Applied Energy 180 (2016) 546–559

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Applied Energy
journal homepage: www.elsevier.com/locate/apenergy

Low temperature techniques for natural gas purification and LNG
production: An energy and exergy analysis
Margaret Baccanelli a, Stefano Langé a,⇑, Matteo V. Rocco b, Laura A. Pellegrini a, Emanuela Colombo b
a
Politecnico di Milano, Dipartimento di Chimica, Materiali e Ingegneria Chimica ‘‘G. Natta”, Piazza Leonardo da Vinci 32, I-20133 Milano, Italy
b
Politecnico di Milano, Dipartimento di Energia, via Lambruschini 4, Milan, Italy

h i g h l i g h t s 

Low-temperature processes for of high CO2 content natural gas have been modelled. 
Energy and exergy analyses have been performed. 
The Dual Pressure distillation scheme has the best thermodynamic performances. 
There is a synergy between cryogenic natural gas purification and LNG production.

a r t i c l e i n f o a b s t r a c t

Article history: Due to the rapid increase of the World’s primary energy demand of the last decades, low-temperature
Received 16 February 2016 processes for the purification of natural gas streams with high carbon dioxide content has gained interest,
Received in revised form 26 July 2016 since they allow to make profitable exploitation of low-quality gas reserves. Low temperature purifica-
Accepted 28 July 2016
tion processes allow the direct production of a methane stream at high purity and at low-temperature,
Available online 9 August 2016
suitable conditions for the direct synergistic integration with natural gas cryogenic liquefaction pro-
cesses, while CO2 is obtained in liquid phase and under pressure. In this way, it can be pumped for trans-
Keywords:
portation, avoiding significant compression costs as for classical CO2 capture units (where carbon dioxide
LNG
Exergy analysis
is discharged in gas phase and at atmospheric pressure), and further uses such as Enhanced Oil Recovery
Natural gas purification (EOR) or underground storage.
Carbon dioxide In this paper, the three most common natural gas low-temperature purification techniques have been
modelled and their performances have been evaluated through energy and exergy analyses. Specifically,
the dual pressure low-temperature distillation process, the anti-sublimation process and a hybrid config-
uration have been considered. It is found that the dual pressure low-temperature distillation scheme
reach the highest thermodynamic performances, resulting in the best values of exergy efficiency and
equivalent methane requirements with respect to the other configurations. This is mainly due to the dis-
tributed temperature profile along a distillation column, resulting in a less irreversible heat exchanging
process.
Ó 2016 Elsevier Ltd. All rights reserved.

1. Introduction CO2 contents between 15% and 80% [2,3]. Sour and acid gas
reserves are located in different geographic areas, such as South-
1.1. The synergic potential of low-temperature natural gas purification East Asia, North Africa, Middle East, USA and Australia [2]. As
processes and LNG production instances, the giant Natuna field in Indonesia is characterized by
a CO2 content higher than 70%; the Kapuni field in New Zealand
According to the known geographic distribution of gas reserves, with a CO2 content of about 43.8% [4]; the Uch field in Pakistan
almost 40% of the global reserves are sour [1] and about 30% have a with 46.2% of CO2 [4]; the LaBarge field in Wyoming (USA) of about
65% [5].
In last decades, low-temperature processes for the purification
⇑ Corresponding author.
of highly acid and/or sour gas reserves have started to gain atten-
E-mail addresses: margaret.baccanelli@mail.polimi.it (M. Baccanelli), stefano.
lange@polimi.it (S. Langé), matteovincenzo.rocco@polimi.it (M.V. Rocco), laura. tion. Beside classical and worldwide adopted absorption processes,
pellegrini@polimi.it (L.A. Pellegrini), emanuela.colombo@polimi.it (E. Colombo). above all chemical scrubbing by means of aqueous alkanolamine

http://dx.doi.org/10.1016/j.apenergy.2016.07.119
0306-2619/Ó 2016 Elsevier Ltd. All rights reserved.

the CryocellÒ process [15. These processes can be classified into two main groups with methane by means of a specific thermodynamic cycle. Baccanelli et al. while anti-sublimation is performed opurÒ process [17] based on the anti-sublimation technique [18] at pressures below the triple point one of CO2 ). one of their major con. able to per. For such reason. while the final purification of the nologies can be found in literature.24] where a bulk CO2 removal is performed form a profitable exploitation of acid and sour natural gas reserves. patented low-temperature dual pressure distillation process cerns resides in the formation of a CO2 solid phase inside the sys. the SprexÒ process [23. / Applied Energy 180 (2016) 546–559 547 Nomenclature Symbols SAT standard ambient temperature COP coefficient of performance [–] SLE solid-liquid-equilibrium Cp specific heat at constant pressure [J mol1 K1] SLVE solid-liquid-vapor-equilibrium Ex exergy [kJ] SRK Soave-Redlich-Kwong E_ x exergy rate [kW] SVE solid-vapor-equilibrium F feed molar flow [kmol h1] V vapor H_ enthalpy rate [kW] VLE vapor-liquid-equilibrium LHV lower heating value [MJ kg1] m _ mass flow [kg s1] Subscripts n_ molar flow [kmol h1] B boiler P pressure [bar] CC combined cycle Q_ duty [kW] ch chemical R ideal gas constant [J mol1 K1] D destroyed T temperature [K] el electric t time [s] F cold V vapor flow [kmol h1] gen generated V volume in Table 4 [m3] i generic component W electric power [kW] id ideal x liquid phase mole fraction [mol mol1] IN inlet y vapor phase mole fraction [mol mol1] j generic index Dh latent heat [kJ kmol1] k generic index g efficiency [–] kn kinetic s Carnot factor [–] mix mixture c activity coefficient [–] OUT outlet p generic index Acronyms ph physical AAD% Absolute Average Deviation % pt potential AHE Anti-sublimation Heat Exchanger q generic index BFD block flow diagram rev reversible CCS Carbon Capture and Storage rif reference state EOR Enhanced Oil Recovery tri triple point EoS Equation of State II second principle of thermodynamics HP high pressure 0 reference state for exergy analysis IEA International Energy Agency JT Joule-Thomson Superscripts L liquid cond condensation LNG liquefied natural gas eV evaporation LP low pressure G gas MDEA methyl di-ethanol amine IN inlet mol molar basis m_ exergy contribution related to material flows NG natural gas Q_ exergy contribution related to heat RHE recovery heat exchanger sub sublimation S solid W _ exergy contribution related to mechanical work SAP standard ambient pressure solutions. is performed under pressure. According to authoritative projections of future energy temperature natural gas purification processes includes: the scenarios [8]. evant to investigate alternative purification processes. while CO2 is . [7.25] designed to bypass the freezing point of CO2 in mixtures tem. operated Several types of low-temperature natural gas purification tech. such as n-butane) is used to resulting in the highest growth trend [9]. the primary energy demand is expected to grow Ryan-Holmes process [20–22] where an entrainer (normally a rapidly over the next twenty years: natural gas will play a key role. The according to how the CO2 is treated: processes designed to handle final product of low-temperature purification processes consists the formation of a solid phase inside equipment and processes that in a high-purity methane stream at low-temperatures and at pres- avoid the CO2 freeze-out. The first group includes the CFZTM process sures depending on the selected technology (typically distillation by Exxon Mobil [5. shift CO2 freezing conditions at lower temperatures and pressures. in a pressurized low-temperature distillation column. away from freezing conditions. Since these processes operate at gas is made with a traditional MDEA unit and.7]. The second group of low- of CO2 [6. M. recently. hydrocarbon heavier than methane.10–14]. a new temperatures below the triple point of CO2 . it is rel. the Cry. low-temperature processes allow to reduce the total and the integrated cryogenic CO2 removal coupled with pressur- operating costs when dealing with gases containing high amounts ized natural gas liquefaction [19].16].

defining moreover possible growing [31]. Baccanelli et al. region at higher temperatures reduces till the triple point pressure vant regeneration and recycle facilities). geographic location of gas production sites and end-markets [28– Moreover. the growing importance of LNG in the global energy market [33–37] can be highlighted considering the increase in liq. form the liquefaction by means of Mixed Refrigerant Cycles (MRC) The phase behavior of the binary system CH4  CO2 at different [39]. rele. Specifically. Moreover. tion column. from less than 1 MT y1 the considered processes. even if forecasting the future market is difficult pathways for process optimization. VLE equilibrium for pure CO2 2. SLVE ones. low-temperatures. The works by Lim et al.25]. such configuration should present in the system. due to the variations in energy prices. Mostly these processes per. tion processes. in the open literature no (Fig. LNG production are present. with the inlet gas feed under pressure It is possible to notice that the Solid-Liquid-Vapor Equilibrium and at temperatures close to the ambient one. giving compactness to the process solution. is close to high pressure and low-temperatures (about 173. considering also phase [26] (1. The anti-sublimation process [17]. avoiding at the same time the formation of a liquid phase for the finishing action. Below this . This work aims to better investigate ery (EOR) or Carbon Capture and Storage (CCS). The reliability of the global natural gas market [9]. cascade cycles with pure component refrigerants and expan. about 50 bar. In order to better investigate the thermodynamic behavior of uefaction train sizes from 1960 to 2011. In order to reach high methane purities avoiding intermediate performances when compared with the previous extremely low temperature levels. the temperature difference between SLVE and tion of LNG is supplied during the purification step. through a comparison with literature available experimental data posed for the production of LNG [38]. the competition with other sources of natural gas and the ever-changing economic situations of different countries [32]. such as geopolitics cation processes in order to determine which solution allows to and safety issues [27]. The behavior of the system is similar when pressure this process does not require any ad-hoc designed equipment is furthermore decreased: the SVE region enlarges and the VLE and/or third components to prevent CO2 freeze-out (i. this paper aims to show that the combination of energy 30] is a key-driver for the development of the LNG market and exergy analysis can provide a reliable tool to better screen pro- [27. of pure CO2 . The maximum pressure of the SLVE locus is above the critical one of pure CH4 . transport of natural gas in liquid temperature technologies with LNG production. In this way. large-scale LNG production. This concept is better explained considering the isobaric diagram at 1 bar Basing on the authors knowledge. at the same time.01325 bar and 113. and Chang the Pressure-Temperature (PT) diagram of the mixture (Fig. 3). Other aspects.3 [42].15 K) is favored when distances a possible combination of two low-temperature natural gas purifi- are higher than 3500 km [27]. The dual pressure distillation process proposed by Pellegrini [25]. other works about the detailed study and assessment (on both From Fig.40] offer a detailed overview of industrial processes for the liq. of Type-I according to the Van Konynenburg and Scott [50] classi- uefaction of natural gas. process [17]. [7. that is the second process considered in this work. locus is crossed twice and the VLE region is separated by a Solid- This process allows the removal of carbon dioxide without Vapor Equilibrium (SVE) region at temperatures between the two incurring in freezing conditions in a distillation unit. Low-temperature (SLVE) locus presents a pressure maximum and his left part. CO2 freezing at triple point occurs at any pressure below temperature natural gas purification processes and LNG produc. These conditions are suitable to operate the anti-sublimation 3. When pressure is decreased from 50 bar to 40 bar the SLVE 1. The hybrid process is the combination of a pressurized distilla. / Applied Energy 180 (2016) 546–559 recovered as a pressurized liquid phase. 1) is [27. with heat exchangers for anti-sublimation stream.15 K) [41]. VLE of pure methane is narrow. Recent studies show that LNG trades are continuously cess technologies and their interaction. the selected simulation framework has been already validated Several natural gas liquefaction technologies have been pro. The phase equilibria in these conditions can be better visu- are here considered: alized by means of isobaric diagrams (Fig. which is suitable to be temperature natural gas purification processes with cryogenic pumped and transported for further purposes: Enhanced Oil Recov. Different technically feasible low-temperature process layouts [7.e. relying on the LNG trade is expected to grow in a significant way. the possibilities of an effective combination of these low- From a technical perspective. giving the SRK Equation of State (EoS) [43] and predicting the solid CO2 for- major contribution to the expansion.30]. Aim of the work to obtain pure methane avoiding CO2 freeze out by means of a sin- gle distillation unit at constant pressure. it is not possible 1. the purification in the SLE region at low pressures. wide SVE region at temperatures down to the SLVE one. Mostly. 2).2. the mismatch between the external fuels and. In such the Vapor-Liquid Equilibrium (VLE) line of pure CH4 . optimizing the use of energy. pressure is essential for this study: it is well known in literature sion processes where a turboexpander is used instead of a Joule. minimizing the consumptions of natural gas transport as LNG. phase equilibria calculations have been (Algeria) up to 8 MT y1 (Quatargas and RasGas) [32]. temperature close to the VLE one of pure CH4 .40]. (50 bar and 40 bar) in order to bypass the SLVE locus of the mixture sis. the graph. The global performed by means of Aspen HysysÒ V7. integration and flexibility of mation by means of the CO2 Freeze-out utility. Thermodynamic framework Despite this. Specifically. at processes. this work assesses the thermodynamic The low-temperature distillation process considered in this performances of different low-temperature natural gas purification work has been designed to operate at two different pressures processes with LNG production through energy and exergy analy. 2. These processes are applied mainly to the fication of phase diagrams. 3 it is possible to notice that the system presents a energy and exergy bases) of the coupling of innovative low. should be taken into account when selecting obtain the best performances. Thomson (JT) valve [27.44]. hence. Below this pressure.548 M. This process allows to remove does not exist anymore and the SLVE locus is crossed only at one dry ice directly over the surface of a dedicated heat exchanger. the volatility of regional markets. part of the overall cooling duty required for the produc. As can be inferred from This work contributes in the synergistic coupling of low. which natural gas purification processes provide liquefied natural gas at goes from the maximum to the triple point of pure CH4 . and it has been studied by several authors [44–49]. it is not possible to operate ones. that performs only a bulk purification so avoiding by frosting CO2 at SVE leaving few ppms in the main methane solid CO2 formation.

temperature. 3.1 0.6 0. this software is not able to perform 283 283 263 Temperature [K] 263 Temperature [K] V V 243 243 L+V L+V L L 223 223 S+L S+L+V 203 203 S+V L+V S+L+V 183 S+L 183 S+L L 163 163 0 0.7 0.2 0.1.99 Pressure [bar] 60 L+V 150 111. Description of the process schemes’ layout required high-purity) is necessary to provide cooling duties at a temperature of about 111. sublimation process (2) and hybrid process (3). The pressure is consistent with that of natural avoid the formation of a CO2 -rich solid phase during expansion gas at the wellhead and such to prevent CO2 freeze-out in distilla- from high pressures to the atmospheric one at which LNG is stored. as recommended for LNG methane in SVE conditions at low pressures. Process schemes design specifications The layouts of the three simulated processes are here presented: the dual-pressure distillation process (1). 2. However.9995 1 S+L+V 30 110 20 S+L 90 10 0 0. Fig. PT diagram of the CH4-CO2 system [7]. The material streams at battery of CH4 limited to 100 ppm in order to enhance the CH4 recovery limits are the same for each considered configuration. is separated in order to recover liquefied of the considered processes and their relative simulation CO2 and pure CH4 . Isobaric diagrams at 50 bar (left side) and 40 bar (right side) for the CH4  CO2 system [7].15 50 LNG 0. a dual pressure Oil Recovery (EOR) [5.01325 bar: the target purity for the lique- during expansion may occur and solid CO2 is separated from fied gas has been fixed at 50 ppm of CO2 . considering the SRK EoS [43] as the thermodynamic package content. In this way. when a distillation technology is adopted for LNG produc- tion.9 1 x CH4 x CH4 Fig.96 40 S+L+V VLCO2 0. Process simulations have been performed through Aspen HysysÒ A flow rate of 5000 kmol h1 of natural gas with high CO2 V7. The [25]. The final product in all the considered During the anti-sublimation process. a Solid-Liquid Equilibrium (SLE) and a narrow VLE Stream xCH4 xCO2 F [kmol h1] T [K] P [bar] region exist. / Applied Energy 180 (2016) 546–559 549 100 210 SL CH4 90 SL CO2 L=V V 190 80 Temperature [K] 112 70 170 S+L+V S+V 111. Baccanelli et al.2.4 5000 308.1 0. such as: reinjection for permanent storage (CCS) or Enhanced is different: as introduced in Section 1.7 0.3 0. an anti-sublimation on heat exchangers surfaces and a coupling of the previous ones is here considered.4 0.5 0. The VLE region is present at very high methane concentrations and in a small temperature range.4 0. Table 1 Molar streams specifications at battery limits.999 0.3. The material balances across the battery limits approaches are summarized in Table 1.15 K. The by-product of the processes Three different process schemes for the production of LNG have is a stream of liquid CO2 available at 50 bar and a mole fraction been considered in this work.3 0. tion process equipment.99995 5e5 3000 111.16.4 0.5 0. considered as a binary CH4  CO2 mix. it INLET NG 0.6 0.98 111.3 0. Thus.9 1 0 0.52].75 1.01325 is possible to obtain anyway methane in liquid phase also at low Liquid-CO2 1e4 0.8 0.2. The main features ture with 40 mol% of CO2 .9985 0. the purity of the produced methane should be high enough to process schemes.2 0.7 0. the anti- The natural gas stream.2 0. To achieve the liquefaction of the produced stream (methane at the 3. the formation of a solid phase case-studies is LNG at 1. 1.5 0. .25.9999 2000 287.8 0. production [51] to avoid freezing problems during liquefaction.6 0. is the feed to all the for calculations. M.1 0. 3. distillation.75 K. These conditions are suitable for its transport and further low-temperature purification technology adopted in each process uses.21 50 pressures (for instance higher than the triple point pressure of pure methane).97 S+L L S+V 50 VL CH4 130 111. Process scheme layouts 3.6 0.8 0. are summarized in Table 1.9 1 SVCH4 SVCO2 0 x CH 4 70 90 110 130 150 170 190 210 230 250 270 290 310 Temperature [K] Fig. available at 50 bar and at 308. Isobaric diagram at 1 bar for the CH4  CO2 system.

the process scheme layouts are pre- phase: for this reason. the duties required at reboiler and scheme approach temperature number condenser of the dual pressure low-temperature distillation pro- cess are similar to the ones of the original patent [25]. (1) for solid CO2 heat top product stream is the methane-rich stream D1 (with about capacity.15808 [59] 1 DhCH4 (111. the methane critical pressure. while the second one at low pressure (LP. With this configuration. stream and a bottom methane-rich liquid stream that is pumped Parameter Value [kJ mol1] Reference back to the HP section.20 [57] on the fourth tray from the top. 4. before entering the HP section of the distillation unit (INcolumn). It has been assumed that this section consists of a gas This Work turbine followed by a cooler.CO2 ¼ 33:972 þ 1:820T þ 1:810  102 T 2 þ 8:600 trade-off between energy consumptions and investment costs  105 T 3  1:496  107 T 4 þ 188:173  T 1 ð1Þ (referring to natural gas purification technologies by means of dis- tillation [21. the natural gas purification is performed J mol1 K1) has been performed using the polynomial Eq. 25 and 20 theoretical trays have Table 2 been adopted for the distillation columns employed. The HP section performs a bulk removal of the inlet T [K] CO2 : the bottom stream is liquid CO2 at high pressure. it is not possible to obtain pure methane performing distillation at 50 bar. about 2 mol% of Process Purification step Purification step Simulation tools CO2). and outlet streams are reported in Table 1 and are the same for all ances have been evaluated separately (see Table 2). by means of the dual pressure low-temperature distillation process where the constant coefficients have been evaluated regressing [25]. while in the original patent [25] 20 and 15 theoretical trays have been used to produce pipeline-quality gas (i. 4). no freezing can occur during distillation at about 50 bar. it has been applied only to simulate process sented by means of block flow diagrams (BFDs).33 [58] introduced at the first tray from the top. the INLET NG stream is precooled 30 using stream D1-A.2. while the liquid reflux (Reflux) is eV DhCO2 (215. Correlations for the evaluation of heat capacities for CO2 and CH4 in gaseous and liquid phases have been derived from litera. In the same way. 1). In this process. In order to estimate energy been used in Figs. correlation well fits experimental data (Fig.3. the LP column works anti-sublimation and cryogenic in thermodynamic in series series balances as the enrichment section of a classic distillation column: it has a partial condenser on the top and the gas feed stream is the top pro- duct from the HP section. The INcolumn stream enters the HP column Dhsub CO2 (183. Comparison between experimental data [56] and Eq.65 [59] CO2 eV 8.550 M. The number of theoretical stages for distillation columns has been chosen considering a qualitative cSp. material and enthalpy bal. The precooled Feed stream is furthermore cooled 10 down to reach its dew point in a second heat exchanger. In the first heat exchanger. operated at about 40 bar. below in Table 3. while the Fig. 5. the purification section consists of two distil- the experimental data reported by Giauque and Egan [56]: the lation columns: the first one is operated at high pressure (HP. 40 Before entering the HP distillation column.15 K) 26. The product gas stream from the top of LP column is composed mainly of methane at the required purity 60 specifications.5 mol% of CO2 ). Solid CO 2 Cp [J mol -1 K-1] The INLET NG stream is fed at the conditions reported in Table 1. According to the phase behavior of the CO2  CH4 0 0 50 100 150 200 mixture (see Figs. The bottom product from the purifi- 50 cation section is highly pure CO2 (Table 1). The final purifica- Table 3 tion is performed in the LP section. The evaluation of heat capacity of solid CO2 (in In the scheme of Fig. it is cooled down to its dew point at 50 bar (INcolumn) using two heat exchangers in ser- ies. 1–3). In particular. above the maximum of the SLVE curve of the PT diagram enthalpies used to solve the energy balances have been collected (Fig.9 bar [54]).65 K) For interpretation of color in Figs. in order to avoid CO2 freezing at the inlet of the LP column. Red1 boxes have equipment that handle fluid phases. using an external utility. The over gas stream D1 Dhfus (Ttriple) 8. 6.1. The CO2 and CH4 thermo-physical properties for balance calculation: phase change produced streams from the LP section are a top methane gas enthalpies. the reader is referred to the web version of this article. (1). LNG is then produced by means of a proper liquefac- Giauque Egan (1936) tion train. 6 and 10. 40 bar). the three presented processes.65 K) 15. 3. while the liquid balances reflux is provided by recycling the liquid stream coming from the 3 Distillation and Low temperature Aspen HysysÒ plus bottom of the LP section. The HP col- 1 Distillation Low temperature Aspen HysysÒ 2 Anti-sublimation Cryogenic Aspen HysysÒ plus umn can be regarded as the stripping section of a common thermodynamic distillation column: it presents only a reboiler. Baccanelli et al. that are much more stringent than pipeline-quality gas ones. Since the HP section operates at a pressure above the methane critical one (45. respectively. The phase change 50 bar).24]) and considering the LNG purity specifications. / Applied Energy 180 (2016) 546–559 detailed process simulations considering the presence of a solid In the following sections. 6 and 10 to highlight the unit operations simu- consumptions and to verify the heat recovery feasibility for equip. lated with Aspen HysysÒ V7. The properties of the main inlet ment in which dry ice formation occurs. Process scheme layout features.e. . that needs to be heated (D1-A1) to provide a superheated gas stream (D1-A2) after expansion to the pressure 20 of the LP section. for process scheme 1. Dual pressure low-temperature distillation process ture [53–55].

where this process is often applied to cation and liquefaction. 3) it is necessary to expand the stream to a be formed during its expansion. The reflux ratio for the LP dis. where it is cooled down. two heat exchangers are operated in dynamic mode. Layout of the dual pressure low-temperature distillation process.RHE Þ Q_ IN _ sub down to stream FEED-1. Once the RHE is cleaned and ready to sup- surfaces to perform natural gas purification. The amount of heat recovery is defined CO2 ¼ n CO2T  D h CO2 ðT CO2. must not be CO2 regeneration (Recovery Heat Exchanger RHE) phases.2 bar [64]). the heat Q_ IN . / Applied Energy 180 (2016) 546–559 551 Fig. The stream is sent to a heat exchanger where it is cooled ðT FEED2 DT min.RHE Þ ð2Þ The stream FEED-1 is fed to RHE. that is fed in turn to the LP section one the. This guarantees that no solid phase can anti-sublimation (Fig. a solid CO2 layer grows and a gas stream with 50 ppm of CO2 (D1) 3. 7. (D1-B1) at 50 bar (away from the SLE boundary) and expanded to The stream FEED-3 enters the AHE. Several studies on this technology AHE is performed to assure continuity in natural gas stream purifi- can be found in literature. while dashed for the regen- phase changes: the solid lines represent the path followed in order eration one. assuming a minimum temperature approach of about 5 K. an amount of dry ice separates from the main stream in SVE.2. ally in adiabatic mode. from the HP section is sent to a splitter.15 K (FEED-2) by melting the dry ice that is recovered as liquid _HFEED1 ðTÞ ¼ n_ CH4  h~ ðT Þ þ CpGCH4 ðTÞdT rif rif CO2 at its triple point (CO2-T). the CO2 removal from flue gases and biogas. investigating the dry ice anti-sublimation process has been simulated according to heat and formation on heat exchanger surfaces and to perform thermody. Different line styles (solid by relations (3)–(5). In this process. pro- vides part of the cooling duty to FEED-1. (2). 6. In the scheme presented With reference to Fig. To achieve CO2 pressure of the LP section. The D1A/D1B split cess. In the case that Q_ IN is higher than Q_ OUT . factor is chosen in order to keep the CO2 level in the Reflux stream To reach the purity specification required for LNG production. to calculate Q_ IN using Eq. material balances across RHE and AHE. The CO2 -T rif rif T rif stream is then pumped to 50 bar (CO2 -int) and heated in a heat . calculated using relation (2).21 K at # 50 bar. RHE has been assumed to operate glob- in Fig. plied by an external refrigeration cycle.frosting). and ensuring less than Q_ OUT . Since CO2 solid phase formation occurs. which separates it into two recovery equipment where coupling of the CO2-int stream with streams (D1-A and D1-B respectively). at VLE.4. Baccanelli et al. calculated through the energy balance expressed the continuous operation of the process. Anti-sublimation process is available at atmospheric pressure and can be liquefied for LNG The LNG production by means of the anti-sublimation process production. cond þ DhCO2 ðT FEED2  DT min. In order to avoid pinch cross prob. stream D1-A is heated up (D1-A1) and expanded expanded from 50 bar to the atmospheric pressure by means of a to the LP section pressure (D1-A2) 5–6 K over its dew point at the Joule-Thomson (JT) valve and turns into FEED-3. The INLET NG stream is fed to the process at the conditions in CO2 " Z Table 1.15 K (TCO2. the port dry ice formation and the AHE presents a solid CO2 layer that purification is performed allowing dry ice formation in a closed needs to be liquefied and recovered. when the c RHE worked as AHE. The the LP section pressure in order to obtain a liquid stream at its cooling duty necessary to perform the CO2 anti-sublimation is sup- bubble point (D1-B2).2. a below 8 mol% to avoid CO2 freezing. During the expansion pro- oretical tray above the gas feed stream D1-A2.frosting Þ þ CpGCO2 ðTÞdT T CO2.RHE) is kept between T IN ~ ðT Þ þ þ n_ CO2  h CpGCO2 ðTÞdT ð3Þ the temperatures of stream FEED-2 and of stream CO2 -T. the gas stream down to 113. The stream FEED-2 from RHE.frosting in order to warm the liquid stream CO2 -int up to 287. A heat exchanger using an external cooling medium (Fig. 8 is useful to understand CO2 lines are used for the operation phase. a switch between RHE and and dedicated unit operation. further CO2 separation is necessary and it is accomplished cooling tillation has been set to 2. The dry ice layer deposited during the previous operating cycle. The flows direction according to the working phase alternation: solid thermodynamic cycle shown in Fig. 5. FEED-1 is cooled down to " Z # T IN 222. Before entering the bottom INLET NG one takes place. is of the LP section. M. T rif " Z # lems a minimum approach equal to 5 K (DTmin. fur- CO2 or dashed) have been adopted in order to describe the material ther solutions can be adopted to liquefy the remaining dry ice. Inside the AHE. To allow the feasibility of the heat recovery izing the operation (Anti-sublimation Heat Exchanger AHE) and process. real. Stream D1-B is cooled down pressure level below the CO2 triple point pressure (5. namic and energy evaluations [60–66]. 6) adopts the anti-sublimation technique on heat exchanger is used for the purpose.

The AHE control volume (Fig. . 7. FEED-1 FEED-2 The duty removed by an external cooling medium through a refrigeration cycle is Q_ OUT . Layout of the anti-sublimation process. (7) and (8). 9. Fig. CO2-T The different terms in balance (6) can be evaluated using Eqs. Thermodynamic cycle for CO2 phase changes. Dry Ice (4). RHE scheme for energy balance in the anti-sublimation process. 8.552 M. / Applied Energy 180 (2016) 546–559 Fig. AHE scheme for energy balance in the anti-sublimation process. ( " Z T OUT # " Z T OUT #)   ( " _HFEED2 ðTÞ ¼ n_ FEED2  V y ~ G ~ G þ n_ FEED2  1  V ~ ðT Þ CH4  hrif ðT rif Þ þ CpCH4 ðTÞdT þ yCO2  hrif ðT rif Þ þ CpCO2 ðTÞdT  xCH4  h rif rif F T rif T rif F Z T OUT #)   ( " Z T OUT #) V ~ ðT Þ þ þ n_ FEED2  1  eV eV þ CpGCH4 ðTÞdT  DhCH4 ðT OUT Þ  xCO2  h rif rif CpG CO2 ðTÞdT  D hCO2 ðT OUT Þ ð4Þ T rif F T rif ( " Z # Q_ OUT ¼ H_ FEED1 ðT IN Þ  H_ FEED2 ðT OUT Þ ð5Þ ~ ðT Þ þ T OUT H_ D1 ðTÞ ¼ n_ D1  yCH4  h rif rif CpGCH4 ðTÞdT T rif " Z #) T OUT ~ ðT Þ þ þ yCO2  h CpGCO2 ðTÞdT ð7Þ rif rif T rif " Z # T OUT _HDryIce ðTÞ ¼ n_ DryIce  h~ ðT Þ þ CpGCO2 ðTÞdT  sub DhCO2 ðT OUT Þ rif rif T rif ð8Þ FEED-2 FEED-3 D1 AHE Dry Ice Fig. RHE (6). 9) includes also the JT valve. H_ FEED2 ðTÞ ¼ H_ D1 ðTÞ þ H_ DryIce ðTÞ þ Q_ OUT ð6Þ Fig. and it is calculated according to Eq. Baccanelli et al. 6.

the duty Q_ OUT . RHE has been assumed to operate adiabatically. The necessary heat amount.frosting Þ þ CpGCO2 ðTÞdT AHE) are operated in parallel in an alternate mode. The natural gas stream rich in CO2 is fed to a distillation column In order to verify the feasibility of the proposed heat recoveries. and with reference to the top of the distillation column. (9). Hybrid process layout. The liquefied CO2 stream is recovered at its triple point (CO2 -T) and is pumped (CO2 -int) and heated (CO2 -int2) in order Fig. 3. . the distilla. removed by the external cooling phase. the gas stream in order to reach the specifications required for liq. recovered as liquid CO2 at its triple point. i. medium through a refrigeration cycle. The T OUT H_ pre-LNG ðTÞ ¼ n_ pre-LNG  ~ ðT Þ þ yCH4  h CpGCH4 ðTÞdT CO2 -int stream becomes then CO2 -int2 and it can be mixed with rif rif T rif the Bottom stream (the CO2-rich liquid stream extracted from the " #) Z T OUT bottom of the HP distillation column) to give the stream Liquid. 10. (10) can be evaluated using cooled by heat recovery with the process stream CO2 -int. is calculated according to The INLET NG stream specifications are summarized in Table 1. Baccanelli et al. This process allows to accomplish a CO2 separation from the main gas stream in order to meet the Fig. The content of CO2 in D1 is 10 mol% due to the limitation AHE of the critical conditions. two identical devices (RHE and sub CO2 ¼ n CO2T  D h CO2 ðT CO2. the INLET NG stream is The different terms in Eq. The stream D1 is then expanded to the Dry Ice atmospheric pressure by means of a JT valve and furthermore cooled down 113. in the subsequent operating cycle. tion of process 1. ~ ðT Þ þ þ yCO2  hrif rif CpGCO2 ðTÞdT ð11Þ CO2 . in order to T CO2. AHE scheme for energy balance. A second heat recovery occurs inside the RHE.15 in AHE. 10. RHE heat exchanger is assumed to operate in recovery In AHE (Fig. dew point at 50 bar. 12). The methane-rich gas tion column used to realize the first part of the purification process stream (Pre-LNG) produced from the AHE is then liquefied in a heat has 25 ideal trays as the HP pressure section of the process consid. 11. which is necessary to ensure Fig. operated at 50 bar. assuming a minimum approach temperature of 5 K. (10). 10. the energy balance is used to verify the feasibility of the inter- removal of CO2 . obtain LNG ready for commercialization.2. / Applied Energy 180 (2016) 546–559 553 Fig. RHE scheme for energy balance in the hybrid process. Hybrid process purity specifications for LNG production. For the sake of clearness. while the AHE works in anti-sublimation phase. a gas product stream (D1) rich in methane is obtained. Before being fed to the HP distillation column. The bottom product (Bottom) is a pressurized liquid CO2 -rich stream under pressure. and the required duty useful to liquefy the dry close to 10 mol%. The distillation column is operated at 50 bar and it has 25 theoretical trays. is melted to produce a liquid CO2 stream at its triple point (CO2 T). recovery is defined in order to warm CO2 -int up to 287. " Z ðT FEED2 DT min. to be mixed with the stream Bottom. M. For this process. 10 combines the purifica. 12. As well as for process 2. INLET NG is cooled at its dew point at 50 bar (INcolumn) by means of three heat exchang. the energy balances must be verified for both the heat exchangers. (11)–(13). The heat Eqs. D1 D1-exp Pre-LNG while. where the solid CO2 . where solid line represents þ DhCO2 ðT FEED2  DT min.21 K at ( " Z # 50 bar. The produced top gas stream has a CO2 content nal heat recovery. H_ D1 ðTÞ ¼ H_ pre-LNG ðTÞ þ H_ DryIce ðTÞ þ Q_ OUT ð10Þ ers in series.3. whose design is similar to the one of the HP sec. from the top. The distillation column performs a bulk way. after exclusion of pinch prob- lems. can be provided by FEED-2 that needs to be cooled down in RHE CO2-T Dry Ice order to reach the INcolumn stream conditions. layer is formed and. In the first heat exchanger. formed during the previous operating FEED-2 INcolumn cycle. The feed stream INcolumn enters on the third tray from the top.RHE Þ ð9Þ the flow of natural gas throughout the process. the balance presented in Eq. The cooled INLET NG stream becomes FEED-1 that is sent to T rif a heat exchanger where an external utility is used to cool this stream down to FEED-2. only one cond operation phase is reported in Fig. The difference is the presence of a condenser at As for the anti-sublimation process.frosting # allow continuous operation. The heat exchangers in series allow to clean ice layer is calculated according to Eq. In this the liquid recirculation. 11.e. With reference to Fig. exchanger by means of an external cooling medium in order to ered in process 1. Inside the AHE a dry ice The hybrid process presented in Fig.RHE Þ Q_ IN _ uefaction. it will be tion approaches of processes 1 and 2.

Therefore. Q_ W CH4 coming from the combustion of methane (with an heating formalized among others by Kotas [68] and Bejan [69]. Finally. / Applied Energy 180 (2016) 546–559 " Z # T OUT required by the Net equivalent methane method [68. method as the energy required to drive a classic vapor- compression refrigeration cycle with a Second Law efficiency gII. ther- methane and the exergy flows are the same of the considered work mal. which is numer- Both the approaches are able to harmonize the different nature ically equal to the work interaction. boundaries.554 M. In a different manner. The electric and mechanical energy flows that assessed by means of energy and exergy analyses. with an energy effi- On the other hand. Energy analysis cross the boundary of the analyzed process are accounted by the is performed according to the Net equivalent methane method [67]: net equivalent methane method as the methane consumed or it accounts for the amount of methane required by defined refer. it is accounted by the Net equivalent methane for each process. On the other hand. Exergy analysis are finally presented and discussed.i Þ  T 0  ðsi  s0. Heat interactions. uniformly expressing them by means of their mechan. if the thermal energy is provided flows absorbed by the system: steam generation. the heat is supplied by means of low-pressure compressors or pumps and vapor-compression refrigeration cycles. Material interactions. Differently. magnitude and direction of the heat exergy flows depend on values On the other hand. which is a prop- " Z #) erty of both the system and the environment: the Baher reference T OUT ~ ðT Þ þ þ yCO2  h CpGCO2 ðTÞdT ð13Þ environment is here assumed and distinguished by the subscript rif rif T rif ‘‘0”.80]. The direction of the equivalent of the energy interactions involved in each process: indeed. Such efficiency is defined as the ratio one of the analyzed process. temperature purification processes introduced in Section 3 are Work interactions.79. the exergy equivalent a by-product is considered as a saving of methane (providing that of the heat interactions (both removed or provided) can be evalu- it is easily recoverable): as an instance. thus allowing to remove the hypotheses not account for the methane required or saved by the inlet and out- Table 4 Equivalent methane and exergy of energy/material interactions of the analyzed system. where energy T rif utilities are produced by different kind of technologies. the electricity obtained ated based on the definition of the Carnot Factor sk ¼ 1  T 0 =T k from expanding flows by means of turbines.15 K) that need to be cooled down can T 0 and of the surfaces T k at which the heat transfer occurs Q_ k . Net equivalent methane analysis Exergy analysis Work interactions (provided/extracted) E_ W _ CH4 ¼ W=gCC _ W ¼ W þ P  dV Ex dt   Heat interactions Extracted from the process: _ Q ¼ Q_ k  s. Results value LHV CH4 of 50 MJ kg1 [54]). all the energy that is produced by the system as ciency gB of 0. Analysis of the low-temperature purification processes the equivalent methane and the exergy of energy and bulk flow interactions that characterize the analyzed system are following In this section.6 [27. With reference to Table 4. it is assumed that the methane that is required to provide such interactions by means mechanical energy absorbed by the refrigerator is produced by of conventional engineering processes. The mechanical energy required by the refrigerator can be thus evaluated thanks to the definition of ideal The Net equivalent methane analysis can be performed by con- COP. the conventions required to evaluate 4. The be seen as useful by-products. with a temperature of 298.55 [77].i Þ þ T 0 R i ½yi lnðci yi Þ . electricity for to the process. steam produced by a methane-fired boiler. The Net equivalent methane analysis does ical energy equivalents. characterized by means of their energy or exergy equivalents. Baccanelli et al. or hot mass flows [78]. exergy analysis between the net power output W _ el and the thermal power input is performed according to the traditional exergy method.mix ¼ i yi  ½ðhi  h0. accounts for the exergy equivalent of the stream.01325 bar [76]. If the thermal energy is removed by the ana- ensuring a coherent assessment of the thermodynamic efficiency lyzed process.8 [7]. On the other hand. saved by a classic combined cycle power plant with energy effi- ence processes to deliver thermal and mechanical energy to each ciency gCC of 0. Ex s ¼ 1  TT 0k k Q_ E_ Q ¼ CH4 gII T o T gCC T Provided to the process: E_ Q ¼ Q_ =g CH4 B Material interactions – Physical exergy of mixtures: P exph. and assuming T 0 as the environmental temperature verting all the energy interactions between the analyzed process (298.f 4. This ~ ðT Þ þ H_ DryIce ðTÞ ¼ n_ DryIce  h CpGCO2 ðTÞdT  sub DhCO2 ðT OUT Þ rif rif feature is particularly relevant in modern economies. mechanical and bulk flows that cross system boundaries are interaction [78]. Z T OUT ~ ðT Þ þ The definition of reference environmental conditions is an H_ D1 ðTÞ ¼ n_ D1  yCH4  h rif rif CpGCH4 ðTÞdT T rif implicit prerequisite for the evaluation of exergy. Net equivalent methane and exergy analyses equal to 0.15 K) and T as the temperature at which the heat is absorbed and the external environment into an equivalent amount of from the considered process. listed.mix ¼ i ðyi  exch.i Þ Chemical exergy of mixtures: P P exch. thermodynamic performances of the low.15 K and a pressure of 1. Exergy analysis allows take into account both quantity and quality of energy streams flowing through the layout and signs of Q_ k and sk . which is based on both the temperatures of the environment (temperature above 373.1. and where ð12Þ distributed generation and penetration of renewables are continu- ( " # ously increasing [73–75].70–72]. assumptions the same methane-fired combined cycle power plant previously are made on the technology used to produce the required energy introduced.

and so on. faction process. With reference to Table 4. chemical exergy is defined as the required to separate and to liquefy the natural gas inlet can be maximum work obtainable taking the stream form environmental derived. ci is the activity required to liquefy the LNG and CO2 streams is equal to the differ- coefficient of the i-th compound. the util- of the system. including and total exergy of such material flows are also reported.5 20185.6851 Molar physical exph J/mol 9347. Notice that only work and heat interac. outlet material streams are collected in Table 5. while the denominator represents the amount of Property Symbol Unit INLET NG LNG CO2 (l) mechanical work that must be delivered to the real analyzed Molar enthalpy h-h° J/mol 787.388 . The proposed values are conventionally established by the produce very high numerical values.5 11462. Despite its theoret.2941 69. Main properties of material flows that cross system boundaries. Magnitude and direction of the equivalent methane and the exergy tions are accounted in such indicator. depending on the temperature level  Rational and Functional exergy efficiencies. values of chem- equivalent of material streams results for all the analyzed pro. The specific chemical exergy of the ence between physical exergy of outlet and inlet flows (6813 kW).666 691. rational exergy efficiency is expected to steam. while the minimum work R is the universal gas constant (8. 6 and to assess the thermodynamic performance of the analyzed 10). namely the ones in which solid exergy efficiency gex. In the evaluation of chemical exergy. of outlet and inlet flows (2353 kW). as in relation (14). nuclear of magnitude lower with respect to the values of physical exergy reactions. Table 6 collects numerical values for the energy associated to processes: heat and work interactions that cross system boundaries. the relation (15). M. Physical since the analyzed systems do not cause a changes in the chemical exergy is defined as the maximum work obtainable bringing the nature of material flows.2 exergy IN Ex P _ P P _ P _ Molar exergy extot J/mol 513826.j ð14Þ boundaries at which heat transfers occur. which is the actual useful product equipment has been assumed as homogeneous: in this way. Moreover. Moreover.8 29500. ously introduced. environ. ity temperature has been estimated assuming 5 K as the minimum ments of the system. values of chemical exergy are about two orders Neglecting the effects due to magnetism.F is defined as the ratio between the change phase formation occurs.4 9314. minimum temperature approach 5 K for refrigerants and 10 K for ically correct approach. cesses as the sum of physical and chemical exergy [81]. Molar entropy s-s° J/mol K 33. More specifically. exergy and equivalent methane associated to a same heat flow may be different. Aspen HysysÒ V7.F represents the minimum amount of mechan.e. Methods application. chemical write a complete exergy balance for the analyzed system.6 process in order to obtain such useful effect. surface tension. On the other hand. allowing to close the environment.3 830132.5 17545. Considering all the at which the heat exchanging process occurs. The minimum work required to separate the methane state to the dead state. values of chemical exergy of temperature approach with respect to the minimum temperature inlet and outlet streams cancel out. the functional current mode. rational exergy efficiency gex. It is equal to the sum of all the mechan. By handling values in Table 5. defined by In order to derive the exergy equivalents of thermal flows. Note that the directions i j of energy.426 16. Baccanelli et al. but only a change in their thermo- material stream (a mixture of chemical compounds) in thermal physical properties. To avoid such problem. bringing it from its Main properties of the natural gas inlet and the LNG and CO2 generic state to the environmental ones in terms of temperature.R . together with values of Carnot factor and the temperature of X X Q E_ CH4 ¼ E_ WCH4. is the ratio between the total exergy outputs temperature at which heat exchange occurs must be known: the and the total exergy inputs.805 11.314 J mol1 K1). Therefore.214 F k Exk þ Exk Exergy Extot kW 713. In this way. As previ- all the material and energy streams that cross its boundaries. On the other hand. Exergy analysis allows to of the same flows (superscript ‘‘°”). results and discussion accounts for the exergy equivalent of a bulk flow stream as the maximum work extractable from that stream. / Applied Energy 180 (2016) 546–559 555 let flows of material streams.3. Values of physical.e. characterized by the chemical equilibrium and the CO2 is equal to the difference between the chemical exergy with the environmental air.82. the following indicators are defined With reference to the analyzed process schemes (Figs. except for AHEs. since the chemical exergy literature [84].622 5174 gex. 5. representing the amount of exergy temperatures of the utilities have been defined starting from the _ D occurring inside each analyzed system (i. and the sum of the exogenous exergy require. E_ CH4 .i is available for atmosphere compounds. except for thermal streams related to heat ical and thermal energy interactions between the process and exchangers where dry ice formation occurs. the Table 5 numerator of gex. analyzed system. Molar enthalpy pressure and chemical composition [78].648 706. ical work required to separate and to liquefy the natural gas stream. the exergy for the natural gas and the LNG streams.2.0 P _ OUT exergy Ex gex. and mechanical equilibrium with the environment (i. while the directions energy and material interactions that cross boundaries of the of exergy and equivalent methane results always the same.8 847677.4 14742. ical exergy of inlet natural gas and outlet LNG are almost equal.83]. These properties are constant for all the three analyzed processes. the temperature inside these in exergy of the treated flows. expressed by means of equivalent methane material and energy balances for all the considered processes. These procedure has been applied to all heat of the treated hydrocarbons are very high compared to their exchangers that have been assumed as operating in counter- physical exergy contents.i þ E_ CH4.R ¼ POUT _ IN .F ¼ PP _ExF ¼ P _ W _ Q  ð15Þ Chemical exergy Exch kW 700. The sum of these two values (9166 kW) represent the reference while for fuels it is calculated using the Van’t Hoff box equilibrium thermodynamic upper limit for the analyzed separation and lique- model [69. change in velocity and elevation.0 Ex OUT N i ðexph þ exch Þi  IN N j ðexph þ exch Þj Physical exergy Exph kW 12. with respect and entropy are accounted with respect to the reference conditions to the Net equivalent methane method. the minimum amount of work mental state). Molar chemical exch J/mol 504479. i-th pure compound exch. the destructions Ex ones of process streams across heat exchangers and assuming as amount of thermodynamic irreversibilities). associated to all the heat/work interactions are also reported. exergy analysis 4. obtaining a more detailed and meaningful performance indicator. Mechan- ical and thermal energy requirements have been calculated using  Net equivalent methane.983 14.9928 108.

160 408.0 28650. the work produced by the Expander in the Dual Pres.0 Total Tot – – – – 35769.  The thermodynamic performance ranking of the three analyzed aries.0 HP distillation column 2 Heat 4302.569 4212.  The numerical differences between all the inlet and outlet flows Therefore. Hybrid Natural Gas cooler 1 1 Heat 2383.775 12464. . Fig.4 1.2 0. processes in the same way.5 13100.e.8 28100. System Component No Type E [kW] Tk [K] sk [–] Ex [kW] ECH4 [kW] 1.6 226. The Hybrid With reference to Fig.2 0.0 LNG cooler 7 Heat 5383.  Only the physical exergy of the material streams (Natural Gas. Moreover. Fig.757 9270. and thus it has been represented by the contribution of mechanical and thermal considered as a saving of the exergy requirements of the plant. Exergy (Ex) and equivalent methane (ECH4) of heat and work streams for all the analyzed systems. The temperature (Tk) and Carnot factor (sk) that characterize the heat transfer processes are also listed.0 0.8 37.4 2985. Pump 1 Work 124. Antisublimation (scheme 2. heat exch. Based stream costs have been neglected. Grassmann diagrams [85] have been reported in Fig.2 0. on the contrary. 10) lies in the middle between the other two processes. 13. more energy intensive because the stream is globally cooled the Antisublimation heat exchanger rejects large amounts of down at the required temperature.000 0. zero-cost utilities (like consumption of equivalent methane (ECH4).0 HP distillation column 4 Heat 3043.R . and also the associated energy (ExD).0 Total Tot – – – – 25685. values of rational exergy efficiencies gex. In the Dual-pressure process.R sure process results as non-negligible (1640 kW) with respect result numerically similar and close to 100%: this is due to to the other exergy flows.5 1. On the other hand. and with reference However.5 1.3 108.1 0. To better understand the exergy flows that cross system bound. while the exergy equivalents of heat and work flows. its thermodynamic perfor- component is numerically lower with respect to its exergy mances are therefore placed in the middle between the two equivalent. whose value is lower inflows.2 achieved on process side.5 0.9 298.8 – – 20.F ).4 1375. as well as for net equivalent methane analysis. exergy analysis provides a compounds are not affected by the analyzed processes of sepa. distillation heat at very low temperatures.5 78097. the Dual Pressure scheme associated to material streams. the following comments can be made: heat is released by the HP distillation column at environmental temperature: this heat flow is considered as not recoverable by  Since the three process layouts have been simulated assuming the exergy analysis (i.444 3731.0 70000.0 LP distillation column 5 Heat 5171. As expected. the Antisublimation process has tion and thus it should be preferred.777 9569. the effects of the chemical exergy of the inlet and outlet flows.7 Pump 2 Work 20.4 560. even if the thermodynamic performance ranking of of the three processes result in the total exergy destructions the three analyzed process is the same according to energy caused by the systems. the definition of functional exergy For the three analyzed processes.0 Expander 6 Work 1640. 5 Heat 5277.4 3. while black arrows represent the (scheme 1.7 107.000 0.2 1.775 12463.757 23180. value for their efficiencies.  Exergy associated to work absorbed by pumps is numerically  Values of rational and functional exergy efficiencies rank the negligible with respect to the exergy equivalents of heat flows.8 659. temperatures of the whole process.4 11900. In some cases. is requirements with respect to the other processes: in particular.083 198.4 – – 1640. resulting in such high exergy involves the latent heat of vaporization. its exergy content is equal to zero). From a the three analyzed processes: grey arrows represent the exergy purely thermodynamic viewpoint. followed by the  The Dual Pressure process results more efficient because distil- Hybrid and the Dual pressure schemes.7 37400. the key factor in the other hand.556 M.0 108.3 298. Moreover.1 51250.0 0. 13 for process is the same with energy and exergy analyses. Since the hybrid layout combines lyzed processes is the LNG cooler: the heat released by this both the purification solutions. As can be inferred from the numerical and exergy analyses.5 206. rational and functional exergy efficiencies (gex. Fig. the latter provides more useful informa- results collected in Table 7.4 – – 308. 5) is the most efficient process.4 Antisub. streams. to relation (15).0 Antisub.0 LNG cooler 6 Heat 7022.4 37400.4 190. since the heat transfer is characterized by the lowest other processes. Baccanelli et al. and it is then methane and Exergy analyses are reported in Table 7 in terms of recommended.7 0.1 107. the lowest thermodynamic performances. exergy destructions water or air) have been considered. lation occurs following a temperature profile along the distilla-  The Anti sublimation process presents the largest exergy tion column. On the same material flows at battery limits.0 LNG cooler 3 Heat 7023.2 1.0 107626.3 180.0 Natural Gas cooler 2 3 Heat 7406. CO2) is depicted.5 HP distillation column 3 Heat 8413. results of Net equivalent efficiency results in more meaningful values.0 2.0 Pump 4 Work 308. Anti-subl.  While energy analysis provides absolute values for the methane LNG.9 275. in the same process a flow of mechanical work determining the efficiency classification for exergy analysis is easily recoverable is produced by the Expander. process is far from the ideal thermodynamic reference process.0 Total Tot – – – – 16218. Dual pressure Natural Gas cooler 1 1 Heat 2556. since values of chemical exergy of single required to sustain each process. the on these results. gex.650 3360. enabling to quantify how much each ration and liquefaction. / Applied Energy 180 (2016) 546–559 Table 6 Energy (E). heat exch. 2 Heat 13194. The Anti-sublimation process. the following comments can be made: solution (scheme 3.3 10550.8 107.1 0.2 257. a critical component of all the three ana- than the sublimation one.6 – – 124. 6) is less efficient.

rational and functional exergy and the operating conditions required for LNG production has efficiencies (gex. In particular. Anti-subl. Baccanelli et al.R . sweetening is required to meet the purity specification specific processes assumed as reference. suggested to evaluate and compare the efficiency of three types ECH4 [kW] ExD [kW] gex.62 anti-sublimation on heat exchanger and a hybrid process configura- 3.520 97. Notice that only values of physical exergy are represented for the streams of Natural Gas. characterized by a high required to supply the overall process energy demands through CO2 level. / Applied Energy 180 (2016) 546–559 557 Fig. The net equivalent methane analysis accounts for the amount of methane In order to liquefy an acid gas stream.f [%] of cryogenic purification solutions combined with LNG 1. Dual pressure 51. The three process schemes have been compared using two different approaches both 5. the . On the other hand. The possible synergy between Results of the net equivalent methane and the exergy analyses: consumption of the average thermal level at which cryogenic purifications occur equivalent methane (ECH4) exergy destructions (ExD). Conclusion able to harmonize the different nature of energy streams.603 96. Grassmann diagrams for the analyzed processes. a dual pressure distillation process.45 25.250 7052 99. 13. LNG and CO2. gex.04 56.F ).626 26.52 production. Hybrid 78. an 2. 107.r [%] gex.68 tion have been considered for this purpose.77 35. M.097 16. Table 7 (50 ppm for CO2 ) of the final product.

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