Hydration of Propylene Oxide by Hydrogen Peroxide over Titania Catalysts

Paper #659 (this paper has not been reviewed for technical content) Takeshige TAKAHASHI, Eiko NAKAO and Takami KAI Department of Applied Chemistry and Chemical Engineering, Faculty of Engineering, Kagoshima University, Kagoshima, 890-0065, JAPAN

ABSTRACT
Propylene oxide (PO) produced by the epoxidation of propylene (PP) with hydrogen peroxide was consecutively hydrated to propylene glycol (PG) over the catalyst with titanium oxide. The hydration resulted in the decrease in PO selectivity in the reaction system. To elucidate the reaction mechanism, the hydration of PO in high pressure batch reactor was carried out to obtain the rate constant in the range of 323K to 353K over TS-1 catalysts with different Ti/Si ratio and titanium oxides with different crystal structures. When the reaction was carried out without catalyst or without hydrogen peroxide, the hydration was not detected at the present reaction temperature. The hydration rate is represented by second order equation related as the concentration of PO and hydrogen peroxide. It was also found that the hydration rate was not related to the epoxidation rate of PP. This result suggested that the epoxidation of PP and hydration of PO were accelerated with different active sites of catalyst. The effect of reaction temperature and solvent on the hydration rate was determined to develop a catalyst with high yield of PO. At the same time, the characterization of catalyst, such as XRD, UV-VIS adsorption and surface area measurements was carried out to clarify the effect of catalyst property and the hydration rate. INTRODUCTION Propylene oxide (PO) is one of industrially important raw materials to synthesize polyurethane and unsaturated polyester resin. Chlorohydrin process, that is current industrial PO manufacturing method, comes to deadlock on the aspect of environmental problems1). Therefore, the development of new process without chlorine as starting reagent is strongly desired. An ideal process should be the oxidation of PP with the mixture of hydrogen and oxygen. Although gold catalyst or zeolite catalyst with titanium was tried to accelerate the direct epoxidation, there is no industrial process for the epoxidation of PP by hydrogen and oxygen mixture so far. It is reported that TS-1 shows excellent catalytic activity and PO selectivity on the epoxidation of propylene (PP) by hydrogen peroxide2-4). Recently, it is reported that the other type of zeolites with larger micro pore than TS-1 has been effective for the epoxidation of PP by hydrogen peroxide5,6). On the other hand, it has been known that the epoxidation of olefins by organic hydroperoxides, such as t-butyl hydroperoxide or 1-phenyl ethyl hydroperoxide1). In the reaction system, t-butyl alcohol or 1-phenyl ethanol was simultaneously produced with main product. The effective employment of the

by-product for the other chemical process is another problem for the system. As a result, the epoxidation by hydrogen peroxide is promising for industrial synthesis of PO. It is found that PO selectivity is lowered by the hydration to propylene glycol (PG) over the catalyst. The production of PG was responsible to decrease in the PO selectivity. The total reaction was represented a series of consecutive reaction scheme as shown in below equation. CH3-CH=CH2 + 1/2O2 = CH3-CH(O)-CH2 (PO production) CH3-CH(O)-CH2 + H2O = CH3-CH(OH)-CH2OH (PO hydration) In the present study, the relationship between reaction rate and catalyst properties, and experimental conditions was obtained to analyze the reaction mechanism of PO hydration reaction. EXPERIMENTAL In the study, TS-1 with different Si/Ti ratio, amorphous titania, anatase titania and rutile titania were used for the synthesis of PO from PP and hydrogen peroxide and for hydration of PO. Although TS-1 was synthesized in our laboratory, the titanias were commercially obtained. The crystal form was determined by XRD. The titanias were used without purification. The autoclave type batch apparatus for the PO hydration rate measurement is shown in Fig.1. The reactor is made of stainless steel and the inner volume is 340ml. The solution in the reactor is mixed by a magnetic stirrer (300rpm). The reaction temperature is controlled with heater and cooling water. The catalyst (0.5g), hydrogen peroxide solution (30ml, 30%), solvent (60ml) and a prescribed amount of PO were fed into the reactor for hydration runs. On the other hand, the synthesis of PO was carried out feeding of PP (2atms) for PO in the above experimental set up.
5 7 8 6 3 9 1 4

1 Ar gas cylinder 2 Propylene gas cylinder 3 Mass flow controler 4 Autoclave 5 Pressuregage 6 Cooling coil 7 Pressure keeping valve 8 Sampling outlet 9 Thermocouple and temperature controler

Fig.1 Experimental apparatus for PO production and hydration.

In the hydration runs, the pressure in the reactor is controlled at 3atms by argon and the reactor is allowed to stand until there is no decrease in pressure. When the reaction temperature reaches to a prescribed value, the sample at starting period is collected from the reactor. The sample is collected with a prescribed time interval until 3 h. The concentrations of PO and PG are measured by a gas chromatograph equipped with glass column (30m) and FID detector. The concentration of hydrogen peroxide is measured by a titration method. RESULTS AND DISCUSSION When the reaction was carried out without catalyst and/or without hydrogen peroxide, the hydration of PO was not observed at the present reaction conditions. These results indicate that the catalyst and hydrogen peroxide are indispensable for accelerating PO hydration reaction. Fig.2 shows the relationship between PO concentration and reaction time at 313K. The reaction rate is assumed to represent 1st order for PO (CA) and for hydrogen peroxide concentration (CB). -rAm=k2mCACB (1) where -rAm is rate constant for A disappearance, k2m is 2nd order rate 0.10 constant. When the concentration of hydrogen peroxide is sufficiently larger 0.08 than PO concentration, the reaction rate is represented by pseudo first order 0.06 equation. (2) -rAm=k1mCA 0.04 Since the hydrogen peroxide concentration is essentially constant, 0.02 km2 can be obtained dividing k1m by the initial hydrogen peroxide concentration 0.00 0 30 60 90 120 150 180 210 CB0. The relationship between PO reaction time [min] concentration and reaction time (t) is obtained from the mass balance of Fig.2 Relationship between PO concentration hydrogen peroxide in batch reactor as and reaction time for PO hydration. shown in Eq.(3) under the initial condition t=0; CA=CA0. (3) CA/CA0=exp (-km1 t) When CA/CA0 and t was plotted on semi-log paper, the straight line was obtained for all reaction conditions. Rate constant km1 was determined from the slope of the straight line. Fig.3 shows the effect of catalyst on PO production rate and PO disappearance rate. The PO production rate over TS-1 was extremely larger than the titanias as described in a previous report3). The surface area of amorphous titania was largest among the titanias, whereas the area of rutile titania was smallest. The PO hydration rate was related to the surface area. This result suggests that the active sites for PO hydration were uniformly dispersed on the titania surface. On the other hand, the active sites for PO production was not dispersed on the surface area.
PO concentration [mol/l]

(PO production rate)*104 [mol/(kg s)]

6 5 4 3 2 1 0

PO production rate PO hydration rate

6 5 4 3 2 1 0

TS-1 amorphous

anatase rutile

Fig.3 Effect of catalyst on PO production rate and PO hydration rate.

Fig.4 demonstrates the relationship between production rate and hydration rate over TS-1 and titanias. The production rate over TS-1 was higher than those over titanias. The UV-VIS absorption spectrum of TS-1 shows a peak near 220 nm, which is assigned to titanium with 4 number of coordination. On the other hand, the spectrum of the amorphous titania shows a peak near 270 nm, assigned to titanium with 6 number of coordination. These results indicate that titanium atoms with 4 coordination number
(PO production rate)*104 [mol/(kg s)]
1400 1200 1000 800 600 4 2 0
TS-1 amorphous anatase rutile

10

15

20

25
6

30

35

40

(PO hydration rate)*10 [mol/(kg s)]

Fig.4 Relationship between PO production rate and PO hydration rate.

(PO hydration rate)*106 [mol/(kg s)]

0.133

3.68*10-5

are effective to production of PO, whereas titanium atom with 6 coordination number are effective to hydration of PO. It is reported that when TS-1 was washed with HCl to remove titania presented at the outer surface of TS-1 crystal, the PO production rate and PO selectivity increased. However, the similar improvements were not observed in the present study. It is considered that since TS-1 used in the study was carefully washed with water and HCl, there is no titania at the outer surface of the crystal. The hydration rate of PO was measured at different reaction temperature. The hydration product was only PG at the reaction temperature. Fig.5 shows the effect of reaction temperature on PO hydration rate over TS-1. The activation energy calculated from the straight line in Fig.5 is about 100 kJ/mol. The activation energy of the hydration was smaller than that of PO production. This result suggests that higher reaction temperature is favorable to increase in PO selectivity.
-8

-9

y=(-1.20*10-4) x + 27.3 E = 100 [kJ/mol]

ln k

-10

-11

-12

0.0030

0.0031

0.0032

1/T [K ]

-1

Fig.5 Relationship between rate constant and reaction temperature.

Fig.6 shows the effect of solvent on hydration rate over TS-1 catalyst. This figure also shows the effect of solvent on PO production rate. When methanol was used for the solvent, the production rate is the largest among the solvents, whereas the hydration is smallest. On the other hand, when ethanol or i-propyl alcohol was used as solvent, the considerable amount of the corresponding ethyl ether or i-propyl ether was observed with PG. The production of ethers was not observed over the present catalyst without hydrogen peroxide. CH3-CH(OH)-CH2OH + C2H5OH = CH3-CH(OH)-CH2OC2H5 CH3-CH(OH)-CH2OH + CH3CH(OH)CH3 = CH3-CH(OH)-CH2OCH(CH3)CH3 When the hydration of PO was carried out in aqueous solution, the hydration rate was faster than that in methanol-water solution, whereas the production rate of PO was slower than that in methanol-water solution. These results indicate that the mixture of methanol and water was effective to suppress PO hydration rate.

PO production rate [mol/(kg s)]

0.10 PO production rate PO hydration rate

1*105

0.05

5*106

0.00

methanol water

ethanol

1,4-dioxane 1-propanol

Fig.6 Effect of solvent on PO production rate and PO hydration rate.

CONCLUSION The hydration of propylene oxide (PO) was carried out over titania catalysts including TS-1 to clarify the effect of reaction condition on the reaction rate in an autoclave type batch reactor in the presence of hydrogen peroxide. The reaction was represented to 2nd order equation related to PO concentration and hydrogen peroxide. The difference between PO production rate and PO hydration rate indicates that the active sites for PO production did not coincide the active sites for PO hydration. Furthermore, UV-VIS spectra showed that PO hydration was accelerated by titania with 6 number of coordination, whereas titania with 4 number of coordination was effective to PO production. The activation energy determined from the dependency of PO hydration rate on reaction temperature. The value was smaller than that of PO production. The hydration rate is also dependent on the kind of solvent. The hydration rate was suppressed in methanol solution. REFERENCES 1. M.Mukoyama, Industrial Organic Chemistry in Japanese, Tokyo-Kagaku-Dojin, p.255 (1991) 2. M.Taramasso,G.Perego,B.Natori, US Patent 4,410,501(1988) 3. M.G.Glerici,B.Bellussi,U.Romano, J.Catal., 129, 159(1991) 4. G.F.Thiele,E.Roland, J.Mol.Catal., A Chem., 117, 351(1997) 5. P.Wu,T.Tatsumi,T.Komatsu,T.Yashima, J.Catal., 202, 245(1995) 6. K.Yamamoto,Y.Tanaka,T.Tatsumi, 84th Meeting of Catalysis Society of Japan, 4C17(1999)

PO hydration rate [mol/(kg s)]