Solar Energy 78 (2005) 4958 www.elsevier.

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Solar thermal power cycle with integration of methanol decomposition and middle-temperature solar thermal energy
Hui Hong, Hongguang Jin *, Jun Ji, Zhifeng Wang, Ruixian Cai
Institute of Engineering Thermophysics, Chinese Academy of Sciences, P.O. Box 2706, 12B Zhongguancun Road, Beijing 100080, China Received 6 November 2003; received in revised form 21 April 2004; accepted 3 June 2004 Available online 23 August 2004 Communicated by: Associate Editor Charles Kutscher

Abstract In this paper, we have proposed a new solar thermal power cycle which integrates methanol decomposition and middle-temperature solar thermal energy, and investigated its features based on the principle of the cascade utilization of chemical exergy. Also, the methanol decomposition with a catalyst was experimentally studied at temperatures of 150 300 C and under atmospheric pressure. The chemical energy released by methanol fuel in this cycle consisted of two successive processes: solar energy drives the thermal decomposition of methanol in a solar receiver-reactor, and the syngas of resulting products is combusted with air, namely, indirect combustion after methanol decomposition. As a result, the net solar-to-electric eciency of the proposed cycle could be 35% at the collector temperature of 220 C and the turbine inlet temperature of 1300 C, and the exergy loss in the indirect combustion of methanol was about 7% points lower than that in the direct combustion of methanol. The promising results obtained in this study indicated that this new solar thermal power cycle could make signicant improvements both in the ecient use of the chemical energy of clean synthetic fuel and in the middle-temperature solar thermal energy in a power system. 2004 Elsevier Ltd. All rights reserved.
Keywords: Middle-temperature solar energy; Methanol decomposition; Thermal power cycle

1. Introduction More recently, methanol as an alternative fuel is receiving more attention and has become a potential application in both the transportation and the power generation sectors (Jean, 2001). For production of methanol, the most promising technologies are based on the intermediate production of synthetic gas which may be

* Corresponding author. Tel.: +86 10 82622854; fax: +86 10 62575913. E-mail address: hgjin@mail.etp.ac.cn (H. Jin).

obtained from natural reforming gas or from coal gasication. The current promising integrated coal-gasication gas combined cycle and methanol synthesis, called a coal based polygeneration (POLYGEN) plant, has great potential for the decrease in the energy consumption used for methanol production. For example, oncethrough liquid-phase methanol synthesis in the-coal based POLYGEN system is expected to save about 20% of energy consumption compared with conventional recycling systems using unconverted syngas (Gao et al., 2002). Particularly in China, the methanol production from coal based POLYGEN system will not only have a broad industry perspective, but will also

0038-092X/$ - see front matter 2004 Elsevier Ltd. All rights reserved. doi:10.1016/j.solener.2004.06.019

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H. Hong et al. / Solar Energy 78 (2005) 4958

Nomenclature A1 A2 A3 Aed Aea Are AT Gf Hu H1 H3 D H1 D H3 DHed DHea qsoth Qrad Qsoth energy level of methanol energy level of solar thermal energy energy level of syngas level of energy donor level of energy acceptor energy level of methanol decomposition energy level of combustion product mole ow rate of methanol fuel input lower heating value of methanol fuel energy of methanol energy of syngas chemical energy released by the direct combustion of methanol chemical energy released by the combustion of syngas energy released by energy donor energy accepted by energy acceptor solar thermal energy absorbed by decomposition of per mole methanol fuel solar radiation process heat provided by solar thermal energy SS W Wref DW gcol gex Dgsol Dgtot,sol e1 esoth e3 D e1 e3 DEXL1 DEXL2 DEXL3 soalr share of the energy input overall power output of the proposed cycle overall power output of the reference cycle incremental ratio of the output work thermal eciency of solar collector systems exergy eciency of the cycle incremental electric eciency of solar thermal energy net solar-to-electric eciency chemical exergy of methanol exergy of solar thermal energy chemical exergy of syngas chemical exergy released by the direct combustion of methanol chemical exergy released by the combustion of syngas chemical exergy loss in the direct combustion of methanol exergy loss in solar thermal decomposition of methanol chemical exergy loss in the combustion of syngas

oer a means of eective and clean use of coal, since coal is Chinas primary energy resource, is relatively high in ash content, and its use has already caused a serious environmental impact. With signicant development in methanol production, how to eectively utilize methanol as a fuel in conventional power systems will therefore become an important issue. Methanol can be decomposed easily by a catalyst at temperatures of about 200300 C (Nakagaki et al., 2001). This process is a middle-temperature endothermic process. In this paper, the temperature range between approximately 200 and 300 C is dened as middle temperature. Concentrating solar collectors with parabolic troughs can oer an attractive means of providing solar thermal energy at middle temperatures. If we concentrate diluted sunlight with the help of a parabolic trough with a suitable concentration ratio and then capture that radiate energy with the help of suitable receivers, we will be able to obtain solar thermal energy at temperatures of about 200300 C that can provide the process heat required for driving methanol decomposition. This combination of solar thermal energy and methanol decomposition has two positive features: the heating value of methanol fuel can be upgraded and made equal to the solar thermal energy input; the middle-temperature solar thermal energy collected can be converted into chemical energy. Traditionally, solar applications for this temperature range of 200300 C are principally for space heat-

ing, and even for the generation of electricity, the Rankine cycle with organic working media is applied and the net solar-to-electric eciency is lower than 10%. On the other hand, when coupled with methanol decomposition, the middle temperature solar thermal energy can be applied to the solar thermochemical process and a storable and transportable fuel can be produced. Thus, there will be a tremendous advance in the ecient use of middle-temperature solar thermal energy. Solar thermal decomposition of methanol can be considered as a process of the solar upgrade of hydrocarbons. In recent years, several researchers have played pivotal roles in investigating solar upgrading or the decarbonization of hydrocarbons. Solar thermal petroleum was proposed by Epstein and Spiewak (1996). Using solar thermal steam to reform natural gas or the steam-gasication of coal was studied (Steinberg, 1999; Steinfeld and Palumbo, 2001). The energy conversion eciencies of solar decarbonization of natural gas and coal have also been analyzed (Hirsch et al., 2001; Zedtwitz and Steinfeld, 2003). Solar upgrading of methane for the generation of electricity was proposed (Tamme et al., 2001) and the SOLASYS project for a 300 kW plant with solar upgrading of natural gas was supported by the European Commission and demonstrated in Israel (Tamme et al., 2001; Romero et al., 2002). Solar upgrading of hydrocarbons often takes place at high temperatures and central receiver systems (CRSs) are

H. Hong et al. / Solar Energy 78 (2005) 4958

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required for providing the process heat for this kind of high temperature endothermic process. In the latest years, for reducing the cost of solar thermal power, a novel combination of power and cooling thermodynamic cycle with using low temperature solar heat source was proposed by Goswami (Goswami, 1998; Goswami and Xu, 1999). This innovative cycle could utilize at plate solar collectors with a potential reduction in the capital costs of solar thermal power by as much as 50%. The evaluating eciency of this combined power and cooling cycle was investigated and the expressions of eciency were proposed (Vijayaraghavan and Goswami, 2003; Hasan and Goswami, 2003). Exergy analysis of a combined power and refrigeration thermodynamic cycle driven by a solar source was analyzed (Hasan et al., 2002), and the performance of this kind of cycle and optimization were examined (Tamm and Goswami, 2003a,b; Lu and Goswami, 2003). Furthermore, an experimental system was developed for demonstrating the feasibility of this cycle (Tamm and Goswami, 2003a,b). The objective of the system in the present study is to investigate a new solar thermal power cycle for the eective use of methanol as a fuel and to research middletemperature solar thermal energy. In this study, we demonstrate the feasibility of the use of a middle-temperature solar collector based on an experimental study on the reactivity of methanol decomposition, and identify the characteristics of the integration of methanol decomposition and middle-temperature solar thermal energy.

Middle temperature solar collectors

Syngas
Reactor Solar thermal receiver Compressor

3 5
Combustor Gas turbine

Concentrated radiation

2
Heater

6
Steam turbine

Air

CH 3OH 1
HRSG

Pump

Condensor

Fig. 1. A ow diagram for solar thermal power cycle with solar decomposition of methanol.

2. Description and model of cycle 2.1. Cycle description Fig. 1 shows a simplied diagram of the new solar thermal power cycle, which integrates methanol decomposition and middle-temperature solar thermal energy. An easily manufactured, parabolic trough-solar collector is used to concentrate the solar energy for methanol decomposition. The solar receiver is divided into two segments containing a heater and a reactor. The receiver-heater is composed of three sections: preheater, evaporator and superheater. Liquid methanol fed (stream 1) is preheated in the preheater, and evaporated in the evaporator. After that, the saturated methanol vapor is superheated to the entry temperature of the catalyst bed of the reactor in the superheater. The solar thermal energy is absorbed as a form of the sensible and latent heat of the methanol in the receiver-heater. The methanol vapor (stream 2) then enters the receiver-reactor and carries out an endothermic reaction driven by solar energy. The reaction path is CH3OH ! CO + 2H2, DH = 62 kJ/mol-CH3OH at a temperature of 220 C and at a pressure of 17 bar. In the reactor, the

concentrated solar energy can be converted into the chemical energy associated with the syngas. After that the upgraded syngas with CO and H2 (stream 3) is fed into a combustor in the gas turbine and burned with the compressed air (stream 4). Since the middle-temperature solar thermal energy is stored in the syngas and is released in the form of higher-temperature gas (stream 5), it can be converted into electricity in the gas turbine. Finally, the gas turbine exhaust gas (stream 6) at a temperature of 500600 C drives a steam turbine through the dual-pressure heat recovery steam generator (HRSG). The parabolic trough concentrators employed in this cycle could be produced commercially and appear to have excellent near-term potential for market penetration. The thermal eciency of the current parabolic trough collectors is higher than 50%, even when the direct solar radiation is at a level of 100 W/m2 and the solar collector average temperature is lower than 200 C. An indirect receiver-reactor (Diver, 1987) may be applied in this cycle. For a real solar receiver-reactor, the system may contain an internal preheater where a counter-owing heat recovery uid extracts heat from the catalyst bed of the reactor to maintain constant catalyst bed temperature. 2.2. Model and results Like other solar hybrid thermal power systems, the performance of this cycle was evaluated by both the overall cycle eciency and net solar-to-electric eciency. Since this cycle employs both methanol fuel and solar energy as its input resources with dierent qualities of energy, the second-law eciency is a more suitable criterion to evaluate the performance of the cycle than the rst-law eciency. The denition of exergy eciency of the cycle was given as follows:

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gex

W Gf H u Gf qsoth 1 T 0 =T col

Table 1 Simulation condition Direct solar radiation Solar collector temperature Solar collector eciencya Pressure of solar receiverreactor Turbine inlet temperature Pressure ratio of gas turbine Polytropic eciency of compressor Polytropic eciency of gas turbine Polytropic eciency of steam turbine Pressure loss of combustor Methanol injection pressure loss Minimum heat transfer temperature dierence Exhaust temperature from HRSG
a

The exergy of methanol fuel was assumed as approximately equal to its lower heating value Hu The exergy of solar thermal energy corresponded to the maximum work availability operating at solar collector temperature Tcol and ambient temperature T0 namely qsoth (1 T0/Tcol). The Gf was treated as the mole ow rate of methanol fuel input. To measure the contribution of solar thermal energy to the cycle performance, the solar shares and the conversion eciencies of solar energy were dened based on the paper given by Buck et al. (2002). The solar share of the energy input (SS) was given as SS Gf qsoth Gf H u Gf qsoth W W ref W 2a

800 W/m2 220 C 0.62 17 bar 1300 C 15 0.86 0.89 0.86 3% 15% 10 C 102 C

Solar collector eciency here represents for the peak value.

and the incremental ratio of the output work (DW) was DW 2b

Table 2 Thermodynamic performance results Parameters Input energy (kJ/molCH3OH) Methanol (LHV) Solar thermal energy Input exergy (kJ/molCH3OH) Methanol Solar thermal exergy Exergy loss (kJ/molCH3OH) Combustion Endothermic reaction Power subsystem HRSG Output exergy (kJ/molCH3OH) Net power Exergy eciency of cycle Thermal solar share Solar-to-electric eciency Reference CC 676.29 Solar CC 676.29 147.88 676.29 58.51 154.61 13.29 65.20 55.50 446.20 60.7% 18% 35%

where Wref is the work output of the conventional gas turbine combined cycle with the same input methanol fuel relative to the proposed cycle. Incremental electricity eciency of solar thermal energy (Dgsol) was given as Dgsol W W ref Gf qsoth W W ref Qrad 2c

676.29

Net solar-to electric eciency (Dgtot,sol) was given as Dgtot;sol 2d

202.54 54.95 48.98 366.44 54.6%

where Qrad denotes the total power coming from the concentrator. Eq. (2d) expresses the incremental total solar-to-electric eciency. For this study, we recognized it as the net solar-to-electric eciency. For evaluation of the cycle performance, the eciency of the trough-type solar collector was based on experimental data (Wyman et al., 1980). The system was simulated by using the ASPEN PLUS code. The most relevant assumptions are summarized in Table 1. Assumptions were made for the solar reactor: the solar thermal reactor was assumed to be a perfect blackbody cavity-receiver and the chemical equilibrium was considered inside the reactor. The product composition of syngas was stoichiometric with only CO and H2, and the RedlichKwongSoave equation was applied to calculate the thermodynamic properties. In addition, the cooling of the hot parts of turbine was not included yet. The work for pumping the liquid methanol fuel was negligible. The simulation results are shown in Table 2. In comparison with the reference cycle, the increase of the second-law eciency of the proposed cycle was about 6% points. Particularly, the chemical exergy loss of the pro-

posed cycle in combustion was about 7% points lower than that of the reference cycle based on the exergy of input fuel. The net solar-to-electric eciency could be expected to be about 35% and the thermal solar share was about 18% at the turbine inlet temperature of 1300 C.

3. Experimental study on the reactivity of methanol decomposition 3.1. Experimental procedure Extensive experimental research has been conducted on methanol decomposition in recent years, and mostly focused on the catalyst activity and selectivity for reac-

H. Hong et al. / Solar Energy 78 (2005) 4958

53

tion as well as the kinetics of reaction (Lindstro m and Pettersson, 2002; Takeda et al., 2002; Yongtaek and Stenger, 2002). This study attempted to realistically predict the eect of solar collector average temperature on methanol decomposition; the reactivity of methanol decomposition was preliminarily investigated at atmospheric pressure. A diagram of the experimental apparatus is shown in Fig. 2. Liquid methanol with a purication of 99.5% was fed into the evaporating section by a liquid pump and was heated to a given temperature in the superheating section. Then the superheated methanol vapor owed into the decomposition section. The gas components of products were separated at the cooling section and were measured using a gas chromatograph. The experiments were carried out over a temperature interval of 150300 C. For all experiments catalysts of 2.0 g were packed in the catalyst bed, and the feed rate of liquid methanol was controlled to 0.3 ml/min by a owmeter. A stainless steel tubular reactor 18 mm in diameter and 435 mm in length was used for reaction tests. The catalysts were ground and charged to the central part of the reactor, which was 135 mm in length. The catalyst used was CuO/ZnO/AL2O3, commercially manufactured by the Institute of Nanjing Chemical Engineering in China (type NC-306). The catalyst was cylindrical, 5 mm in diameter and 5 mm in length. To ensure isothermal conditions along the reactor tube, four electric heaters were used and the temperature was measured by two thermocouples which were located at the inlet and middle on the outer surface of the tube. 3.2. Experimental results Methanol decomposition with catalysts was studied. The main gas products were hydrogen and carbon monoxide as well as a minor product of carbon dioxide and methyl formate. Fig. 3 illustrates the conversion rate of

Methanol conversion (%)

100 80 60 40 20 0 100 150 200 250 300

o

P = 1 bar Equilibrium conversion Experiment

Reaction temperature ( C)
Fig. 3. Conversion of methanol with reaction temperature.

Fig. 2. Experimental apparatus.

methanol versus reaction temperature at the pressure of 1 bar. Experimental results are plotted by a solid line. Here we considered the wall temperature of the reactor as the reaction temperature. At temperatures below 175 C, the conversion rate increased slowly with the temperature, while at temperatures above 175 C, it increased rapidly. The methanol conversion was more than 90% at between 220 C and 300 C. These trends are consistent with the recent results reported by Yongtaek and Stenger (2002). The experimental results obtained in this study suggest that solar thermal energy at 220300 C collected by parabolic trough collectors can meet the need of methanol decomposition, and the conversion of methanol can exceed 90%. The chemical equilibrium conversion of methanol is illustrated by a dashed line in Fig. 3. It can be seen that the variation of equilibrium conversion versus reaction temperature was similar to that of experimental results. The methanol conversions of both the cases were more than 90% in a range of 220300 C, and when the temperature continued to rise, they did not seem to increase further. This means that solar collector temperatures between 220 C and 300 C would be more appropriate for solar thermal decomposition of methanol. In addition, the experimental data at 150200 C were apparently dierent from equilibrium conversion. To acquire higher methanol conversion in a range of 150200 C, the unconverted methanol may be recovered during the experiment. That is to say, the unconverted methanol separated at the cooling section could be delivered into the evaporator and reactor for further continuous decomposition (as shown by the recycle line in Fig. 2). Thus, the relatively complete conversion of methanol can be expected to be achieved at temperatures of 150 200 C compared with the previous once-through methanol decomposition. This indicates that when this route of recycling unconverted methanol is applied into the proposed cycle, the lower temperature parabolic trough collector or even higher eciency at plate should be able to collect solar energy to drive methanol decomposition.

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H. Hong et al. / Solar Energy 78 (2005) 4958

4. Features of the new solar thermal power cycle 4.1. Integration of methanol decomposition and middletemperature solar thermal energy 4.1.1. Upgrade of energy level from solar thermal energy to chemical energy The middle-temperature solar thermal energy can be converted into chemical energy through methanol decomposition. From the viewpoint of energy level, this will be a breakthrough in middle-temperature solar thermal energy. Energy level A proposed by Ishida and Kawamura (1982, 1997) is used as the property that represents the quality of released or accepted energy for a given process. It is dened as the ratio of exergy change De to energy change DH, namely, A = De/DH = 1 T0DS/DH. For transferred heat, its energy level AT may be simplied to AT = 1 T0/T where T0 is the environmental temperature and T is the temperature of the heat source. Thus, the energy level of solar thermal energy may be given as A2 = 1 T0/Tcol where Tcol is an average collector temperature. Solar driving methanol decomposition composes a dual process of energy transformation: the solar thermal energy as an energy donor releases the heat and the methanol decomposition as an energy acceptor accepts the heat (shown as a dashed rectangle in Fig. 4b). For the combined processes, energy balance and exergy balance are given, respectively, as H 1 Qsoth H 3 e1 esoth e3 DEXL2 3a 3b

The values of H1 and e1 of methanol are equal to DH1 and De1 released by methanol combustion. The values of H3 and e3 of syngas are equal to DH3 and De3 released by syngas combustion. Then Eqs. (3a) and (3b) are also rewritten as DH 1 Qsoth DH 3 De1 esoth De3 DEXL2 4a 4b

For the denition of energy level A, the exergy change De may be given De = DHA. Thus we have De1 DH 1 A1 De3 DH 3 A3 esoth Qsoth A2 5a 5b 5c

The exergy loss DEXL2 caused by a mismatch of energy levels between the solar thermal energy and methanol decomposition may be obtained, based on EXL = DHea(Aed Aea) (Ishida, 1997), where Aed and Aea represent, respectively, the levels of energy donor and energy acceptor: DEXL2 Qsoth A2 Are 5d

By applying Eq. (5a) to Eq. (5d) into Eq. (4b) we have DH 1 A1 Qsoth A2 DH 3 A3 Qsoth A2 Are DH 3 A3 DH 1 A1 Qsoth Are Introduction of Eq. (4a) into Eq. (6a) becomes Qsoth A3 DH 1 A1 A3 Qsoth Are 6b 6a

(a)

Air (O2 )

QsothA3 states the conversion of solar thermal exergy into the chemical exergy associated with the syngas. Subtracting solar thermal exergy QsothA2 on both sides of Eq. (6b) gives: Qsoth A3 A2 DH 1 A1 A3 Qsoth A2 Are 7a

CH3OH

EXL1

CO2 +H 2O

T, A T

H 1 , 1

H 1 , 1
Air (O 2)

The term of (A3 A2) represents the energy level upgraded from solar thermal energy A2 to chemical energy A3. The relative upgrade in energy level of solar thermal energy may be given by dividing QsothA2 on both sides of Eq. (7a): A3 A2 A1 A3 =A2 A2 Are A2 Qsoth =DH 1 A2 7b

(b)

Middle-temperature thermal energy

Q soth , soth
CH3OH
EXL

H 2 + CO
2

H 1 , 1

H 3 , 3

EXL 3

CO2 + H 2O

T,

AT

H 3 , 3

Fig. 4. (a) Direct combustion of methanol. (b) Indirect combustion of methanol.

The energy level dierence between methanol A1 and syngas A3 acts as a driving force to raise the low grade of solar thermal energy to the higher one of chemical energy. Qsoth/DH1 denotes the ratio of the solar thermal energy absorbed to the heat of the combustion of methanol, and measures the conversion of solar thermal energy into chemical energy. The dierence between A2 and Are refers to the match of energy levels between solar thermal energy and methanol decomposition.

H. Hong et al. / Solar Energy 78 (2005) 4958

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Eq. (7b) shows that the relative upgrade in the energy level of solar thermal energy is dependent on the interactions of these three factors. Fig. 5 illustrates the relative upgrade in energy level of solar thermal energy (A3 A2)/A2 with the average temperatureTcol of the solar collector. At the Tcol of about 200300 C corresponding to an A2 of about 0.390.48, the relative upgrade in the energy level of solar thermal energy has a relatively higher value compared with other ranges of A2 as shown on the curve of U. This means that collecting this temperature range of solar thermal energy could bring about the higher conversion of solar thermal energy into chemical energy (the higher ratio of Qsoth/DH1) and a good match between solar thermal energy and methanol decomposition (the smaller dierence of A2 Are). Thus, the driving force (A1 A3) may boost the energy level of solar thermal energy to the higher one of chemical energy to the greatest extent. At temperatures higher or lower than 200300 C, the mismatch of energy levels between solar thermal energy and methanol decomposition causes the lower relative upgrade in the energy level of solar thermal energy. Furthermore, a comparatively lower temperature such as 150 C cannot obtain the higher conversion of solar thermal energy into chemical energy. The curve of W in Fig. 5 shows the relative upgrade in the energy level of solar thermal energy by means of methane-steam reforming with the product of CO and H2. The results show that W by solar energy is lower than through methanol decomposition. Reforming methane requires a higher energy level of thermal energy with about 0.720.77 (8001000 C) which is near the energy level of syngas of 0.95 (Jin and Ishida, 2000). Consequently, in comparison with methanol decomposition, there is not enough driving force for enhancement of the energy level of high-temperature solar thermal energy in methane-steam reforming.

4.1.2. Potential for reducing chemical exergy loss in combustion In the proposed cycle, the chemical energy of methanol is released through two steps: an endothermic reaction (CH3OH ! CO + 2H2) and exothermic reaction (CO + 2H2 + 1.5O2 ! CO2 + 2H2O) at high temperatures, as shown in Fig. 4b. In this study, the coupling of two processes was called the indirect combustion of methanol, which diered from the traditionally direct (single-step) combustion of methanol (CH3OH + 1.5O2 ! CO2 + 2H2), as shown in Fig. 4a. In the direct combustion of methanol, the chemical energy of methanol is directly degraded to low-quality thermal energy. On the other hand, in the indirect combustion of methanol, the chemical energy of methanol could rst be harvested in the solar decomposition of methanol; thus, the degradation in the energy level from chemical energy into thermal energy may be decreased in succession of the combustion of syngas. That is to say, there is a feature of cascade utilization of the chemical energy in the indirect combustion of methanol. An important point here is how this advantage of cascade utilization of chemical energy brings about the reduction of chemical exergy loss in the indirect combustion of methanol. Fuel combustion can be considered as an exothermic combustion reaction coupled with the heat sink. The energy transformation in the combustion process takes place between the exothermic combustion reaction and the heat sink. The combustion reaction plays the role of energy donor and releases the chemical energy to the heat sink as an energy acceptor. Assume that the direct and indirect combustions of methanol proceed at the same temperature T, and the combustion products are considered as the heat sink. Thus, based on the exergy loss EXL = DHea(Aed Aea) (Ishida, 1997), the chemical exergy loss in the direct combustion of methanol DEXL1 can be given as DEXL1 DH 1 A1 AT 8a

Upgraded energy level (

1.5

Solar upgrading of methanol Solar upgrading of methane

Upgraded energy level (

0.37 0.56 0.66 0.72 0.77 0.80 ( A 2) 0.3

and the chemical exergy loss in the combustion of syngas DEXL3 is DEXL3 DH 3 A3 AT 8b

Fig. 5. Upgraded level of solar thermal energy with collector temperature.

1.0

0.2

0.5

0.1

Considering the exergy loss DEXL2 = Qsoth(A2 Are) in the methanol decomposition as a part of the chemical exergy loss in the indirect combustion of methanol, then the total chemical exergy loss in the indirect combustion of methanol is given as DEXL3 DEXL2 DH 3 A3 AT DH 2 A2 Are 8c Thus, the reduction of the chemical exergy loss in the indirect combustion of methanol is taken as follows:

0.0 200 400 600 800 1000 1200

o

0.0

Collector average temperature Tcol ( C)

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H. Hong et al. / Solar Energy 78 (2005) 4958

DEXL1 DEXL3 DEXL2 DH 1 A1 AT DH 3 A3 AT QSoth A2 Are 9 By substituting Eq. (4a) for DH3(DH3 = DH1 + DH2) we have DEXL1 DEXL3 DEXL2 DH 1 A1 A3 QSoth A3 AT QSoth A2 Are 10 Introduction of Eq. (6b) gives rise to DEXL1 DEXL3 DEXL2 QSoth AT A2 11

13.26 kJ/mol-CH3OH in methanol decomposition (as shown on the shaded area of 1). This indicates a decrease of about 7% points compared with direct combustion (202.54 kJ/mol-CH3OH). The increased theoretical work output of the cycle is shown in the shaded area of 2. 4.2. Advanced thermodynamic performance 4.2.1. Signicant improvement in middle-temperature solar thermal energy for electricity Fig. 7 illustrates the solar-to-electric eciency of the proposed cycle versus the solar collector temperature for dierent turbine inlet temperature (TIT) and at a given pressure ratio of 15. At collector temperatures of about 220300 C, the net solar-to-electric eciency for dierent TIT is higher than 30%, and has the maximum value at about 220 C. For example, at the turbine inlet temperature of 1300 C the solar-to-electric eciency of the cycle should be about 35%. This signicant improvement in the middle-temperature solar thermal energy for the generation of electricity can be attributed to the conversion of low-level solar thermal energy into high-level chemical energy, resulting in the generation of electricity in a high eciency gas turbine. It is noteworthy that at collector temperatures above 220 C, the solar-to-electric eciency of the cycle gradually slows down for a given turbine inlet temperature due to the mismatch of energy levels between the solar thermal energy and the methanol decomposition. This shows that in a region for a given solar radiation condition, collecting solar thermal energy at a temperature of about 220 C would be a preferable option for the higher solar-to-electric eciency in the cycle. In addition, Fig. 8 illustrates the eects of the pressure ratio p on the net solar-to-electric eciency of the cycle at given collector temperatures of 150 C and 220 C. The solar-to-electric eciency for dierent turbine inlet temperatures has an optimum pressure ratio (as shown by the dashed line) due to the characteristics of the gas turbine combined cycle.
Solar to electric efficeincy (%)
4

Since the temperature of combustion products is much higher than that of solar thermal energy, namely, AT is higher than A2, Eq. (11) is always positive. This reduction of chemical exergy loss could increase the maximum work available of combustion products, enhancing the work output of the gas turbine in the cycle. Fig. 6 depicts the chemical exergy losses in the direct and indirect combustions of methanol at a temperature of 1300 C. The abscissa refers to energy change DH and the ordinate denotes energy level A. In direct combustion, the average energy level of methanol A1 is directly degraded from 1.03 to combustion products AT of 0.8. Consequently, the greater degradation in energy level from chemical energy to thermal energy results in a chemical exergy loss of 202.54 kJ/mol-CH3OH (as shown on the shaded area of adcb). Comparatively, in the indirect combustion of methanol, the energy level from A1 to AT can be divided into two stages. The rst stage is the use of the chemical energy level from A1 to A3 for boosting the lower level of solar thermal energy A2(A2 = 0.40) to syngas A3(0.95). The second stage is the degradation from syngasA3 to combustion products AT of 0.8 in the combustion of syngas. As a result, the total exergy loss reaches 167.91 kJ/mol-CH3OH, including a chemical exergy loss of 154.61 kJ/mol-CH3OH in combustion (as shown on the shaded area of adcb) and an exergy loss of

1.0

a a' b

A1 A3 A 2, solar thermal energy A re,methanol decomposition

Q Soth

35 30 25 20 15

d d' c' 2

3 = 15 2 1

A T Q (A -A ) c Soth T 2

1
0 0

1: TIT = 1300 oC 2: TIT = 1200 oC 3: TIT = 1100 oC 4: TIT = 1000 oC

150

200

H ea [kJ/mol-CH 3OH]

400

600

800

Solar collector temperature Tcol ( oC)

200

250

300

Fig. 6. Chemical exergy loss in direct and indirect combustions.

Fig. 7. Variation of solar-to-electric eciency with solar collector temperature.

H. Hong et al. / Solar Energy 78 (2005) 4958

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57

TCol=220oC ( Col= 0.62)

Net solar to electric efficiency sol (%)

34 32 30 17 16 15 14 4 6 8 10 12 14 16 18 20

TCol=150 C ( Col=0.65)

TIT (o C) 1300 1200 1100 1000

should be 61% at a given TIT of 1300 C and a collector temperature of 220 C, with about 6% points higher than that of the reference cycle for an optimum pressure ratio of about 16 (55%). This is mainly due to the decrease in the chemical exergy loss of the combustion of syngas in the proposed cycle.

5. Conclusion A new solar thermal power cycle with the integration of middle-temperature solar thermal energy and methanol decomposition has been proposed. The experimental study on the reactivity of methanol decomposition demonstrated the feasibility of the use of parabolic trough collectors in the new cycle. Especially, we have claried that combining solar thermal energy and methanol decomposition can upgrade the lower level of solar thermal energy to a higher one of chemical energy with syngas and reduce the chemical exergy loss in the indirect combustion of methanol. As a result, the net solar-toelectric conversion eciency in this new cycle (with a turbine inlet temperature of 1300 C) could be as high as 35%, and the exergy loss of combustion could be reduced by about 7% points. The exergy eciency could also be increased by about 6% points compared with the conventional gas turbine combined cycle. This new solar thermal power cycle could build a bridge connecting both high eciency use of middle-temperature solar thermal energy and eective utilization of chemical energy of methanol fuel, and shows promise as a new solar thermal power plant competitive with conventional power plant in the near future.

Pressure ratio

Fig. 8. Variation of solar-to-electric eciency with pressure ratio at two dierent collector temperatures.

4.2.2. Comparison with the conventional combined cycle Fig. 9 illustrates a comparison of the exergy eciencies between the proposed cycle and the reference cycle. The variation in the exergy eciency of the proposed cycle with the pressure ratio p for dierent turbine inlet temperatures is similar to that of the reference cycle. For both cycles the pressure ratio has an optimum value for the exergy eciency of the cycle (as shown by a short solid line). This means that the new solar thermal power cycle has the same thermodynamic characteristic as the conventional combined cycle. For a given pressure ratio and turbine inlet temperature, the exergy eciency of the proposed cycle is higher than that of the reference cycle. For example, the exergy eciency for an optimum pressure ratio of about 16

Acknowledgement This work was supported by the Natural Scientic Foundation of China (no. 90210032 and no. 59925615).

The exergy efficiency of cycle (%)

References
60 57 54 51 48

Proposed cycle TIT ( C) 1300 1200 1100 1000 Reference cycle

o

45 4 6 8 10 12 14 16 18 20

Pressure ratio

Fig. 9. Comparison of the exergy eciencies between proposed cycle and reference cycle.

Buck, R., Bra uning, T., Denk, T., Pfa nder, M., Schwarzbo zl, F., Tellez, F., 2002. Solar-hybrid gas turbine-based power tower systems (REFOS). J. Sol. Energy Eng. 124, 29. Diver, R.B., 1987. Receiver/reactor concept for thermochemical transport of solar energy. J. Sol. Energy Eng. 109, 199203. Epstein, M., Spiewak, I., 1996. Solar experiments with a tubular reformer. In: Proceedings of the 8th Int. Sym. Solar Thermal Concentrating Technologies, Cologne, Germany, 611 October, 1996, pp. 12091229. Gao, L., Jin, H., Liu, Z., Zheng, D., 2002. In: Proceedings of the 15th Int. Confer. on Eciency, Costs, Optimization, Simulation and Environmental Impact of Energy Systems, Berlin, Germany, 35 July, 2002, Pro. ECOS 2002, pp. 137 144.

58

H. Hong et al. / Solar Energy 78 (2005) 4958 Romero, M., Buck, R., Pacheco, J.E., 2002. An update on solar central receiver systems, projects, and technologies. J. Sol. Energy Eng. 124, 98108. Steinberg, M., 1999. Fossil fuel decarbonization technology for mitigating global warming. Int. J. Hydrogen Energy 24, 771777. Steinfeld, A., Palumbo, R., 2001. Solar thermochemical process technologies. In: Meyers, R.A. (Ed.), Encyclopedia of Physical Science and Technology, vol. 15. Academic Press, pp. 237256. Takeda, K., Baba, A., Hishimuma, Y., Chikahisa, T., 2002. Performance of a methanol reforming system for a fuel cell powered vehicle and system evaluation of a PEFC system. JSAE Rev. 23, 183188. Tamm, G., Goswami, D.Y., 2003a. Novel combined power and cooling thermodynamic cycle for low temperature heat sources. Part I: theoretical investigation. J. Sol. Energy Eng. 125, 218222. Tamm, G., Goswami, D.Y., 2003b. Novel combined power and cooling thermodynamic cycle for low temperature heat sources. Part II: experimental investigation. J. Sol. Energy Eng. 125, 223229. Tamme, R., Buck, R., Epstein, M., Fisher, U., Sugarmen, C., 2001. Solar upgrading of fuels for generation of electricity. J. Sol. Energy Eng. 123, 160163. Vijayaraghavan, S., Goswami, D.Y., 2003. On evaluating eciency of a combined power and cooling cycle. J. Energy Resour. Technol. 125, 221227. Wyman, C., Castle, J., Kreith, F., 1980. A review of collector and energy storage technology for intermediate temperature application. Solar Energy 24, 517540. Yongtaek, C., Stenger, H.G., 2002. Fuel cell grade hydrogen from methanol on a commercial Cu/ZnO/Al2O3 catalyst. Appl. Catal. B: Environ. 38, 259269. Zedtwitz, P.v., Steinfeld, A., 2003. The solar thermal gasication of coal-energy conversion eciency and CO2 mitigation potential. Energy 28, 441456.

Goswami, D.Y., 1998. Solar thermal power technology: present status and ideas for the future. Energy Sources 20, 137145. Goswami, D.Y., Xu, F., 1999. Analysis of a new thermodynamic cycle for combined power and cooling using low and mid temperature solar collectors. J. Sol. Energy Eng. 121, 9197. Hirsch, D., Epstein, M., Steinfeld, A., 2001. The solar thermal decarbonization of natural gas. Int. J. Hydrogen Energy 26, 10231033. Hasan, A.A., Goswami, D.Y., 2003. Exergy analysis of a combined power and refrigeration thermodynamic cycle driven by a solar heat source. J. Sol. Energy Eng. 125, 5560. Hasan, A.A., Goswami, D.Y., Vijayaraghavan, S., 2002. First and second law analysis of a new power and refrigeration thermodynamic cycle using a solar heat source. Solar Energy 73 (5), 385393. Ishida, M., 1997. Process System Synthesis and Available Information Proceedings of TAIES, pp. 370376. Ishida, M., Kawamura, K., 1982. Energy and exergy analysis of a chemical process system with distributed parameters based on the energy-direction factor diagram. Ind. Eng. Chem. Process Des. Dev. 21, 690695. Jean, P.L., 2001. Methanol synthesis: a short review of technology improvements. Catal. Today 64, 38. Jin, H., Ishida, M., 2000. A novel gas turbine cycle with hydrogen-fueled chemical-looping combustion. Int. J. Hydrogen Energy 25, 12091215. Lindstro m, B., Pettersson, L.J., 2002. Steam reforming of methanol over copper-based monoliths: the eects of zirconia doping. Power Sources 106, 264273. Lu, S., Goswami, D.Y., 2003. Optimization of a novel combined power/refrigeration thermodynamic cycle. J. Sol. Energy Eng. 125, 212217. Nakagaki, T., Ogawa, T., Murata, K., Nakata, Y., 2001. Development of methanol steam reformer for chemical recuperation. ASME J. Eng. Gas Turbines Power 123, 727 733.