Plug Flow Reactors (PFR/ RAP)

Pertemuan 10

Reaktor Alir Pipa (RAP), atau Plug Flow Reactors (PFR)

Pada bab ini dipelajari analisis unjuk kerja dan perancangan RAP Seperti RATB, RAP selalu dioperasikan secara kontinyu pada keadaan tunak, selain daripada periode i d startup t t d dan shutdown h td Tidak seperti RATB yg digunakan terutama untuk t k reaksi2 k i2 f fasa cair, i RAP d dapat t di digunakan k untuk reaksi2 fasa cair dan fasa gas.

Ciri-ciri utama RAP

1. 2. 3.

4.

5.

Pola P l aliran li adalah d l h PF PF, dan d RAP adalah d l h vesel l tertutup t t t Kecepatan aliran volumetris dapat bervariasi secara kontinyu kearah aliran sebab perubahan densitas Setiap elemen fluida mrp sistem tertutup (dibandingkan RATB); yaitu, tidak ada pencampuran kearah axial, meskipun terjadi pencampuran sempurna searah radial (dalam vesel silinder) Sebagai konsequensi dari (3) sifat2 fluida dapat berubah secara kontinyu kearah radial radial, tapi konstan secara radial (pada posisi axial tertentu) Setiap elemen fluida mempunyai residence time yg sama seperti ti yg lain l i (dibandingkan (dib di k RATB)

Kegunaan RAP

Model RAP seringkali digunakan untuk sebuah reaktor yg mana sistem reaksi (gas atau cair) mengalir pada kecepatan relatif tinggi (Re>>, (Re , sampai mendekati PF) melalui suatu vesel kosong atau vesel yg berisi katalis padat yg di packed Disini tidak ada peralatan seperti pengaduk pengaduk, untuk menghasilkan backmixing Reaktor dapat digunakan dalam operasi skala besar untuk t k produksi d k i komersial, k i l atau t di l laboratorium b t i atau t operasi skala pilot untuk mendapatkan data perancangan

Ilustrasi contoh RAP skematik

Persamaan perancangan untuk RAP

Tinjau reaksi: A + cC Neraca Massa: Untuk mendapatkan volume:
(15.2-2) (15.2-1)

P Pers 2 di dinyatakan t k d dalam l space ti time

(15.2 3) (15.2-3)

karena Bila pers (1) dituliskan kembali dalam gradien fA terhadap perubahan posisi x dalam RAP Asumsi reaktor berbentuk silinder dg jari-jari R. Volume reaktor dari pemasukan sampai posisi x adalah:

Substitusi dV ke pers (1) diperoleh

(15 2 4) (15.2-4)

Gambar: Interpretasi pers (2) atau (3) secara grafik

Neraca Energi

Pengembangan neraca energi untuk RAP, kita pertimbangkan hanya operasi keadaan tunak, jadi kecepatan akumulasi diabaikan. Kecepatan entalpi masuk dan keluar oleh (1) aliran, (2) transfer panas, (3) reaksi mungkin dikembangkan atas dasar diferensial kontrol volume dV seperti gambar b ik t berikut:

1)

Kecepatan entalpi masuk oleh aliran kecepatan entalpi keluar oleh aliran

2)

Kecepatan transfer panas ke (atau dari) kontrol volume

Dengan U adalah koef perpindahan panas k keseluruhan, l h TS adalah d l ht temperatur t sekitar kit diluar pipa pada titik tinjauan, dan dA adalah perubahan luas bidang transfer panas

3)

Kecepatan entalpi masuk/ terbentuk (atau keluar/ terserap) oleh reaksi

Jadi persamaan neraca energi keseluruhan (1), (2) dan (3) menjadi: (2),
(15.2-5)

Persamaan (5) mungkin lebih sesuai ditransformasi ke hubungan T dan fA, karena
(15.2-6)

dan

(15.2-7) ( )

dengan D adalah diameter pipa atau vesel, substitusi (6) ke (7):

(15.2-8)

Jika digunakan pers (1) dan (8) untuk mengeliminasi dV dan dAp dari pers (5), didapatkan
(15 2 9) (15.2-9)

Secara alternatif, pers (5) dapat ditransformasi ke temperatur sebagai fungsi x (panjang reaktor), gunakan pers (6) dan (7) untuk eliminasi dAp dan dV
(15.2-10)

Untuk kondisi adiabatis pers (9) dan (10) dapat disederhanakan dg menghapus term U (Q = 0)

Neraca Momentum; Operasi Nonisobarik

Sebagai S b iR Rule l of f Th Thumb, b untuk t k fluida fl id kompresibel, k ib l jik jika perbedaan tekanan antara pemasukan dan pengeluaran lebih besar dp 10 sampai 15%, perubahan tekanan seperti ti ini i i mempengaruhi hi k konversi, i d dan h harus dipertimbangkan jika merancang reaktor. Dalam situasi ini, perubahan tekanan disepanjang j g reaktor harus ditentukan secara simultas dengan perubahan fA dan perubahan T Dapat ditentukan dengan pers Fanning atau Darcy untuk aliran dalam pipa silinder dapat digunakan (Knudsen and Katz, 1958, p. 80) (15.2-11)

Dengan g P adl tekanan, x adl p posisi axial dlm reaktor, adl densitas fluida, u adl kecepatan linier, f adl faktor friksi Fanning, D adl diameter reaktor, kt dan d q adl dl l laju j alir li volumetrik; l t ik , u, dan d q dapat bervariasi dengan posisi Nilai f dapat ditentukan melalui grafik utk pipa smooth atau dari korelasi. Korelasi yg digunakan untuk aliran turbulen dalam pipa smooth dan untuk bilangan Re antara 3000 dan 3000.000
( (15.2-12) )

Constant-Density System
Pertemuan 11

1. Isothermal Operation

For a constant-density system, since

14.3 12 14.3-12

then

15.2-13

The residence time t and the space time are equal.

15.2-14

and

15.2-15

The analogy follows if we consider an element of fluid (of arbitrary size) flowing through a PFR as a closed system, that is, as a batch of fluid. Elapsed time (t) in a BR is equivalent to residence time (t) or space time () in a PFR for a constant-density system For dV from equation 15 and for dfA system. from 13, we obtain, since FAo = cAoqo,
15.2-16

we may similarly write equation 2 as

15.2-17

A graphical interpretation of this result is given in Figure 15.4.

Example 15-2
A liquid-phase double-replacement reaction between bromine cyanide (A) and methyl-amine takes place in a PFR at 10C 10 C and 101 kPa kPa. The reaction is first-order with respect to each reactant, , with kA = 2.22 L mol-1 s-1. If the residence or space time is 4 s, and the inlet concentration of each reactant is 0.10 mol L-1, determine the concentration of bromine cyanide at the outlet of the reactor.

SOLUTION
The reaction is:

Since this is a liquid-phase reaction, we assume density y is constant. Also, , since the inlet concentrations of A and B are equal, and their stoichiometric coefficients are also equal, at all points, i cA = cB. Therefore, Th f the h rate law l may b be written as A

From equations 16 and (A), which integrates to On insertion O i ti of f the th numerical i l values l given i f for kA, t, and cAO, we obtain 1 cA = 0 0.053 053 mol L-1

EXAMPLE 15-3
A gas-phase reaction between methane (A) and sulfur (B) is conducted at 600C and 101 kPa in a PFR to PFR, t produce d carbon b disulfide di lfid and dh hydrogen d sulfide. The reaction is first-order with respect to each reactant reactant, with kB = 12 m3 mole-1 h-1 (based upon the disappearance of sulfur). The inlet molar flow rates of methane and sulfur are 23.8 and 47.6 mol h-1, respectively. Determine the volume (V) required to achieve 18% conversion of methane, and d th the resulting lti residence id or space ti time.

Solution Reaction:

CH4 + 2 S2 CS2 + 2 H2S

Although this is a gas-phase reaction, since there is no change in T, P, or total molar flow rate, density is constant. Furthermore, since the reactants are introduced in the stoichiometric ratio, neither is limiting, and we may work in terms of B (sulphur), since k, is given, with fB( = fA) = 0.18. It also follows that cA = cB/2 at all points. The rate law may then be written as

(A) From the material-balance equation 17 and (A), (B) Since FBo = cBOqO, and, for constant-density, cB = cB0(l - fB), equation (B) may be written as (C) To obtain q0 in equation (C), we assume idealgas behavior; thus,

From equation (C),

From equation 14, we solve for T:

2. Non isothermal Operation

To characterize the performance of a PFR

subject to an axial gradient in temperature, the material t i l and d energy b balances l must tb be solved l d simultaneously. This may require numerical integration using a software package such as E-Z Solve. Example 154 illustrates the development p of equations q and the resulting profile for fA, with respect to position (x) for a constant-density reaction.

EXAMPLE 15-4
A liquid-phase reaction A + B 2C is conducted in a non isothermal multi tubular PFR. The reactor tubes (7 m long, 2 cm in diameter) are surrounded by a coolant which maintains a constant wall temperature. The reaction is pseudo-first-order with respect to A, with kA = 4.03 X l05 e-5624/T, s-1. The mass flow rate is constant at 0 06 kg s-1, the density is constant at 1 0.06 1.025 025 g cm3, and the temperature at the inlet of the reactor (T0) is 350 K. (a) Develop expressions for dfA/dx and dT/dx. (b) Plot fA(x) profiles for the following wall temperatures (TS): 350 K, 365 K, 400 K, and 425 K. Data: CA0 = 0.50 mol L-1; cp = 4.2 J g-1 K-1; HRA = -210 kJ mol-1; U = 1.59 kW m-2 K-1.

Solution
(a) The rate law is (A) where kA is given in Arrhenius form above. Substitution of equation (A) in the materialbalance equation 15 15.2-4, 24 results in (with R = D/2 and FA0/CA0 = q0):

Figure 15 15.5 5 Effect of wall temperature (Ts) on conversion in a non-isothermal PFR (Example 15-4)

3. Variable-Density System

When the density of the reacting system is not constant through a PFR, The general forms of performance equations of Section 15.2.1 must be used. The effects of continuously varying density are usually ll significant i ifi t only l for f a gas-phase h reaction. Change in density may result from any one one, or a combination, of: change in total moles (of gas flowing), change in T , and change in P . We illustrate these effects by examples in the following sections.

I th Isothermal, l Isobaric I b i O Operation ti

Example 15.6 Consider the gas-phase decomposition of ethane th (A) to t ethylene th l at t 750C and d 101 kP kPa (assume both constant) in a PFR. If the reaction is first first-order order with kA = 0.534 s-1 (Froment and Bischoff, 1990, p. 351), and is 1 s, calculate fA. For comparison, repeat the calculation on the assumption ti that th t density d it i is constant. t t (In (I both b th cases, assume the reaction is irreversible.)

S l ti Solution
The reaction is C2H6(A) ( ) C2H4(B) ( ) + H2(C). ( ) Since the rate law is (A) Stoichiometric table is used to relate q and q0. The resulting g expression p is

q = q0 (1+fA)
With this result result, equation (A) becomes ( ) (B)

The integral g in this expression p may y be evaluated analytically with the substitution z = 1 - fA. The result is
(C) Solution of equation (C) leads to fA = 0.361

If the change in density is ignored, integration of equation 15.2-17, with (-rA) = kACA = kACAo(1 - fA), leads to

from which

N i th Nonisothermal, l I Isobaric b i O Operation ti

Example 15.7 A gas-phase reaction between butadiene (A) and ethene (B) is conducted in a PFR, PFR producing cyclohexene (C) (C). The feed contains equimolar amounts of each reactant at 525C (T0) and a total pressure of 101 kPa. The enthalpy of reaction is - 115 k k.I I (mol A)-1, and the reaction is first-order with respect to each reactant, with kA = 32,000 e-13,850/T m3 mol-1 S-1. Assuming the process is adiabatic and isobaric isobaric, determine the space time required for 25% conversion of butadiene. Data: CPA = 150 J mol-1 K-1; CPB = 80 J mol-1 K-1; Cpc = 1 K-1 1 250 J mol l-1

S l ti Solution
The reaction is C4H6(A) + C2H4(B) C6H10 (C). Since the molar ratio of A to B in the feed is 1: 1, and the ratio of the stoichiometric coefficients is also 1: 1, CA = CB throughout the reaction. Combining the material-balance material balance equation (15.2-2) with the rate law, we obtain

(A)
Since kA depends on T, it remains inside the integral, and we must relate T to fA. Since the density (and hence q) changes during the reaction (because of changes in temperature and total moles), we relate q to fA and T with the aid of a stoichiometric table and the ideal-gas equation of state.

Since at any point in the reactor, q = FtRT/P, and the process is isobaric, 4 is related to the inlet flow rate q0 by

That is, Substitution of equation (B) into (A) to eliminate q results in

(C) To relate fA and T, , we require q the energy gy balance ( (15.2-9) ) (D) (E) Substituting equation (E) in (D), and integrating on the assumption that (-HRA) is constant, we obtain (F)

(G)

RECYCLE OPERATION OF A PFR

In a chemical process, the use of recycle, that is, the return of a portion of an outlet stream to an inlet to join with fresh feed feed, may have the following purposes: (1) to conserve feedstock when it is not completely converted to desired products, and/or (2) to improve the performance of a piece of equipment such as a reactor.

FAR

CA

FAR

(15 3 1) (15.3-1)

where subscript R refers to recycle and subscript 1 to the vessel outlet. Equation 15.3-1 is applicable to both constantdensity and variable-density systems

R may y vary y from 0 ( (no recycle) y ) to a very y large g value (virtually complete recycle). Thus, as shown quantitatively below, we expect that a recycle l PFR may vary i in performance f b between t th that t of fa PFR with no recycle and that of a CSTR (complete recycle), depending on the value of R

Constant-Density System
= Material balance for A around M: (15.3-2)

(15.3-3)

material balance for A around the differential control volume dV

(15.3-4)

Therefore Therefore, = (15.3-5)

Figure 15 Fi 15.7 7 G Graphical hi l i interpretation t t ti of f equation ti 15 15.3-4 34f for recycle PFR (constant density)

Example 15-9
(a) For the liquid-phase autocatalytic reaction

gp place isothermally y at A + . . . B + . . . taking steady-state in a recycle PFR, derive an expression for the optimal value of the recycle ratio, ti Ropt, that th t minimizes i i i th the volume l or space time of the reactor. The rate law is (-rA) = kAcAcB. (b) E Express th the minimum i i volume l or space ti time of f th the reactor in terms of Ropt.

Variable-Density System

For the reaction A + . . . products taking place in a recycle PFR

From a material balance for A around the mixing point M, the molar flow rate of A entering the reactor is
(15.3-8) At the exit from the system at S S, or at the exit from the reactor, =

Correspondingly, at the inlet of the reactor

= and at any point in the reactor,

(15.3-9)

(15.3-10)

Equating molar flow input and output output, for steady-state operation, we have

from equation 15.3-10. Therefore, (15.3-11)

That is, as R 0, V is that for a PFR without recycle; as R , V is that for a CSTR