Catalytic Propylene Production from Ethylene Using Zeolite Catalysts

Toshihide Baba Department of Environmental Chemistry and Engineering, Tokyo Institute of Technology, 4259 Nagatsuta, Midori-ku, Yokohama 226-8502, Japan. E-mail: tbaba@chemenv.titech.ac.jp Abstract Two new methods for the catalytic synthesis of propylene using solid acid catalysts are presented. The first approach is a new method for the activation of methane, involving conversion of methane to propylene over metal cations exchanged zeolites, such as silver-exchanged zeolite, in the presence of ethylene. In the second method, ethylene conversion proceeds directly and selectively over proton-exchanged zeolite. The heterolytic dissociation of methane over silver cationic clusters (Agn+) in Ag+-exchanged zeolites, leading to the formation of silver hydride (Agn-H) and CH3d+ species, which reacts with ethene to form propene around 673 K. Using 13C-labeled methane as a reactant, propene is shown to be a primary product from by methane and ethene. Thus, a significant proportion of propene was singly 13C-labeled (13CC2H6). H+-exchanged zeolites, such as H-ZSM-5 do not catalyze the methane conversion, only ethylene being converted into higher hydrocarbons, such as propylene. Ethylene is selectively converted to propene over SAPO-34 at 723 K with a yield of 52.2 % and selectivity of 73.3 % at ethene conversion of 71.2 %. Introduction Ethylene (C2H4) and propylene (C3H6) are indispensable in petrochemical industries, and the demand for propene in particular has grown rapidly due primarily to the high growth in direct propene use.1) Both chemicals are produced mainly through the cracking of naphtha, especially in European and East Asian countries. In these processes, the co-production of propene by steam cracking is determined largely by the feeding conditions, and the yield of propene is relatively low in terms fluid catalytic cracking (FCC) units. Expected capacity additions in the ethylene industry over next few years will result in less propylene production per ton of ethylene from conventional ethylene plants as a result of shifts towards lighter cracker feedstocks. Over this same period the demand for propylene is growing slightly faster than ethylene demand. Investigations on alternative routes for light olefin synthesis were conducted following the 1973 oil crisis, leading to four broad categories (Category 1 ~ Category 4) of production routes, as detailed below. Category 1: Conversion of syngas using Fischer-Tropsh (FT) Fe-, Co-, Ru-, or Rh-based catalysts. Although a large number of studies have been conducted in

attempts to improve the FT-type catalyst for the purpose of olefin synthesis, this synthetic route is essentially restricted by the Shultz-Flory law with regard to the carbon number distribution of the products. The products are usually aliphatic saturated hydrocarbons. Category 2: Oxidative coupling of methane to produce ethane and propane.2, 3) This process requires the use of oxygen. The formation of oxygen-containing products, such as CH3OH and H2O, provides a thermodynamic driving force such that the reaction has negative free energy. However, with the kinetically controlled direct oxidation reaction, the formation of CO2, an undesired product, severely limits the yields of light olefins. Category 3: Conversion of methanol to olefins (MTO) using shape-selective zeolitic catalysts such as HZSM-5 and SAPO-34.4,5) This route is regarded as an indirect olefin synthesis from natural gas. The potential to realize practical applications for olefin synthesis appears to be higher than for other direct syntheses. Category 4: Non-oxidative coupling of methane to aromatic hydrocarbons such as benzene (C6H6) at high reaction temperatures.6-8) Methane conversion under non-oxidative conditions is thermodynamically unfavorable, while methane is converted to higher hydrocarbons without the formation of CO2 or CO. In this presentation, I propose a new category, Category 5 for the production of C3H6. Category 5 (This work): Two new routes for propene production: methane conversion using silver-exchanged zeolite in the presence of C2H4, and direct ethene conversion over proton-exchanged zeolite. C3H6 is produced by the conversion of CH4 and C2H4.9, 10) CH4 + CH2=CH2 CH3CH=CH2 + H2 The second synthetic route is suitable for ethylene conversion. 3 CH2=CH2 2 CH3CH=CH2 Motivation Our group has found that the heterolytic dissociation of H2 occurs over silver cationic clusters (Agn+) produced in silver exchanged zeolites, such as Ag-Y.11) 1H MAS NMR showed that hydrogen dissociatively adsorbed on Ag-Y to generate acidic protons (ZO-H, ZO: zeolite lattice) and silver-hydride species (Agn-H). This reaction is reversible. Thus, prolong evacuation of the system resulted in disappearance of the peaks due to ZO-H and Agn-H and the intensities of these peaks restored by exposing the evacuated samples to hydrogen again. ZO-Agn+ + H2 AgnH + ZOH We have also found that the adsorption of methane on Ag-Y gives rise to the peak due to Agn-H, indicating that heterolytic dissociation of CH4 proceeds on Ag-Y to simultaneously produce highly polarized methoxy groups (ZO -CH3+).11) ZO-Agn+ + CH4 Agn-H + ZO - CH3 +

If ZO -CH3 + is formed, they should be very reactive. Our group has revealed through the use of 13C-labeled methane that labeled propene is produced over Ag+-exchanged zeolites such as Ag-Y, while unlabeled one is formed over H+-exchanged zeolites, such as H-ZSM-5.9, 12) These results suggest that propene production in methane conversion in the presence of C2H4 involves following processes: Process [1] is activation of methane by silver cationic species and C3H6 production by reaction of activated methane with C2H4, as shown in Scheme. Process [2] is C3H6 production by conversion of C2H4 at Brnsted acid sites. On the basis of Process [1], there is a possibility that activation of methane proceeds over zeolites exchanged with metal cations other than Ag+. On the basis Scheme of Process [2], it is expected that both the acid strength of Brnsted acid sites and the pore size of solid acid catalysts, such as a zeolite influence the formation rate of C3H6 in the conversion of C2H4. In this presentation, I focus the following two points. Point 1: the activation of methane over metal cation exchanged zeolites is examined and the reaction mechanism for the formation of C3H6, benzene and toluene are proposed. Point 2: the conversion of C2H4 is carried out using H+-exchanged zeolites to examine the effects of the acid strength of acidic protons and the pore size of these catalysts on the conversion of C2H4 and the formation of C3H6. Reaction of 13CH4 with C2H4 There is a possibility that heterolytic dissociation of the CH bond of methane may occur at metal cation (Mn+) sites other than Ag+ on exchanged zeolites. If the highly polarized methoxy groups (ZOCH3+) are formed together with metal-hydride species [MH](n1)+ as in the case of silver-exchanged zeolites, the conversion of methane may proceed in the presence of ethene in a similar manner:12, 13) ZOMn+ + CH4 [MH](n1)+ + ZO-CH3+ The results of 13CH4 conversion in the presence of ethene at 673 K using various metal cation-exchanged ZSM-5 zeolites are shown in Table 1.12, 13) The main product in all cases is propene, and 13C was found in propene to varying extents. These results indicate that methane is activated on metal cationic species and that 13CC2H6 is produced by the methaneethene reaction, demonstrating that methane is also activated

on metal cationic species other than silver.

Table 1. Reaction of 13CH4 with C2H4 over ZSM-5 zeolites Metal cation Pressure /kPa
13CH4

Ag

In

Fe

Mo

39.5 0.412

39.4 0.346

39.5 0.359

39.6 0.346

39.5 0.399

C 2H 4 Conversion / mol% C 2H 4 Selectivity / mol% C 2H 6 C 3H 6 C 4H 8 Benzene (C6H6) Toluene (C7H8)

10

13

9.2

4.0

0.8

0 100 0 0 0

17 65 0 41 19

33 28 0 0 0

37 100 0 0 0

10 71 19 0 0

(Singly 13C labeled hydrocarbon / hydrocarbon) 100

13CCH6

in C3H6 in C6H6 in C7H8

87

33 9 54

62

24

13CC5H6

13CC6H8

Catalyst, 0.1 g; temperature, 673 K; Reaction time, 1 min

In the case of InZSM-5 (In/Al = 0.7), ethene conversion reached 13%, and ethane (17%), propene (23%), benzene (41%), and toluene (19%) were observed as gaseous hydrocarbon products (values in parenthesis denote selectivities in mol%).12) Among these hydrocarbons, 13C-labeled ethane (13CCH6 and 13C2H6) and 13C-labeled benzene (13CC5H6) are negligible, with mole fractions of only 2% and 7%, respectively (close to natural abundances). This result indicates that ethane (C2H6) and benzene (C6H6) originate solely from ethylene. Propylene and toluene, on the other hand, exhibit singly 13 C-labeled fractions of 33% and 54%, respectively. No significant amounts of multi-13C-labeled propylene (13CC2H6) or toluene (13C2C5H8) are produced by these reactions. Propylene is thus formed by the reactions of 13CH4 with ethene and the oligomerization/cracking of ethene. As 13C-labeled benzene is not formed, propylene is not converted to benzene in these reactions. The formation of 13C-labeled toluene (13CC6H8) and the absence of 13C-labeled benzene suggest that a fraction of the toluene is formed by reaction between methane and benzene.48) Reaction of benzene over InZSM-5 under 39.8 kPa of 13CH4 and 1.63 kPa of benzene at 673 K produced only toluene and hydrogen as reaction

products. The similarity in the rates of benzene conversion (5.6%) and toluene yield (4.9%) suggests that side reactions such as the disproportionation of toluene to benzene and xylenes does not occur. The fraction of 13C-labeled toluene is 97%, indicating that CH3+ species formed on InZSM-5 are subsequently reacting with benzene to form toluene. Thus, methane can be activated not only on cationic Agn+ clusters but also on other metal cations and/or cationic species. HZSM-5, on the other hand, does not show any catalytic activity for the reaction between methane and benzene under the same reaction conditions, as expected. As it was mentioned above, 13CH4 is activated in the presence of C2H4 over metal cation-exchanged ZSM-5 (M-ZSM-5) to form 13C-labled propene and toluene. This result encouraged us to investigate also the conversion of CH4 over M-ZSM-5. The reaction of CH4 (33.3 kPa) in the presence of C2H4 (33.3 kPa) was carried out at 673 K in a flow reactor. M-ZSM-5 were active to convert methane to higher hydrocarbons, as expected. The conversions of CH4 at running time of 1 h are listed as follows: Ag(13.2 %) > Mo(9.5 %) > In(8.1 %) > Fe(7.9 %) > Mo(9.5 %) > V(7.6 %) > Ga(7.0 %) > Pd(5.5 %) > Pb (5.4%) > La(2.5 %) > Zn(1.8 %) > Cu(1.5 %) > H(0%) Selective production of propene by conversion of ethene over proton-exchanged zeolites Proton-exchanged zeolites (e.g., HZSM-5) have been shown to catalyze the conversion of C2H4 to produce C3H6, yet are unable to activate CH4 for conversion. In the conversion of CH4 over silver-exchanged zeolites in the presence of C2H4, AgA exhibits higher selectivity for the production of C3H6 than AgY due to the smaller pores of the A-type zeolite. It is therefore expected that both the acid strength of Brnsted acid sites and the pore size of the catalyst material influence the rate and selectivity of C3H6 formation in the conversion of C2H4. (1) Effect of pore size on selectivity for C3H6 formation To examine the effect of pore size on the selectivity for C3H6, the conversion of C2H4 at 723 K was conducted under 33.3 kPa of C2H4 using the silicoaluminophosphate molecular sieve SAPO-34, the aluminosilicate molecular sieves H[Al]ZSM-5 and CaA, and the borosilicate molecular sieve H[B]ZSM-5 as solid acid catalysts.14) The catalytic performance of these materials after 1 h time on stream is summarized in Table 2.14) These results indicate that the selectivity for C3H6 formation is strongly dependent on pore size. SAPO-34 exhibits the highest selectivity for C3H6 (ca. 80%), while the selectivity for 2-methyl propene (iso-butene) is very low. The accompanying alkenes are 1- and 2-butenes, produced with selectivities of 3.1% and 8.9%, respectively. The pore size of these catalysts decreases in the order H[Al]ZSM-5 = H[B]ZSM-5 > CaA > SAPO-34. The SAPO-34 structure includes a CHA cage (0.75 nm diameter 0.82 nm), which is accessible via six eight-member rings

(0.45 nm 0.41 nm). The pore size of SAPO-34 (0.45 nm 0.41 nm) is thus approximately equal to the kinetic diameter of C3H6 (0.45 nm) and smaller than the kinetic diameter of 2-methyl propene (0.50 nm). C2H4 has a kinetic diameter of 0.39 nm, while that for 1-butene is 0.45 nm).
Table 2 Catalytic performances of silicoaluminophosphate and aluminosilicate catalysts for the conversion of ethene at 723 K.
Pore size 1) / nm

Catalyst

W/F
/ g h mol-1

C2 = conv. /%

Product selectivity / C-atom% C3 = 1-C4=

2-C4= (C/T 2)) 79.5 3.1 8.9 (0.64) 0.1

Rate of C3= formation

C5 C6
/ mmol g-1 h-1

Rate of butane conversion 3)

i-C4=

C1 - C4 alkane 6.6

/ mmol g-1 h-1

SAPO-34 Si/(P + Al + Si) = 0.10 H-[Al]-ZSM-5 Si/Al = 11.9 H-[B]-ZSM-5 Si/B = 64.2 Ca-A Si/Al = 1.0

0.38 x 0.38

2.0

7.9

1.8

0.0

7.0

0.29

0.56 x 0.53 0.55 x 0.51 0.56 x 0.53 0.55 x 0.51 0.50

0.050

6.3

48.4

4.0

11.2 (0.72)

14.3

5.0

16.3

0.8

130

6.3

47

7.5

37.9

6.0

16.6 (0.72)

16.1

1.4

12.2

9.8

0.13

0.080

240

2.0

51.5

5.0

12.7 (0.73)

1.1

24.6

5.1

0.0

0.0095

0.043

C2= : ethene, C3= : propene, 1-C4= : 1-butene, 2-C4= : 2-butene, i-C4= : iso-butene, C1 - C4 alkane : (CH4 + C2H6 + C3H8 + C4H10), C5 : (pentenes + pentanes), C6 : aliphatic hydrocarbons with 6 carbon atoms. 1) Crystallographic free diameter (nm) 2) Molar ratio of cis-2-butene to trans-2-butene. 3) Cracking of n-butane: reaction temperature = 773 K, partial pressure of n-butane = 4.05 kPa. C2H4 pressure = 33.8 kPa, 1 h of time on stream.

(2) Effect of acid strength on selectivity for C3H6 formation Although the pore size of A-type zeolite (CaA) is similar to that of SAPO-34, SAPO-34 exhibits higher selectivity for C3H6. The rate of C3H6 formation over SAPO-34 is also much greater than that over CaA (Table 2). These results intimate that acid strength is also an important factor determining the activity for C3H6 formation. The acid strength of the catalysts was thus estimated based on the rate of n-butane cracking at 773 K at an n-butane pressure of 4.0 kPa.15) The cracking of n-butane is a typical reaction that proceeds on Brnsted acid sites, and it is natural that the reaction rate would increase with acid strength. The rate of n-butane cracking over SAPO-34 is 6.7 times greater than that over CaA, demonstrating the higher acid strength of SAPO-34. To examine the effect of acid strength on C3H6 formation, it is reasonable to compare the catalytic performance of H[Al]ZSM-5 and H[B]ZSM-5, which have the same structure and pore size yet dissimilar acidities. As shown in Table 2, the two catalysts exhibit different activities for n-butane cracking. The acid strength of H[Al]ZSM-5 is much higher than that of H[B]ZSM-5, and the former displays a much faster rate

of C3H6 formation than the latter. These results indicate that the rate of C3H6 formation is higher over acid sites with greater acid strength. CaA, which has the lowest acid strength of the materials tested, also exhibits the lowest rate of C3H6 formation. The acid strength, on the basis of the rate of n-butane cracking, decreases in the order H[Al]ZSM-5 >> SAPO-34 >> H[B]ZSM-5 > CaA, whereas the selectivity for C3H6 decreases in the order SAPO-34 > CaA > H[Al]ZSM-5 > H[B]ZSM-5. H[Al]ZSM-5, which has higher acid strength than SAPO-34, converts propene to other hydrocarbons, such as C5 hydrocarbons, whereas H[B]ZSM-5 and CaA, with lower acid strength than SAPO-34, exhibit a lower rate of C3H6 formation than SAPO-34. These results show that SAPO-34, with modest acid strength, achieves the highest selectivity for propene among the catalysts examined. Effect of Conversion of C2H4 on Propene yield over SAPO-34 The reaction of ethene over SAPO-34 at 673 K was further examined as a function of contact time (W/F) as a means of controlling the conversion level of C2H4. The yield of C3H6 in the reaction at 33.3 kPa C2H4 partial pressure is plotted as a function of C2H4 conversion in Fig. 1.14) The yield of C3H6 increases with ethene conversion to a maximum yield of 52.2% C3H6 at 71.2% C2H4 conversion. At C2H4 conversion greater than ca. 70%, the yield of C3H6 decreases accompanied by an increase in the yield of propane. Fig. 1 Hydrocarbon yield as a function of ethene These results show that propene conversion over SAPO-34 at 673 K under ethene formed by catalysis is further partial pressure of 33.8 kPa. 49) converted to C3H6 and higher ( : CH4 + C2H6 + butanes, : propene, hydrocarbons, such as hexenes. : propane, : butenes, : C5+ hydrocarbons) Effect of particle size on the selectivity for C3H6 The influence of particle size of SAPO-34 on the selectivity for C3H6 was examined at 673 K in the conversion of C2H4 using SAPO-34. In all cases, the conversion of C2H4 varied with time on stream. The selectivity for C3H6, and the rate of C3H6 production were plotted against the particle sizes of SAPO-34 at ~10% conversion of C2H4 at 1 h time on stream. The ~10% level of C2H4 conversion was controlled with

varying the contact time (W/F), where W and F denote the catalyst weight (g) and the total molar flow rate (mol h-1), respectively. As shown in Fig. 2, the selectivity for C3H6 depended on the SAPO-34 particle size, although the mole fractions of Si were different. The selectivity was nearly constant at ~80% for particle sizes smaller than ~3 m. However, selectivity was lower for particle sizes larger than ~6 m. Thus, SAPO-34 with particle sizes from 6~17 m gave C3H6 with a constant selectivity of ~75%. The selectivity decreased to 12.5% when the particle size was increased to 26 m, the largest observed in this study. SAPO-34 with a 26 m particle size had the lowest mole fraction of Si(OAl)4 determined by its 29Si MAS NMR spectrum.

Fig. 2

Selectivity for C3H6 and the rate of C3H6 production at ~10% conversion of

C2H4 plotted against the particle size of SAPO-34 at 1 h time on stream. The reaction temperature was 673 K, C2H4: 33.3 kPa. (): Selectivity for C3H6. (): Rate of C3H6 production.

The rate of C3H6 production, which was determined at 1h time on stream, at which the conversion of C2H4 was ~10%, is plotted against particle size in Fig. 2. The rate varied considerably with variation in the particle size, and had a tendency to increase with decreasing particle size. The variation in the rate of C3H6 production could have been caused by not only the particle size, but also by the different Si mole fractions, which would influence the amount of protons (H+) acting as Brnsted acid sites. To determine the effect of particle size in more detail on the rate of C3H6 production and the selectivity for C3H6, the catalytic performance of SAPO-34 with the same

mole fraction of Si and varying particle size was examined. The catalysts were SAPO-34 with identical values of mole fraction of Si, but different particle sizes, which were 3.6, 6.2, and 17 m, respectively. The rate of C3H6 production depended strongly on the particle size, and the rates increased with decreasing particle size. The selectivity for C3H6 and other hydrocarbons also depended on the particle size. However, the dependence of the rate of C3H6 production on particle size was much stronger than on the dependence of the selectivity for C3H6, as shown in Table 3.
Table 3 Effect of particle size of SAPO-34 on the rate of C3H6 production and the

selectivity for C3H6 and other hydrocarbons. Particle size / m Mole fraction of Si Conversion of C2H4 Rate of C3H6 production / mmol g-1h-1 Selectivity / C-atom% C 3H 6 C 4H 8 CH4 C 2H 6 C 3H 8 C4H10 C 5+ Rate of n-butane cracking / mmol g-1h-1
Conversion of C2H4 into C3H6 Reaction conditions: Reaction temperature 673 K, C2H4 33.3 kPa. Cracking of n-butane Reaction conditions: Reaction temperature 803 K, n-butane C2H4 4.0 kPa.

3.6 0.154 8.2

6.2 0.153 8.3

9.0 0.162 7.3

17 0.146 7.1

5.9

2.7

2.4

2.0

78.9 2.9 0.9 7.6 9.1 0.2 0.3 0.28

64.8 1.4 1.5 10.5 21.2 0.1 0.4 0.24

64.5 2.4 1.9 12.6 17.8 0.2 0.6 0.26

65.3 2.0 2.4 11.5 18.2 0.2 0.4 0.27

The rates of n-butane cracking over these SAPO-34 samples are also shown in Table 3. SAPO-34 samples having the same amount of Si have a similar number of protons. The rates of n-butane cracking did not depend on the particle size, indicating that the acid strength over SAPO-34 did not change. The particle size of SAPO-34 has a stronger influence on the rate of C3H6 production than on the selectivity for C3H6. To further investigate the influence of Si mole fraction, the conversion of C2H4 was carried out using SAPO-34 with a fixed particle size (~2.5 m) and varying Si mole

fraction. The results are shown in Table 4. The selectivity for C3H6 was similar, about 78%, for the mole fraction of Si from 0.084 to 0.170. This suggests that the acid strength of protons over SAPO-34 did not vary significantly. However, the selectivity for C4H8 depended on the mole fraction of Si and that lower alkanes (CH4, C2H6 and C3H8) increased with increasing the mole fraction of Si. On the basis of results shown in Tables 3 and 4, the effect of SAPO-34 particle size on the selectivity for C3H6 was stronger than the effect of the mole fraction of Si in the SAPO-34 lattice.
Table 4 Effect of mole fraction of Si in the lattice of SAPO-34 on the selectivity for

C3H6 and other hydrocarbons Particle size / m Mole fraction of Si C2H4 conversion / % Selectivity / C-atom% C 3H 6 C 4H 8 CH4 C 2H 6 C 3H 8 C4H10 C 5+ 74.6 18.1 0.3 2.8 3.3 0.5 0.4 80.0 10.1 0.5 3.8 4.1 0.6 0.9 81.9 6.4 0.9 4.8 2.2 0.5 3.3 78.7 2.2 1.0 8.3 9.2 0.5 0.1 2.6 0.084 10.0 2.5 0.086 9.1 2.5 0.095 9.3 2.6 0.170 10.1

Reaction conditions: Reaction temperature 673 K, C2H4 33.3 kPa.

Conclusion A new approach for the activation of methane over silver-exchanged zeolites was presented based on a consolidation of work by the authors group. The conversion of 13 C-labeled methane in the presence of ethylene showed that propylene is produced by the reaction of CH4 with ethylene. This reaction also proceeds over other metal cation-exchanged zeolites. Catalysis involving metal cations such as Agn+ in zeolites is a new concept for the activation of methane, and may be expandable to alkane activation for the generation of alkyl carbenium ions by abstraction of hydride propene. Propylene is also produced over proton-exchanged zeolite materials such as SAPO-34 by the conversion of ethene. SAPO-34, which has intermediate acid strength and pore size comparable to the kinetic diameter of propylene, selectively affords propylene with high yield in the conversion of ethylene.

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