Improvement of distillation column efficiency by integration with organic Rankine power generation cycle. Introduction

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1 Improvement of distillation column efficiency by integration with organic Rankine power generation cycle Dmitriy A. Sladkovskiy, St.Petersburg State Institute of Technology (technical university), Saint- Petersburg, Russia Introduction Fractional distillation is the most common form of separation technology used in petroleum and chemical process industries. It consumes greater than 40% of the energy used by the refining or chemical plants due to low energy efficiency of a distillation column. It is well-known that significant energy savings can be achieved if complex column configurations and heat integration are used, although it withdraw the attractive advantages of conventional distillation column such as flexibility, low capital investment and low operational risk. A wide range of distillation columns can be integrated with organic Rankine cycle to reach as high as 95% efficiency of electricity generation. The Organic Rankine Cycle (ORC) is a proven method of converting low temperature heat to electrical energy. The ORC process works like a Clausius Rankine steam power plant but uses an organic working fluid instead of water. The disadvantage of such cycle is that the efficiency does not exceed 24%. The integration of distillation column reboiler and ORC allows to increase the efficiency of the power generation cycle and to reduce it s capital cost by combining heat exchanger equipment. The purpose of this paper was to analyze the efficiency of integration the ORC and various distillation columns using simulation on Aspen HySys. Combined cycle principle The operating principle of distillation column with power generation cycle is illustrated in the following example which is based on an i-pentane/n-pentane splitter column. The column separates binary mixture of equimolar composition into pure component streams with a product purity of 97.5 %mass. Figure 1 shows the basic principle of distillation column integrated with ORC (DCORC). The liquid stream from the column s bottom is pressurized by a pump to a pressure of 2000 kpa. The high pressure liquid is heated up to 163 C and vaporized in the reboiler (vaporizer). The resultant high pressure vapor stream drives the expansion turbine, which is coupled to the electricity generator or another rotating equipment. The output power of turbine is 1845 kw, assuming an 80% isentropic efficiency. Vapor stream expands to the operation pressure of the column. The turbine exhaust vapor, superheated by 98.1 C, enters the column bottom to supply heat for separation process. Inside the column, the downflowing reflux liquid provides cooling and condensation of upflowing vapors. Both the working fluid condensation and mixture separation processes take place in distillation column. Required cooling for the vapor condensation is supplied by the overhead condensing system of the column.

2 Figure 1. Distillation column integrated with ORC for ic5/nc5 separation As compare to conventional column reboiler duty the heat duty of vaporizer is increased by 1.84 MW (due to higher pressure). But mass flow through vaporizer is reduced by 27.3 t/h as a result of superheated vapor entering to the first tray of the column. 107 kw of turbine output power is required for pumping the working fluid. Thus the net output power of the cycle is 1739 MW, determined from W W η η W η where, W pump duty of distillation column integrated with ORC, MW; W turboexpander output power, MW; mechanical efficiency of turboexpander gear. 99%; η η electricity generator efficiency. 96%; η mechanical efficiency of pump. 99%; Values W and W are calculated using HYSYS according to specified adiabatic efficiencies. HYSYS calculates the expansion process rigorously by following the isentropic line from the inlet to the exit pressure [1]. The basic ORC thermal efficiency η is defined as net power out divided by thermal heat in: where, Q DCORC vaporizer duty, MW. η W Q For this example, basic ORC thermal efficiency equals to 12.8%, that is common value for such working fluid as n-pentane and for such pressure as 2000 kpa. When distillation column

3 integrated with ORC is considered, the reboiler heat load is used not only for power generation. Most of heat is used for separation. The heat used for power generation is reboiler heat load subtract conventional column reboiler heat load. The heat required for the distillation remains the same as in conventional column and is not included in the efficiency calculation. So the power generation thermal efficiency of distillation column integrated with ORC can compute as η W Q Q where, Q reboiler duty of conventional distillation column, MW. If turboexpander effectively utilizes the energy of adiabatic expansion without heat loss, the calculation shows that power generation thermal efficiency of distillation column integrated with ORC is equal to 94.7%. According to the first law of thermodynamics this efficiency value is almost independent from turboexpander adiabatic efficiency because the flow energy of pressurized vapor, not converted to mechanical work, will be transformed to internal energy which is used to produce vapor for separation. In practice, the efficiency can decrease due to mechanical and generator losses. For measuring the thermodynamic perfection of a process the perfection degree (exergy efficiency) is used. It is defined as the ratio of the useful exergy effect to the consumption of the driving exergy [2]. The perfection degree of conventional column is determined from η where, B exergy of distillate stream, MW; B exergy of bottom product stream, MW; B exergy of feed stream, MW; T environmental ambient temperature, ºC; B B B Q 1 T T T temperature in conventional column reboiler, ºC; The perfection degree of distillation column integrated with ORC includes works of pump and turbine expander: η where, T temperature of DCORC vaporizer, ºC; B B W B Q 1 T W T Considering pressure equal to 101 kpa and temperature equal to 15 ºC as the specified dead reference state the exergy of the material process streams is determined from: B m h h T s s 10 where, h, h stream mass enthalpy at process and reference states, kj/kg; s, s stream mass entropy at process and reference states, kj/kg ºK; m stream mass flow rate, kg/s; Perfection degree of conventional column is 2.8% while perfection degree of DCORC is 52.2%.

4 Influence of expander inlet pressure and temperature As for basic ORC expander inlet pressure and temperature affect on net power generation, expander inlet and outlet temperature. Optimal parameters are determined by the properties of working fluid. For distillation column integrated with ORC the working fluid has the same composition as bottom product. Working fluids can be classified as a dry, isotropic, or wet fluid depending on the slope of the saturation vapor curve on a T S diagram [3]. For dry working fluid there is no need for vapour superheating before turbine to avoid condensation during the expansion. For isotropic and wet fluids slightly superheating is required. Organic fluids with low critical temperatures and pressures can be compressed directly to their supercritical pressures and can be heated to their supercritical state before expansion. Supercritical ORC can achieve a better thermal match with the heat source [3]. The heating process of a supercritical ORC does not pass through a two-phase region like a subcritical ORC, resulting in a better thermal match in the evaporator. The outlet pressure of the expander is equal to column bottom pressure. Bottom pressure depends on condensing temperature of distillate, which in turn, depends on the cooling utility temperature. If reflux ratio, column top pressure, feed flow, feed composition and composition of products remain constant, the higher expander inlet pressure gives higher net power output. In example of i-pentane/n-pentane separation (concerned above) the influence of expander inlet pressure on net power output is illustrated on figure 2. Figure 2. Influence of expander inlet pressure on net power output Net electricity power out, kw Expander inlet pressure, kpa Starting from pressure 3000 kpa the working fluid (n-pentane) must be superheated by 0.5ºC to avoid condensation during the expansion. Increasing of expander inlet pressure leads to rise of difference between expander outlet temperature and n-pentane boiling temperature as shown on figure 3. That is, also, leads to working fluid flow rate decreasing (Fig. 3). The mass flow rate decreases because the heat of expander effluent must be constant to separate given amount (25 t/h) of the i-pentane/n-pentane feed mixture. The actual volumetric flow rate decreases more sharply than mass flow rate due to the pressure increasing, which in turn, affects on density of working fluid.

5 Figure 3. Influence of expander inlet pressure on working fluid temperatures and flow Temperature, 0 C Flow rate, t/h Expander input pressure, kpa Expander outlet temperature Working fluid mass flow rate Expander inlet temperature Figure 4 illustrates studying cycle in T-S diagram for pressures of 2000 kpa (subcritical) and 3500 kpa (supercritical cycle). From point 1 to 2 the saturated liquid working fluid is pressurized by feed pumps. From 2 to 3 heat is added at constant pressure first raising the liquid temperature to the boiling point and then evaporating it to a saturated vapor. Process from 2 to 3' is the heating of supercritical fluid. From 3(3') to 4(4') the pressurized vapor is expanded adiabatically in a turbine developing mechanical energy. From 4(4') to 1 the vapor is cooling and condensing at first tray of the column. Figure 4. T-S diagram for sub- and supercritical DCORC

6 Analysis of different separation tasks This abstract shows 4 potential distillation columns for integration with ORC. Each separation task determines composition and outlet turbine pressure of power generation cycle. Table 1 describes simulation basis is used for performance analysis which was carry out in terms of calculation procedure defined above. Table 1. Separation tasks (conventional distillation columns) Parameters Case 1 Case 2 Case 3 Case 4 Feed composition, % mass Bottom product composition (working fluid), % mass Column bottom pressure, kpa Column bottom ic5-50%, nc5-50% ic5-2.5%, nc5-97.5% ic4-50%, nc4-50% ic4-2%, nc4-98% ic4-25%, nc4-25% ic5-25%, nc5-25% nc4-0.2% ic5-49.8%, nc5-50% Benzene-50%, Toluene-50% Benzene-0.1%, Toluene-99.9% temperature, ºC Feed flow rate, t/h Distillate flow rate, t/h Number of theoretical trays Reflux ratio Reboiler duty, MW Reboiler outlet vapour flow, t/h Perfection degree, % % Operating cost, m$/y The detailed results of the simulations are displayed in Table 2. Expander inlet pressures are chosen for different heat sources such as steam 50 psi, steam 250 psi and furnace heat. In simulations the minimum temperature difference between the heat source and the working fluid does not exceed 20 ºC. Another restriction is the expander inlet pressure which does not exceed 3 MPa. The operating cost of the column is determined for 8000 h of operation per year with energy cost factors of 62 $/MW for steam at 50 psi, 66 $/MW for steam at, 72 $/MW for furnace heat and 98.8 $/MWh for electricity. The cost of cooling water is neglected. Operating cost for DCORC includes profit from electricity generation

7 Table 2. Simulation results (DCORC) Parameters Case 1 Case 2A Case 2B Case 3 Case 4A Case 4B Heat source 50psi Furnace Expander inlet pressure, kpa Expander inlet temperature, ºC Net power out, MW Vaporizer duty, MW Increasing of duty, % Operating cost, m$/y Decreasing of op. cost, m$/y Expander inlet vapour flow, t/h Perfection degree, % Conclusions Integration of distillation column with ORC increases overall heat load of the column by 10-20% but almost whole of extra heat transforms to electricity power. The theoretical DCORC electricity generation efficiency is more than 90% if conventional column reboiler duty is taken into account. The exergy efficiency of DCORC is higher than of conventional column. For high expander inlet pressures it can be as high as 50%. Only thermodynamic properties and thermal stability of column s bottom product impacts on DCORC feasibility, but not the temperature difference between top and bottom of the column. This is an advantage of suggested technology to compare with heat integrated column with heat pumps where temperature difference is quite important. For studied separation task net output electricity power is MW depending on heat source and column feed flow rate. According to the simulation results and the fact that such chemical components and their mixtures as propane, i-butane, n-butane, i-pentane et al. are utilized or considered as ORC working fluids, the DCORC is seem to be practically feasible. References 1. Aspen HYSYS operations guide. Version 3.2, Cambridge, USA. pp Szargut J. (1991), Exergy Method: Technical and Ecological Applications, WIT pres 2005, ISSN pp Chen, H.J.; Goswami, D.Y.; Stefanakos, E.K. (2010), A review of thermodynamic cycles and working fluids for the conversion of low-grade heat. Renew. Sustain. Energy Rev. 2010, 14. pp

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