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Supercritical Carbon Dioxide Turbo-Expander and Heat Exchangers

The Southwest Research Institute (SWRI) and its partners, under the 2012
Concentrating Solar Power (CSP) SunShot R&D funding opportunity announcement
(FOA), are developing a supercritical carbon dioxide (s-CO2) power cycle that
combines high efficiencies and low costs for modular CSP applications.

Approach

The SWRI team is working to advance the state-of-the-art s-CO2 turbo-expander
design from laboratory testing to full prototype demonstration.

The project goals are to:

·0 Develop a novel, high-efficiency s-CO2 hot-gas turbo-expander optimized for
CSP applications

·1 Optimize novel printed-circuit heat exchangers for s-CO2 applications to
drastically reduce their manufacturing costs

·2 Test the s-CO2 turbo-expander and novel s-CO2 heat exchanger in a 1-MWe s-
CO2 test loop

(Conceptual layout of an integrated, high-efficiency supercritical CO2 hot gas turbo-expander
that is optimized for the highly transient solar power plant duty cycle profile.)

Demonstrate component performance and the performance of the optimized s-CO2
Brayton cycle over a wide range of partial-load conditions and during transient
operations representative of a typical CSP duty cycle.

Technology Development for Supercritical Carbon Dioxide (SCO2) Based Power Cycles The Advanced Turbines Program at NETL will conduct R&D for directly and indirectly heated supercritical carbon dioxide (CO2) based power cycles for fossil fuel applications. The focus will be on components for indirectly heated fossil fuel power cycles with turbine inlet temperature in the range of 1300 . like that in Figure 1. not unlike the way steam would be heated in a conventional boiler. This allows a large amount of energy to be extracted at high temperature from equipment that is relatively small in size.Innovation The scalable s-CO2 expander design and improved heat exchanger close two critical technology gaps required for an optimized CSP s-CO2 power plant. Successfully developing these systems represents a major stepping-stone on the pathway to achieving a levelized cost of energy of $0. and increasing energy conversion efficiency to greater than 50%. The cycle is operated above the critical point of CO2 so that it does not change phases (from liquid to gas). SCO2 turbines will have a nominal gas path diameter an order of magnitude smaller than utility scale combustion turbines or steam turbines. the CO2 is heated indirectly from a heat source through a heat exchanger. but rather undergoes drastic density changes over small ranges of temperature and pressure. Remaining heat is extracted in one or more highly efficient heat . In this cycle. The supercritical carbon dioxide power cycle operates in a manner similar to other turbine cycles.06 per kilowatt-hour. Energy is extracted from the CO2 as it is expanded in the turbine. The cycle envisioned for the first fossil-based indirectly heated application is a non- condensing closed-loop Brayton cycle with heat addition and rejection on either side of the expander.1400 ºF (700 - 760 ºC) and oxy-fuel combustion for directly heated supercritical CO2 based power cycles. but it uses CO2 as the working fluid in the turbomachinery.

The mixture is further cooled to condense the water out and then compressed for storage.recuperators to preheat the CO2 going back to the main heat source. Figure 2 illustrates a potential configuration of this cycle. In this particular cycle. . the remaining heat in the steam/CO2 mixture is recuperated to preheat the cooled and compressed CO2 that is used as the combustion diluent. These recuperators help increase the overall efficiency of the cycle by limiting heat rejection from the cycle. (Closed Loop SCO2 Recompression Brayton Cycle Flow Diagram) Directly fired SCO2 cycles combust fossil fuels with oxygen and the resulting steam/CO2 mixture is used to drive the turbine.

particularly coal. can provide an ideal heat source for SCO2 cycles. Studies suggest that a supercritical CO2 oxy-fuel PFBC system has the potential to significantly increase efficiency by 9 percentage points over other pulverized coal oxy-fuel combustion configurations with a 20 percent lower levelized COE and the potential for near 100 percent CO2 capture. Supercritical carbon dioxide extraction of compounds with pharmaceutical importance from microalgae Abstract . There are also opportunities to advance these performance numbers with higher firing temperatures made possible by advanced airfoil cooling technology. Water consumption and other emission profiles are also very attractive for this cycle.( Oxygen Fueled Directly Heated SCO2 Cycle) Fossil fuels.

0 MPa and temperature of 313. The yield of supercritical extraction of carotenoids was also compared at several conditions of pressure and temperature. The cyanobacteria Arthrospira (Spirulina) maxima can produce in large amounts the g-linolenic acid (GLA).1 K. 20. and decreased with temperature at 20. The hydrocarbons of this microalga were selectively extracted and this selectivity increased with pressure. . of the lipids and GLA were determined and compared with those obtained with organic solvents.5. it was shown that the cis/trans ratio. Dunaliella salina. remained practically constant with temperature. Arthrospira maxima) were object of supercritical CO2 extraction studies.5 and 35.1 K. It increased with pressure at constant temperature. C18:3 v6. Supercritical extracts obtained at 313. Chlorella vulgaris.1 and 333. unlike those obtained with organic solvents.0 and 30.0 MPa. using CO2 and CO2 doped with ethanol. were golden and limpid. which produces b-carotene in high yield. Natural b- carotene (cis and trans mixture) from this alga was submitted to supercritical carbon dioxide and it was assessed. increased significantly.1 K and pressures up to 35. in the supercritical extracts. at pressures of 27.Four microalgae (Botryococcus braunii. at pressures up to 30. crushed and slightly crushed algae at a pressure of 35. The microalga Botryococcus braunii produces extracellular alkadienes. when the Dunaliella was submitted to supercritical CO2. Moreover.0 MPa and a temperature of 328. The microalga Chlorella vulgaris is a carotenoid producer of canthaxanthin and astaxanthin.1 K.0 MPa. The extraction yields of lipids and carotenoids were compared for whole. that both isomers presented higher solubility than the synthetic trans-b-carotene and that the cis isomer was much more soluble in supercritical CO2 than the trans isomer.0 MPa. relatively to the original one in the microalga. and pressures of 12. The yield and selectivity of the supercritical extraction.0 MPa. The third alga studied was the Dunaliella salina. which were carried out in a flow apparatus at temperatures between 313.

This compound presents important pro-vitamin A and anti-oxidant properties. Chlorella vulgaris. of b-carotene and luthein [3]. such as Botryococcus braunni. in minor amounts. therefore. Dunaliella salina and cyanobacteria Arthrospira (Spirulina) maxima. has been applied in several pharmaceutical applications.Microalgae are eucaryotic photosynthetic microorganisms that can be used to produce high value compounds. but with a high yield [4]. Dunaliella salina is also a producer of bcarotene. This polyunsaturated fatty acid has an important role in the human metabolism pathway and. These natural compounds have important applications in pharmaceutical industry. which is a producer of astaxanthin. canthaxanthin. Botryococcus braunii is a green microalga that produces hydrocarbons whose content can reach 85% of the dry biomass. The race A of this microalga produces mainly extracellular alkadienes. Moreover. Chlorella vulgaris is a microalga of orange colour. as well as. diabetes and rheumatoid . having already been proposed as a future renewable source of fuels [1]. multiple sclerosis. the cyanobacteria Arthrospira (Spirulina) maxima can produce in large amounts the g-linolenic acid (GLA). At the Department of Renewable Energy (INETI-Portugal) several microalgae species are grown. C18:3 v6. such as the treatment of schizophrenia. which can substitute parafinic and natural waxes in pharmaceutical industry [2].

since the before mentioned limitation can be avoided. Dunaliella salina [4] and the cyanobacteria Arthrospira (Spirulina) maxima [8.arthritis [5]. because the compounds can be obtained without contamination by toxical organic solvents and without thermal degradation. has been developed to use the supercritical extraction to obtain compounds with pharmaceutical interest from microalgae. CO2 has been the most used supercritical solvent. . Severe legislative restrictions are currently being proposed to eliminate the traces of the corresponding toxical solvents [6]. involving Laboratory of Experimental Thermodynamics (IST) and the Department of Renewable Energy (INETI). The before mentioned compounds are traditionally obtained by solvent extraction. supercritical fluid extraction (SFE) has received increased attention as an important alternative to the traditional separation methods. An experimental program. The aim of this work was to assess the capability of supercritical CO2 extraction of compounds with pharmaceutical importance from these microalgae. Supercritical CO2 extraction studies have been performed in a flow apparatus involving the microalgae: Botryococcus braunni [7]. In recent years.9]. Chlorella vulgaris [3].

1. in 1861. Tc. In this diagram the vapour/liquid equilibrium curve starts at the triple point (TP). The corresponding values of temperature. are designated by critical temperature and pressure. solid. liquid and vapour are in equilibrium. 1 the CO2 is in the supercritical state if its temperature and pressure are higher than the corresponding critical values. reported in the IUPAC International Tables for this compound [10]. In the . On the other hand. This behaviour was observed for CO2. allowed the construction of the pressure/temperature phase diagram shown in Fig. where the tree phases. respectively. This curve ends at the critical point (CP). at the Queen’s College ofBelfast [11]. in Fig. In Table 1 are presented the values of the critical temperature and pressure for CO2 and other fluids with interest in SFE.Basic principles on supercritical fluids Accurate PVT measurements on CO2 carried out by several workers. and pressures. Pc. for the first time by Andrews. where the meniscus separating the liquid and the vapour phases disappears and only a single phase occurs.

1. the efficiency of the separation of compounds from a vegetable matrix with a Fig. therefore. The solvent power of the supercritical fluids can also be influenced by its transport properties. the supercritical fluid is capable of a faster and deeper penetration into a vegetable matrix containing the substance to be extracted than a liquid. Since the density of the supercritical fluid is similar to that of the liquid. its solvent power can also be almost the same and can be adjusted by the control of pressure and temperature. by the density of the solvent. . Therefore. the density of the fluid phase is particularly sensitive to small changes in pressure and temperature [12].supercritical fluid region. namely by the viscosity and mass diffusivity. The solubility of a solute in a solvent is strongly influenced by the heteromolecular interaction and. Table 2 shows the ranges. On the other hand. Pressure/temperature phase diagram for carbon dioxide. of the above mentioned thermophysical properties for a gas. Then. near the CP. a supercritical fluid and a liquid. as the values of the diffusivity and the viscosity are between those of the gases and liquids. it is expected that a supercritical fluid to be a bad solvent in states with low or gas-like densities and a good solvent at high or liquid-like densities. in terms of orders of magnitude.

The cells are immersed in a water bath. In fact. at constant temperature. 9. which was described in detail in a previous paper [16]. which was also placed at the top to avoid entrainment of the material extracted. is compressed with a pump. 2. 1. from its pressure. Liquid CO2 from a cylinder. the CO2 is . The pressure is controlled through a back-pressure regulator. before it reaches the extraction cells. 8. and measured with a Bourdon type manometer.Experimental Supercritical fluid apparatus Supercritical CO2 extraction of compounds from microalgae were carried out using a flow apparatus. The extraction of the compounds from the microalgae depends of the density of the supercritical fluid and therefore. 7. the lower part of the extractors is filled with glass wool. 16. After the extraction of the compounds. The alga is placed inside the extractors and occupies only a part of them. schematically represented in Fig. and preheated in a heat exchanger. 10 and 11. 5.

which replaced the micrometering valve. as well as of the downstream tubing. 15. The gas flow-rate is monitored with the rotameter. . being their amount assessed gravimetrically. the expansion of the fluid was carried out via a three-way valve. at the end of each run. the washing of the inside of the valve.expanded to atmospheric pressure through the micrometering valve. 13. To ensure a total recovery of the solutes in the solubility measurements. This allowed. the extracted compounds are practically insoluble in CO2 and they are collected in a cooled glass U-tube. heated to the temperature of the water bath. At this pressure. 14. 12. by acetone (having in view the recovery of the precipitated carotenes for further analysis). and the total volume of gas is measured with a wet test meter.