20th Annual Saudi-Japan Symposium Catalysts in Petroleum Refining & Petrochemicals Dhahran, Saudi Arabia - December 2010

Conversion of Heavy Reformate into Xylenes over Mordenite-based Catalysts in a Fluidized-Bed Reactor
Y. Wangb, S. A. Alia, A. M. Aitania, M. A. Alia, C. Ercanb, S. Al-Khattafa*
a

Center of Research Excellence in Petroleum Refining & Petrochemicals, King Fahd University of Petroleum & Minerals, Dhahran 31261, Saudi Arabia
b

Research & Development Center, Saudi Aramco, Dhahran, 31311, Saudi Arabia

* Dr. Sulaiman Al-Khattaf, Tel.: +966-3-860-1429; Fax: +966-3-860-4234; E-mail: skhattaf@kfupm.edu.sa

1. Introduction Transalkylation of heavy reformate to value-added xylenes is considered a practical route to utilize the excess heavy reformate. With more refineries opting for refinery-petrochemical integration, transalkylation of heavy reformate is becoming one of the favorable routes to boost their operating profit margins. Heavy reformate contains mainly TMBs and MEBs, together with some minor quantities of C10+ aromatics. Due to the variety of compounds present in heavy reformate, parallel and consecutive set of reactions takes place during the transformation of heavy reformate as illustrated in Figure 1. The desired reaction is the transalkylation of TMBs and toluene to produce two moles of xylenes. When heavy reformate is converted, the amount of toluene required for this reaction is produced from the dealkylation of heavier aromatics. In addition, the disproportionation of TMBs and toluene and dealkylation of alkylbenzenes take place. Activity and selectivity of catalysts used in the conversion of large aromatic molecules such as TMBs, MEBs and heavier alkyl substituted (C10+) aromatics are significantly influenced by the dimensions and the pore structure of the catalysts. Al-Khattaf et al. (2010) reviewed the application of zeolites as shape selective catalysts for transalkylation reactions. Several zeolite-based catalysts have been reported in laboratory studies by Tsai et al. (1999) on the transformation of toluene and TMBs. Serra et al. (2005) reported the performance of multizeolitic catalysts with different zeolites and metals impregnation in the transalkylation of heavy reformate. It was found that zeolite pore size and geometry have a direct influence on dealkylation and transalkylation of the different alkyl groups. The present study investigates the conversion of heavy reformate to xylenes over Hmordenite-based catalysts with different concentrations of acid sites in a fluidized bed reactor. Two mordenite catalysts with, widely different Si/Al ratios, were the key components of the catalysts. The effects of a mixture of mordenite and ZSM-5 catalysts on C9 conversion, selectivity to xylenes and product distribution have been studied as well. 2. Experimental 2.1. Materials Table 1 lists the six mordenite-based catalysts with or with ZSM-5 zeolite used in this study. Commercial heavy reformate, used as feed, was obtained from a refinery.

Table 1. Catalyst Composition and Ammonia TPD Results

Composition*, wt.% H-Mordenite 66 33 33 H-ZSM-5 66 33 Weak Acid Site Amount (mmol/g) 0.50 0.47 0.48 0.01 0.11 0.10 Peak Temp. (C) 185 185 185 150 180 180 Strong Acid site Amount (mmol/g) 1.08 0.91 0.96 0.16 0.19 0.19 Peak Temp. (C) 500 500 490 410 400 370 Total Acid Amount (mmol/g) 1.58 1.38 1.44 0.17 0.30 0.29

Catalyst ID M1 M1Z1 M1Z2 M2 M2Z1

M2Z2 33 * Balance: 34wt.% alumina binder (AP-3)

2.2. Catalyst Characterization Acidity measurement of the mordenite-based catalysts was carried out by temperature programmed desorption (TPD) of ammonia. The results are presented in Table 1. 2.3. Riser simulator Catalytic tests were carried out in a riser simulator reactor which is a bench-scale system with internal recycle unit invented by de Lasa (1992). All experiments were conducted at a catalyst/reactant ratio of 5 (mass of catalyst = 0.81g, mass of reactant feed injected = 0.162 g); residence times of 5, 10, 15 and 20 s; and temperatures of 400 C. 2.4. Feed and Product Analyses Heavy reformate feed and reaction products were analyzed using an Agilent 6890N GC equipped with a flame ionization detector (FID). The composition of heavy reformate feed, as presented in Table 2, includes about 96 wt.% C9 and 4% C10 aromatics. Among the C9 components, TMBs (55.7 wt.%) and MEBs (34.1 wt.%) were the major constituents. Table 2. Composition of the Commercial Heavy Reformate
Major Compound Iso-propyl benzene n-propyl benzene 1-methyl 2-ethyl benzene 1-methyl 3-ethyl benzene 1-methyl 4-ethyl benzene 1,2,3-tri-methyl benzene 1,2,4-tri-methyl benzene 1,3,5-tri-methyl benzene n-butyl benzene 1,4-diethyl benzene 1,3-diethyl benzene 1,3-dimethyl, 5-ethyl benzene 1,4-dimethyl, 2-ethyl benzene Others C10s Abbreviation iPB nPB 1M2EB 1M3EB 1M4EB 1,2,3TMB 1,2,4TMB 1,3,5TMB Total C9 aromatics nBB 1,4DEB 1,3DEB 1,3DM5EB 1,4DM2EB Total C10 aromatics Composition (wt.%) 1.7 4.3 6.5 18.5 9.1 6.6 39.0 10.1 95.9 0.5 0.8 0.4 0.8 0.4 1.2 4.1

3. Results and Discussion 3.1 Characterization of the Catalysts The results of catalyst characterization by TPD are presented in Table 1. M1 catalyst possessed weak as well as strong acid sites while M2 exhibited lowest weak as well as strong acid sites. Mixing M1 with ZSM-5 (Z1) resulted in decrease in total acidity from 1.58 to 1.38 mmol/g. Mixing M1 with Z1 caused slightly more reduction in both weak and strong acidity than mixing with Z2. However, mixing M2 with ZSM-5 (Z1 or Z2) resulted in increase in total acidity from 0.17 to about 0.30 mmol/g. 3.2 Conversion over Mordenite Catalysts with Different Si/Al Ratios The conversion of heavy reformate was investigated over two mordenite-based catalysts (M1 and M2). Figure 1 presents the composition of products obtained at different reaction times over M1 and M2 catalysts.
100 Catalyst: M1 90 80 70
Product Distribution (wt.%)
Product Composition (wt.%)

100 Catalyst: M2 90 80 70 C9s 60 50 TMBs 40 MEBs 30 20

Xylenes Toluene C10s Benzene

60 50 40 MEBs 30 20 10 0 0 5 10 15 Time (secs) 20 25 TMBs C9s

Xylenes 10 0 0 5 10 15 Time (secs) 20 C10s Toluene Benzene 25

Figure 1. Product distribution over M1 and M2 catalysts Table 3 presents the composition of products and conversions obtained at 400oC and reaction time of 20s. C9 aromatic content in the heavy reformate decreased from 95.9 wt.% to 52.5 wt.% with M1 and to 63.8 wt.% with M2 after 20 s reaction time. This result indicates that mordenite having higher acid site concentration (M1) exhibited higher C9 conversion. The conversion of MEBs was 58.4 wt.% and 50.7 wt.% over M1 and M2, respectively. These values are higher compared to the conversion of TMBs (35.4 wt.% and 20.1 wt.% over M1 and M2, respectively. These results indicate that MEBs are more reactive than TMBs. The conversion of TMBs as well as MEBs was higher over M1 than M2.

Table 3. Product Distribution and Conversion of Heavy Reformate at 400 C and 20 s Reaction Time
Feed Composition (wt.%) 0.0 0.0 0.0 0.0 0.0 0.0 0.0 1.7 4.3 6.6 39.0 10.1 6.5 18.5 9.1 4.2 100.0 0.0 55.7 34.1 95.8 4.2 ----M1 10.7 3.5 13.3 0.3 3.9 8.5 4.2 0.6 1.3 3.5 25.9 6.6 2.6 7.6 4.0 3.1 100.0 16.6 36.0 14.2 52.5 3.1 45.2 35.4 58.4 26.2 M1Z1 9.1 2.8 13.1 0.3 4.7 10.2 4.9 0.5 1.2 3.6 25.6 7.0 2.3 6.9 3.6 3.8 100.0 19.8 36.2 12.8 51.1 3.8 46.7 35.0 62.5 9.5 M1Z2 9.9 2.8 13.7 0.4 5.0 11.0 5.1 0.5 1.1 3.3 24.1 6.9 2.1 6.4 3.3 4.0 100.0 21.1 34.3 11.8 48.1 4.0 49.8 38.4 65.4 4.8 M2 2.6 0.9 6.2 0.8 3.7 8.0 4.0 0.0 1.3 4.3 31.1 9.1 2.9 9.2 4.7 10.0 100.0 15.7 44.5 16.8 63.8 10.0 33.4 20.1 50.7 -M2Z1 4.6 2.0 11.5 0.6 5.3 11.6 5.5 0.4 0.8 3.8 26.4 8.3 1.9 5.7 2.9 7.9 100.0 22.4 38.5 10.5 51.0 7.9 46.8 30.9 69.2 -M2Z2 4.3 2.2 11.7 1.0 4.0 8.7 4.1 0.3 0.7 4.3 29.5 10.1 1.9 5.8 2.8 7.7 100.0 16.8 43.9 10.5 56.3 7.7 41.2 21.2 69.2 --

Light gases (C1-C4) Benzene Toluene Ethylbenzene para-Xylene meta-Xylene ortho-Xylene i-Propylbenzene n-Propylbenzene 1,2,3-TMB 1,2,4-TMB 1,3,5-TMB 1M2EB 1M3EB 1M4EB C10 aromatics Total Grouped amounts Xylenes TMBs MEBs C9 aromatics C10 aromatics Conversions, wt.% C9s Conversion TMBs Conversion MEBs Conversion C10s Conversion

Dealkylation of MEBs: Higher content of toluene and light gases from M1 catalyst indicate that this catalyst favors dealkylation of MEBs to toluene and ethylene Once the toluene is formed, the transakylation of TMBs and toluene to form xylenes takes place. On the other hand, the products from M2 contain lower amount of toluene and light gases indicating significantly lower dealkylation of MEBs. Such a difference in dealkylation of MEBs between M1 and M2 can be attributed to acid site concentration. Disproportionation of TMBs: Another interesting difference between two mordenite catalysts is the amount of C10 aromatics in the reaction product mixtures. C10 aromatics, specially tetramethyl benzenes, can be formed either from transalkylation of TMBs and toluene or from disproportionation of TMBs. For this transalkylation reaction to occur, the presence of toluene is necessary. As mentioned earlier, M2 does not favor dealkylation of MEBs to form toluene. Hence the formation of significantly higher amount of C10 aromatics in products from M2 can be attributed to disproportionation of TMBs resulting in formation of xylenes and tetra methyl benzenes. This result indicate that the catalyst with lower acid site concentration (M2) favors the formation of xylenes via disproporationation of TMBs.

Xylenes Yield: Xylene yield after 20 s of the reaction time was 16.6 wt.% and 15.7 wt.% with M1 and M2, respectively. The difference in the total xylenes yield over M1 and M2 is narrow (about 1 wt.%) despite the significant difference in acid site concentration. This result indicates that, depending on the catalyst acid site concentration, the formation of xylenes can take different reaction pathways with little difference in overall yield. 3.3 Conversion over Mixture of Mordenite/ZSM-5 Catalysts Compared to M1, the M1Z1 catalyst resulted in slight increase (1.5 wt.%) in C9 aromatics conversion. A higher increase (4.6 wt.%) in C9 aromatics conversion was observed with M1Z2 (Table 3). Compared to M2, M2Z1 catalyst exhibited significantly (13.4 wt.%) increase in the conversion of C9 aromatics. However, M2Z2 resulted in a lesser enhancement (7.8 wt.%) of C9 aromatics conversion (Table 3). Dealkylation of MEBs: Compared to M1, the M1Z1 catalyst resulted in an increase (4.1 wt.%) in MEBs conversion. Further increase (7.0 wt.%) in MEBs conversion was observed with M1Z2. However, toluene yield remained almost constant in products from M1, M1Z1 and M1Z2 catalysts. Compared to M2, both M2Z1 and M2Z2 catalysts resulted in a significant increase (18.5 wt.%) in MEBs conversion. It was also observed that the toluene yield increased (5.5 wt.%) in products from M2Z1 and M21Z2 compared to M2 catalyst. An increase in C1-C4 gaseous products was also observed. Therefore, it can be stated that dealkylation of MEBs was enhanced by mixing ZSM-5 with both M1 and M2. Disproportionation of TMBs: Compared to M1, the C10 aromatic conversion decreased in products from M1Z1 and further decreased in products from M1Z2. For M2 catalyst, however, an increase in C10 aromatic content from 4.2 wt.% in feed to 10.0 wt.% is observed. Compared to M2, the C10 aromatic content in products from M2Z1 and M2Z2 decreased to 7.9 wt.% and 7.7 wt.%, respectively. These results indicate that mixing M2 with ZSM-5 resulted in somewhat lower disproportionation of TMBs, probably due to higher acid site concentration of M2Z1 and M2Z2 compared to M2. Xylenes Yield: Xylenes yield changed significantly upon mixing mordenite with ZSM-5. The results, are presented in Table 3. Compared to M1, M1Z1 and M1Z2 catalysts exhibited 3.2 wt.% and 4.5 wt.% higher yield of total xylenes, respectively. This can be attributed to higher dealkylation of MEBs compared to M1 catalyst. Compared to M2, M2Z1 and M2Z2 exhibited 6.7 wt.% and 1.1 wt.% higher yield of total xylenes, respectively. Since M2 has very low acid site concentration, mixing of of ZSM-5 resulted in increase in acid site strength. Hence the dealkylation of TMBs to toluene and ethylene was significantly enhanced. Subsequently, more transalkylation of toluene and TMB resulted in higher xylene yield. 3.4 Conversion of Heavy Reformate and Toluene The transalkylation of TMBs and toluene is desired reaction for the production of xylenes. However, toluene, required for this reaction, has to be produced from dealkylation reaction. In order to enhance the transalkylation of TMBs, some refiners add a certain percentage of toluene to the heavy reformate feed. To study the effect of such conversion, different amounts of toluene were mixed with heavy reformate. The four mixed feedstocks used for conversion over M1Z2 and M2Z1 catalysts contain heavy reformate and toluene in the following molar ratio: (i) 20:80; (ii) 40:60; (iii) 60:40; and (iv) 80:20.

The effect of heavy reformate/toluene feed on xylene yield is presented in Figure 2. For 100% toluene feed, xylenes yield over M2Z1 was 13.7 wt.%. It increased with addition of heavy reformate and reached a maximum of 25.3 wt.% when the feed was a 70:30 mixture of heavy reformate/toluene. Further increase in the heavy reformate/toluene ratio resulted in a decrease in xylene yield. With M1Z2 catalyst, the xylenes yield increased with the increase in heavy reformate/toluene ratio in feed. However, an increase of heavy reformate/toluene ratio above 80:20 did not change the xylene yield. M1Z2, having higher acid site concentration, was able to produce the required amount of toluene for transalkylation of TMBs by dealklyation of MEBs. While M2Z1, having lower-acidity, was unable to do so. Therefore, in the case of M2Z1, conversion of toluene and heavy reformate was quite advantageous.
35 M1Z2 30 M2Z1

25

Xylenes Yield (wt.%)

20

15

10

0 Heavy Reformate (wt.%) 0 Toluene (wt.%) 100

20 80

40 60

60 40

80 20

100 0

Figure 2. Xylenes yield from the conversion of heavy reformate and toluene over M1Z2 and M2Z1 catalysts Xylenes yield obtained in the reaction of toluene and heavy reformate was compared with the yields from toluene and 1,2,4-TMB at their 1:1 molar mixture (Figure 3) as well as from the conversion of heavy reformate and toluene over M1Z1 and M1Z2. Comparison of xylene yields obtained over M2Z1 indicates that 1:1 molar mixture of toluene and 1,2,4-TMB yielded 31.3 wt.% xylenes, which was much higher than for pure toluene (13.7 wt.%) or 1,2,4-TMB alone (18.2 wt.%). Conversion of heavy reformate resulted in a xylenes yield of 22.5 wt.%, which was also higher than the xylenes yield of 18.2 wt.% from conversion of 1,2,4-TMB. The conversion of 1:1 molar mixture of heavy reformate and toluene resulted in only marginal (from 22.5 wt.% to 25.3 wt.%) increase in xylenes yield compared to significant (from 18.2 wt.% to 31.3 wt.%) increase in the conversion of 1:1 molar mixture of 1,2,4-TMB and toluene. These results indicate that, for processing of heavy reformate, toluene required for transalkylation reaction was produced from deakylation of MEBs and hence higher yield of xylenes was obtained from 1:1 molar mixture of heavy reformate and toluene than from 1,2,4-TMB alone.

40 35 30
Xylenes Yield (wt.%)

Catalyst: M1Z2

25 19.6 20 15 10 5 0 Toluene 124TMB 12.4

23.5 19.8 18.7

12.4

Toluene + 124TMB (1:1)

Toluene

Heavy Reformate

Toluene + Heavy Reformate (1:1)

40 35
Xylenes Yield (wt.%)

Catalyst: M2Z1 31.3 25.3

30 25 20 15 10 5 0 Toluene 124TMB Toluene + 124TMB (1:1) Toluene Heavy Reformate Toluene + Heavy Reformate (1:1) 13.7 18.2 13.7 22.5

Figure 3. Comparison of xylenes yield from conversion of toluene, 1,2,4-TMB and heavy reformate over M1Z2 and M2Z1 catalysts The results obtained from the conversion of heavy reformate and toluene over M1Z2 catalyst with higher-acid sites, were somewhat different. Comparison of xylenes yields obtained from toluene and 1,2,4-TMB indicates that 1:1 molar mixture of toluene and 1,2,4-TMB yielded 23.5 wt.% xylenes, which was higher than toluene alone (12.4 wt.%) or 1,2,4-TMB alone (19.6 wt.%). Conversion of heavy reformate alone resulted in a xylenes yield of 19.8 wt.%, which was almost same as the xylenes yield of 19.6 wt.% from conversion of 1,2,4-TMB alone. The conversion of 1:1 molar mixture of heavy reformate and toluene resulted in marginal (1.1 wt.%) decrease in xylenes yield compared to 3.9 wt.%) increase in the conversion of 1:1 molar mixture of 1,2,4-TMB and toluene. These results indicate that the rate of dealkylation of MEBs to produce toluene was much higher over higher-acidity M1Z2 catalyst. This resulted in the production of required amount of toluene from heavy reformate alone. Therefore, addition of toluene to heavy reformate did not result in an increase in xylenes yield. In fact, a slight decrease in xylenes yield was observed possibly due to reduction of methyl groups in the reaction system.

4. Conclusions This study showed that the composition of heavy reformate can significantly alter the reaction rates and product yields over mordenite-based catalysts. Among the C9 components, MEBs were found to be more reactive than TMBs. Mordenite with higher acid site concentration (M1) favored dealkylation reactions while mordenite with lower acid site concentration (M2) favored disproportionation of C9 aromatics. The yield of total xylenes increased significantly by mixing mordenite with ZSM-5 zeolite. While mixing ZSM-5 and mordenite has shown appreciable advantage, mixing lower-acidity M2 with higher-acidity Z1 resulted in the highest xylenes yield (22.5 wt.%). It appears that such a mixture strikes the balance in catalytic properties for enhancing desirable reactions (such as dealkyation of MEBs to toluene, disproportionation of TMBs and transalkylation of TMBs and toluene, etc.), while limiting undesirable reactions (such as dealkylation of toluene etc.). The conversion of toluene and heavy reformate over lower-acidity M2Z1 increased xylenes yield to a maximum of 25.3 wt.% from a feed mixture containing 70:30 heavy reformate and toluene. Comparison of results for heavy reformate and 1,2,4-TMB indicates that toluene required for transalkylation was produced by deakylation of MEBs; hence more xylenes yield was obtained from heavy reformate compared with 1,2,4-TMB alone. The results from the conversion of toluene/1,2,4-TMB and toluene/heavy reformate indicate that catalyst acidity plays a key role in promoting different reactions and hence the yield of total xylenes. Acknowledgements This work is conducted at KFUPM-RI under the project No. CRP02238 sponsored by Saudi Aramco. The authors would like to thank KFUPM and Saudi Aramco for permission to publish this paper. Acknowledgement is also due to the Ministry of Higher Education for establishing the Center of Research Excellence in Petroleum Refining and Petrochemicals (CoRE-PRP) at KFUPM. References
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