversion of olefins and the composition of different additives is presented in Figure 2. The aromatics used in this experiment were obtained from SZRCC. As shown in Figure 2, the catalysts B, C and D all demonstrated higher conversion than the catalyst A at the beginning of the reaction, whereas the activity of the catalyst D declined quickly and the catalyst C almost showed the same activity as the catalyst A after
·

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 4 Comparison of the products refined by the commercial clay and the ROC catalyst
■—raw oil; ■—product treated by commercial clay; ■—product treated by ROC catalyst

3.5 Study on the acidity of different samples
To investigate the type and number of surface acidic sites, the FT-IR spectra of catalyst samples for adsorption of pyridine at 473 and 723 K, respectively, were obtained (see Figure 5). The spectrograms displayed many bands in the wavenumber range of 1 400—1 600 cm-1, which were attributed to the interaction of pyridine with the Lewis (L) acid sites and the Br nsted (B) acid sites on the sample surfaces. It can be seen from Figure 5 that the spectra represented bands of adsorption at 1 450 cm-1 and 1 490 cm-1, which were typical of adsorbed pyridine[10]. A band at around 1 450 cm-1 was identified, which appeared due to 19b ν(C—C) vibration of pyridine adsorbed at the Lewis acid sites. Another band could be seen at around 1 490 cm-1 due to contributions of both the Lewis and Br nsted acid sites[11]. There was no band identified at 1 540 cm-1, so the amount of total B acids could not be calculated. Table 3 shows the amount of the total L acids,
·

Figure 3 Evaluation of catalytic performance of ROC

3.4 Comparison of the hydrotreated products
The gas chromatography-flame ionization detection (GCFID) analyses were carried out on a Hewlett-Packard Model HP5890 gas chromatograph equipped with a capillary column (AT-WAX, with 50 m in length, 0.32 mm in inside diameter, and 0.30 μm in film thickness) for investigating the changes in the content of aromatics after reaction. The ROC catalyst and the commercial clay were compared on their performance, and the test results are presented in Figure 4. The reaction products obtained by hydrotreating in the presence of the ROC catalyst con-

47 ·

China Petroleum Processing and Petrochemical Technology

2012,14(2): 44-49

weak L acids and strong L acids.

and the ROC catalyst had higher content of weak L acids as compared to other samples, and especially the ROC catalyst contained 2.756 5×10-4 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 5×10-4 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 5 FTIR spectra of pyridine adsorbed on different samples at 473 K and 723 K
A—no additive; B—metal halide used as additive; C—zeolite used as additive; and D—activated carbon used as additive

4 Conclusions
(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.

Table 3 Acidic properties of different catalyst samples
Acidity amount, ×10–4 mol/g Sample A B C D ROC Commercial clay Total L acid sites 2.152 2 2.543 9 2.294 0 5.833 7 3.002 7 0.320 8 Strong L acid sites 0.414 0 0.089 5 0.391 7 5.572 6 0.246 2 0.134 3 Weak L acid sites 1.738 2 2.454 4 1.902 3 0.261 1 2.756 5 0.186 5

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

dustrial testing in aromatic refining[J]. Ind Eng Chem Res,

Commercial Application of Silver Catalyst YS-8810 in EG Unit of Shanghai Petrochemical Company
The high-selectivity silver catalyst YS-8810 developed by the Yanshan Branch of Beijing Research Institute of Chemical Industry and manufactured by SINOPEC Catalyst Branch Company has been applied commercially in No. 2 ethylene glycol unit at the Shanghai Petrochemical Company (SPC) since October 22, 2011. After one month of operation in the EG unit, all performance indicators of the catalyst have reached the expected norm along with high activity and operating stability of the catalyst, while its selectivity is comparable with the overseas catalyst. In May 2010 the high-selectivity catalyst YS-8810 had passed the appraisal and review by SINOPEC’s experts group. The appraisal results came to conclusion that this catalyst has reached the performance level of the similar international catalysts, which has prompted the application of this catalyst in the #2 EG unit at SPC. The outstanding outcome on application of the said catalyst has promoted the scheduled application of catalyst YS-8810 at Tianjin Petrochemical Co. and on the #1 EG/EO unit of SPC, and currently the staffs of these two petrochemical enterprises are actively engaging in technical exchange with relevant catalyst research and production personnel.
·

49 ·