A) Propylene As mentioned earlier, Pacific Northwest National Laboratory (PNNL) estimated potential energy savings for 26 commercial chemicals

through improved catalysts. Propylene is on this list with a potential energy savings of 98 trillion BTUs per year (Pellegrino, 2000). Propylene is produced commercially by using steam cracking of hydrocarbons. Two new processes are compared to the conventional process for propylene production, one from carbon dioxide and one from propane. The conventional process for the manufacture of propylene is the steam cracking of hydrocarbons. It is obtained as a co-product with ethylene. Propane, naphtha, or gas oil is used as a feedstock (Speight, 2002). The flow diagram representing this process is shown in Figure 3.1. Typical capacities range from 30,000 to 1400,000 tonnes per year (Wells, 1999). The overall chemical reaction involved in the process using propane as feedstock is given below. 2C3H8 C3H6 + C2H4 + CH4 + H2 H = 205.5 kJ/mol, G =127.5 kJ/mol. The above reaction is endothermic and requires substantial heat input. The hydrocarbon stream is heated with high-pressure steam before entering a tubular reactor. Heat recovered from the exit gases of tubular reactor is used to generate the required highpressure steam. The reaction takes place at a temperature of 1023 1143K and at a pressure of 31 37 atm (Wells, 1999). The yield of propylene ranges from 14 18 percent and the ethylene ranges from 42 45 percent (Wells, 1999). The mixture containing hydrogen and methane are separated in the demethanizer, and ethylene is recovered in a deethanizer tower by fractionation. Effluent from the base of deethanizer, which is a mixture of propane, propylene, propadiene (C=C=C) and propyne (C-CC) with traces of C2 and C4 hydrocarbons, passes to the depropanizer (Wells, 1999).

Hydrogen is added to convert propadiene (C=C=C) and propyne (C-CC) to propylene. The reaction is carried out in gas phase using a palladium catalyst at a temperature of 323 393K and at a pressure of 18 bar. Propylene is separated from propane in a single or double-column process using a reflux ratio between 0.90 0.97 (Wells, 1999).

The new process for propylene production will be described. Propylene can be produced from propane, but there are no plants in the lower Mississippi River Corridor that use this process. A new propylene plant built and operated by BASF Sonatrac PropanChem S.A. has started its trial operations at Tarragona, Spain (C & EN, June 2003, p.15). The $262 million plant has a production capacity of 350,000 metric tons per year of propylene, and is the first plant in Europe to use UOP LLCs C3 Oleflex technology. This plant produces only propylene, and no by-product ethylene is produced. As only propylene is needed at the Tarragona site, it is more economical to use the propane dehydrogenation process than the conventional process (C & EN, June 2003, p.15). The use of steam cracking (conventional process) to produce the same amount of propylene costs

three to four times as much as Oleflex (C & EN, June 2003, p.15). At a propane price of $180 per metric ton, the cost of production is $265 per metric ton of polymer-grade propylene. Propylene is produced in this process according to the following reaction. C3H8 C3H6 + H2 H = 124 kJ/mol, G = 86 kJ/mol. The propane feedstock containing 98 wt% propane is heated in excess of 600C and fed to the reactors, which operate slightly above atmospheric pressure. The dehydrogenation reaction is carried over a proprietary platinum catalyst from UOP, called DeH-14. The selectivity to propylene is above 85% and propane conversion per pass is about 40% (C & EN, June 2003, p.15). During product recovery, the reactor effluent is cooled, compressed and dried. Hydrogen is recovered at 90-93 mol% purity. Separator liquid is sent to a selective hydrogenation unit where a small quantity of hydrogen reacts with diolefins and acetylenes over a Pd catalyst. The reactor effluent goes to a deethanizer and propanepropylene splitter to produce a chemical or polymer-grade propylene (C & EN, June 2003, p.15). Unconverted propane, which is in excess of 60% of the feed, is recycled. The catalyst is regenerated. A comparison shows that the conventional process operates at a temperature of 1023 1143K (750-870C) and at a pressure of 31 37 atm whereas the new process operates at 600C and 1 atm. Thus, this process operates at lower temperature and pressure than the conventional process. No by-product ethylene is produced, and the conversions of propane and selectivity to propylene are comparable to the conventional process. The reaction occurring in the new process is endothermic but requires less supply of heat compared to the conventional process. The new process is three to four times more economical compared to the conventional process (C & EN, June 2003, p.15). The information for this process is based on a new plant that has started its trial operations at Tarragona, Spain. Thus, this process is more realistic than laboratory scale processes. Though this process does not use CO2 as a raw material, it is more economical than the conventional process. The by-product H2 obtained in the process can be used as a feedstock in other CO2 hydrogenation processes. In conclusion, this process is selected for HYSYS simulation because it provides a source of propylene and hydrogen for the chemical complex.

A new propylene plant with a production capacity of 350,000 metric tons of propylene was built and operated by BASF Sonatrac PropanChem S.A., and it has started its trial operations at Tarragona, Spain (C & EN, June 2003, p.15). The process description was given in Chapter Three. Propylene was produced from propane dehydrogenation over a

proprietary platinum catalyst (DeH-14). The conversion of propane per pass was 40% (C & EN, June 2003, p.15). The following reaction occurs in the reactor. C3H8 C3H6 + H2 H = 124 kJ/mol, G = 86 kJ/mol Although this process does not use CO2 as a raw material, it was selected for HYSYS simulation as it provides a source for hydrogen needed for other processes in the chemical complex. As shown in HYSYS flow sheet, Figure 4.2, unreacted propane was recycled ensuring a 100% propane conversion. Hydrogen is a by-product of this process, and the purity of the produced propylene was 99.99%. The plant capacity used in this simulation was 41,800 metric tons of propylene per year (4,767 kg/hr). This was based on Union Texas Ethylene Corporation plant, located in Geismar, LA, that produces propylene at a production capacity of 92 million lb/year (41,732 metric tons/year) (Louisiana Chemical & Petroleum Products List, 1998). Based on the HYSYS flow sheet, the energy required for this process was 750 x 105 kJ/hr, and the HP steam required to supply this energy was 45,000 kg/hr. The energy liberated from this process was 609 x 105 kJ/hr. The cooling water required to absorb this heat was 728 x 103 kg/hr, as shown in Table 4.2.

Table 4.2. Economic Results for the HYSYS Simulated Propylene Production Process described in C & EN, June 2003, p.15.