Study of Chemical Process Structures for Process Synthesis
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STUDY OF CHEMICAL PROCESS STRUCTURES FOR PROCESS SYNTHESIS Hiroshi OAKI and Masaru ISHIDA Research Laboratory of Resources Utilization, Tokyo Institute of Technology, Yokohama227 Whenthermodynamic characteristics of processes are represented by a vector on the (JH, TqJS) diagram, the processes may be classified into six types: heating, separation, refrigeration, heat source, mixing, and refrigerant. Based on this classification, which is quite appropriate to process synthesis, the analogy between chemical reactions and physical operations is discussed. Since a chemical process system is considered to be an isolated system, the criterion for those processes to constitute a process system is examined and a new criterion based on the dissipation factor, D=T0JS/JH9 is proposed. It is shown that there are only six basic patterns for the combination of processes to makeup a process system. Whenan endergonicprocess and an exergonic one constitute a process systemand the former process is carried out with the help of the latter, the exergy transformation between these two processes becomes an important factor. The concept of the ideality index is introduced and the relationship between this ideality index and the dissipation factor Dis discussed. state to another2\ we mayevaluate the changes in Introduction enthalpy, AH, and entropy, AS, for each process. In chemical engineering, the process has usually Then we may describe thermodynamic character- been classified according to the type of equipment or istics of the process by a vector on the {AH, TQAS) operations such as heat generation, heat transfer, diagram shown in Fig. 1. distillation, absorption, extraction, and so on8>11). In this diagram, the enthalpy change is chosen as Such classification is suitable for equipment design abscissa and the entropy change multiplied by the calculations. However, based on this classification, ambient temperature To is selected as ordinate. Then many kinds of chemical reactions have been cate- the axis for Ae=0is represented by the oblique line gorized into only one group. given by AH=T0AS, since the exergy function e is In the previous paper7\ the authors proposed a new defined as methodto analyze a chemical process system from the e=H-T0S (1) viewpoint of exergy transformation between the target Therefore, we may divide the plane shown in Fig. 1 process and coupled processes such as exergy donors, into six regions by these three lines, AH=0(ordinate), exergy acceptors, accelerators, and mediators. It AS=0 (abscissa), and As=0 (oblique line). As will was shownthat there maybe several patterns for coupl- be explained later, these six regions may be called ing between the target and the coupled processes. Fromthat discussion, it was concluded that such clas- heating, separation, refrigeration, heat source, mixing, sification of processes based on type of equipments is and refrigerant types. not suitable for the energy analysis or synthesis of processes. The purpose of this paper is to classify processes into six types from the viewpoint of thermodynamics. Based on such classification, the criterion for several processes to constitute a process system is discussed. Finally, the efficiency of the exergy transformation in a basic binary process system is obtained. 1. Classification of Processes on (AH, TQAS) Plane Since a process is the transition ofa system from one Received April 10, 1981. Correspondence concerning this article should be addressed to H. Oaki. Fig. 1 Six types of processes on (AH, T0JS) diagram VOL. 15 NO. 1 1982 51 and O<Z)<1, corresponding to region (4) in Fig. 1. Since this substance maygive heat to the other material, this region is called heat source type. 4) Refrigerant The vector for heating a substance to the temperature To is located in region (6) in Fig. 1. Since this process maybe coupled with the refrigera- tion process, this region is called refrigerant type. Figure 2 summarizes the characteristics of the vec- tors of these four types of thermal processes to give and Fig. 2 Vectors for thermal processes at various take a certain amount of heat. As the temperature T temperatures on (dH, T0JS) diagram is increased, the vector approaches the abscissa, giv- ing rise to D=0. On the other hand, as the tempera- The vector (AH, T0AS) for a process may also be ture is decreased, the effect of the entropy change is specified by the values of AHand the slope, T0AS/AH. increased, resulting in D=ooat T=0 K. Therefore, The later indicates the increase in entropy per unit the direction of the vector for these thermal processes enthalpy increase and maybe called the dissipation is significantly affected by temperature. factor, D. 1. 2 Polytropic processes D= T0AS/AH (2) Compression and expansion are important proc- By this dimensionless factor, the increase in exergy esses in chemical industry. The changes in enthalpy for the process is given as follows. and entropy of n moles of an ideal gas from the state Ae=AH(l -D) (3) at T± and P1 to T2 and P2 can be obtained as follows. Whena computer is utilized to analyze or to synthe- JH=n^2cpdT=ncp(T2 - T1) (6) size a process, this dissipation factor D maybe used as a quantitative parameter denoting the direction of the vector on the {AH, T0AS)diagram. ,HL>--»l:H"(iro* co Let us examine several typical processes and draw Then the dissipation factor for a polytropic process, their vectors on the (AH, T0AS) diagram. i>Kw=const3)4), is given as 1. 1 Thermal processes 1) Heating Whenn moles ofa certain substance is AH (cp/cm)Tln W heated from Tt to T2, the dissipation factor D for this where m is the polytropic exponent and cm is the poly- heating process is obtained as tropic molar heat capacity3} defined by ToncX"dInT }n(TlT^ cm=cv(r-m)/(l -m) (9) V- ?t2 = lo~^-j^-=i o/i ln (4) ncA dT T2~Tl Wehave m=l and cm=oofor isothermal compres- sion, giving rise to D=oo, while m=y9cm=0, and D= 0 for adiabatic compression. Consequently, the where Tln, denned by (r2-TO/ln (r2/r0, is the loga- direction of the vector ofpolytropic processesis affected rithmic mean of Tx and T2 and the heat capacity cp is by the exponent m. assumedto be constant over that temperature range. Since the heating process above the ambient tem- 1. 3 Separation and mixing 1) Separation The changes in enthalpy and entropy perature TQgives AH>0 and O<Z><1, its vector is are positive and negative, respectively, in regular located in region (1) in Fig. 1. Hence, this region is separation processes and their dissipation factor be- called heating type. comes negative. Hence, their vector (AH, T0AS) Aheat sink at a constant temperature T is a special appears in region (2) in Fig. 1. case for such heating processes. Since T1 and T2 in For example, when 250 moles of aqueous solution Eq. (4) are equal to T9 the dissipation factor for such a of 40 mol% methanol is distilled and separated into heat sink is given by aqueous solutions of 95.8 mol%methanol and 5.8 D= T0/T (5) mol%methanol, we have 2) Refrigeration Refrigeration is the process of {100 CH3OH+150 H2O}-»{91 CH3OH+4 H2O} cooling a substance to a temperature below the am- +{9 CH3OH+ 146 H2O} (10) bient temperature To. Since Eq. (4) holds also for J#=0.18 kJ4), T0AS=~55.l kJ4), Ae=553 kJ this process, its vector appears in region (3) in Fig. 1. Hence, this region is called refrigeration type. and 3) Heat source Cooling a certain substance at high D=-306 temperature to a temperature above To gives AH<0 where the brackets in Eq. (10) mean the mixture. 52 JOURNAL OF CHEMICAL ENGINEERING OF JAPAN The exergy increase of the above separation process is almost equal to that of the decomposition of a mole of methane or the refrigeration of 16 moles of nitrogen from 298 K to 100K, as shown in Fig. 3. However, the methodsto realize these endergonic processes are quite different from each other, as will be discussed in detail in the next section. Therefore, the process of which the vector is located in region (2) in Fig. 1 is called separation type. 2) Mixing Since mixing is the reverse of separa- tion, the changes in enthalpy and entropy are usually Fig. 3 Three kinds of endergonic processes with negative and positive, respectively. Therefore, its almost equivalent amount of As vector (AH, T0AS) appears in region (5) in Fig. 1. Hence, this region is called mixing type. 1. 4 Chemical reaction To perform detailed energy analyses for chemical reactions, information about concentrations of both reactants and products are required. Then the changes in enthalpy, entropy, exergy, and the dissipation factor for reactions can be calculated. For primary discussions for process synthesis, however, the stand- Fig. 4 Examples of endergonic reactions ard dissipation factor D°, defined by the following equation, may be utilized. D°=T0AS0/AH (ll) where S° is the entropy of each componentunder unit pressure. Figure 4 shows the vectors on the (AH, T0AS) diagram for several endergonic reactions based on thermodynamic data compiled in the literatures1>9). Figure 5 shows those for exergonic reactions. Since the vector of the reverse reaction appears in the op- posite direction, all six types can be observed in chemi- cal reactions. The reactants of exergonic reactions with negative or small positive values of D such as ATP, shown in Fig. 5, have been called high-energy compounds5 }. Figure 6 shows the effect of temperature on the value of dissipation factor D. It is found that D for chemi- cal reactions is almost constant over a wide range of temperature.