化學反應工程第三部份講義

Textbook: Fogler, Elements of Chemical Reaction Engineering

Chapter 10 Catalysis and Catalytic Reactors

Catalysts
Catalytic reactions
Rate expression
Mechanism
Reactor design
Chemical Vapor Deposition (CVD)
Deactivation
Reactors-packed bed, fluidized bed, moving bed

Chapter 11 External Diffusion Effects on Heterogeneous Reactions

Diffusion Fundamentals
Binary Diffusion
External Resistance to Mass Transfer

Chapter 12 Diffusion and Reaction

Diffusion and reaction in spherical catalyst pellets

Internal effectiveness factor
Overall effectiveness factor
Determination of limiting situations from reaction data

• Grading
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 Chapter 10 Catalysis and Catalytic Reactors

Objective:
To develop an understanding of
catalysts: define a catalyst and describe its properties
reaction mechanism: describe the steps in a catalytic reaction and
apply the concept of a rate-limiting step to
derive a rate law
catalytic reactor design

Contents:
Catalyst definitions and properties
Steps in catalytic reactions
Rate expression and parameters
Catalyst deactivation
Catalytic reactors
Conversion or catalyst weight for reactors
Chemical vapor deposition ( CVD )

References:
1. 翁鴻山老師講義
2. G. C. Bond: Heterogeneous Catalysis, Oxford, 1987.
(胡興中編譯: 觸媒原理與應用, 高立)
3. 科學發展（月刊），第 370 期(92 年 10 月)（觸媒專輯）

本講義乃以翁鴻山老師教學多年的講義改編而成，在此感謝翁老師的
熱心提供!

101
1. Catalysts
。A catalyst is a substance that affects the rate of a reaction but emerges
from the process unchanged.
。A catalyst changes a reaction rate by promoting a different molecular
path (mechanism) for the reaction.
。A catalyst makes it possible to obtain an end product by a different
pathway with a lower energy barrier; it can affect both the yield and
the selectivity.
。A catalyst changes only the rate of a reaction; it does not affect the
equilibrium.
* 增加反應速率 改變反應途徑
增加選擇率 可在低溫反應

。Two types of catalysis

(1.) Homogeneous catalysis: the catalyst is in solution with at least one
of the reactants
Example: oxo process

(2.) Heterogeneous catalysis: involves more than one phase usually the
catalyst is a solid
Example: dehydrogenation of cyclohexane

102
The simple and complete separation of the fluid product mixture from the
solid catalyst makes heterogeneous catalysis economically attractive,
especially because many catalysts are quite valuable and their reuse is
demanded. Only heterogeneous catalysts will be considered in this
chapter.

。Catalyst Properties
催化反應都是發生於流體-固體的交界面(interface)，欲獲得明顯的反應速率必須
具備a large interfacial area。許多觸媒的交界面積是由內部的孔性結構所提供(即
固體內部含有許多小孔洞，這些孔洞的表面積提供高反應速率所需的面積)。典
型的矽-鋁觸媒之孔隙體積為0.6 cm3/g，孔徑的平均半徑為4 nm，其對應的表面
積高達 300 m2/g。(10 g catalyst posses more surface area than a football field)

孔性
Porous: interfacial area is provided by an inner porous structure.
－Molecular sieves: pores are so small that they will admit small
molecules but prevent large ones from entering. e.g. clays and
zeolites 沸石. (see Fig. 10-2)
Nonporous (monolithic 單石): some catalysts are sufficiently active
so that the effort required to create a porous catalyst would be
wasted.
擔體
Supported: a catalyst consists of minute particles of an active
materials dispersed over a less active substance called a support.
The active material is a metal or alloy. 如 Pt on Al2O3 (p.683) or
Ni on SiO2
Unsupported

。Support 之作用
分散活性物質; 使反應物容易經擴散進入觸媒內; 增強活性、選擇
性 、 穩 定 性 ; 本 身 亦 有 活 性 (dual-function catalyst 如 Pt on
Al2O3 )。

103
Figure 10.2 One example of the high selectivity of zeolite catalysis is the formation
of xylene from toluene and methane. 孔洞出口的大小只允許對二甲苯通過，內部
另有某些部位可將鄰、間二甲苯異構化為對二甲苯，故生成對二甲苯的選擇性非
常高。

。Catalyst Deactivation 失活

1. Poisoning 中毒: the irreversible deposit of a foreign material on the

active site. e.g. thiophine on Ni catalyst ; quinoline on
Al2O3 硫化物沉積
2. Coking 碳化 or fouling 污垢: the deposit of carbonaceous material
( as in the catalytic cracking of naphthas 石油腦).

3. Aging 老化: sinter 燒結 or structure change; a gradual change in

surface crystal structure 因高溫所造成之結構改變

。Chemical Properties:

(1.) Activity (Turnover frequency): one parameter used to quantify

the activity of a catalyst is TOF 轉換頻率.
(2.) Selectivity (vs. yield)
(3.) Stability (deactivation)

名詞解釋
。Active site: an active site is a point on the catalyst surface that can form
strong chemical bonds with an adsorbed atom or molecule.
。Dispersion (D): the dispersion of active metal on a catalyst is the
fraction of the metal atoms deposited that are on the

104
 surface.
。Turnover frequency: no. of molecules reacting per active site per
second at the condition of the experiment. 每個活性
部位每秒反應的分子數

Deactivation mechanisms: A) Coke formation, B) Poisoning, C) Sintering of the

active metal particles, and D) Sintering and solid-solid phase transitions of the
washcoat (擔體塗料) and encapsulation of active metal particles

Example 10-1 (p.651) TOF

The Fischer-Tropsch synthesis was studied using a commercial 0.5 wt%

Ru on -Al2O3. The catalyst dispersion percentage of atoms exposed,
determined from hydrogen chemisorption, was found to be 49%. At a
pressure of 988 kPa and a temp. of 475K, a turnover frequency, fCH4, of

105
0.044 s-1 was reported for methane. What is the rate of formation of
methane, r’M, in mole/sg of catalyst (metal plus support)?
Solution

※Chemisorption is the type of adsorption that affects that rate of

chemical reaction. 影響化學反應速率的吸附方式為化學吸附

Fig. 10-4 Range of turnover frequency as a function of temp. and type

of rxns.

106
。Classification of Catalysts

。主要成分-適用反應
Metals Hydrogenation, hydrogenolysis, oxidation
Metal oxides Partial oxidation, dehydrogenation
Acids Hydration, polymerization, cracking
Metal + Acid Isomerization, hydrogenlysis

Table 10-1. Types of reactions and representation catalysts (p. 655)

Reforming Catalyst
One common reforming catalyst is Pt on Al2O3. This is a bifunctional
catalyst that can be prepared by exposing alumina pellets to a
chloroplatinic acid solution, drying, and then heating in air 775 to 875 K
for several hrs. Next, the material is exposed to hydrogen at 725 to 775 K
to produce very small clusters of Pt on Al2O3. These clusters have sizes on
the order of 1 nm.

107
2. Steps in a Catalytic Reaction 觸媒反應之步驟
Isomerization 異構化: A B

Table 10-2. Steps in a catalytic reaction

1. Mass transfer (diffusion) of the reactant (species A) from the bulk
fluid 整體流體 to the external surface of the catalyst pellet (Chap.
11)
2. Diffusion of the reactant from the pore mouth through the catalyst
pores to the immediate vicinity of the internal catalytic surface (Chap.
12)
3. Adsorption of reactant A onto the catalyst surface
4. Reaction on the surface of the catalyst (A B)
5. Desorption of the products (B) from the surface
6. Diffusion of the products from the interior of the pellet to the pore
mouth at the external surface
7. Mass transfer of the products from the external pellet surface to the
bulk fluid

In this chapter we focus on:

3. Adsorption
4. Surface reaction
5. Desorption

108
(1) Adsorption Isotherms: The amount of a gas adsorbed on a solid at
different pressures but at one temp.

A+S A·S
active site

Ct = molar conc. of active sites per unit mass of catalyst, mole/g cat
(= no. of active sites per unit mass / Avagadro’s no.)
Cv = molar conc. of vacant sites, mole/g cat
Pi = partial pressure of species i in the gas phase, atm
Cis = surface conc. of sites occupied by species i, mole/g cat.

A. Molecular Adsorption (Nondissociated Adsorption)

At equilibrium, the net rate of adsorption ≈ 0:

rAD = 0 (If kA is very large, rAD/kA ≈ 0) CCOS = KACvPCO
∵Ct = CV + CCOS = CV ( 1+ KA PA )

Ct
CV =
1 + KA PA

Ct K A PCO
CCO.S 
1  K A PCO
Evaluation of constants

109
B. Dissociative Adsorption

CCS = COS

At equilibrium, rAD = 0:

For CCS = COS , COS = (KAPCO)1/2CV

Site Balance: Ct = CV + CCS + COS = CV + 2 CCS = CV (1+2 (KAPCO)1/2)

( K A PCO ) 1 / 2 C t
C OS 
1  2 ( K A PCO ) 1 / 2
Evaluation of constants
1/ 2
PCO 1 2 1/ 2
 1/ 2
 PCO
C OS Ct K A Ct

＊ Adsorption of H2 and CO
Nondissociated
H2 + S  H2S CO+S  COS
Dissociated
H2 + 2S  2HS CO+2S  CS+OS

。Homework (加分題): If both A and B are adsorbed as molecules, the

adsorption of both A and B are first-order processes. 試推導:
KAPACt
CAS =
1 + KAPA + KBPB

1010
(2) Surface Reaction (Langmuir-Hinshelwood Mechanisms)
(A) Single-Site Mechanism
AS BS

(B) Dual-Site Mechanism for one reactant

AS + S BS+S

(C) Dual -Site mechanism for two reactants

AS + B S CS+DS

(D) Dual-Site Mechanism for two reactants adsorbed on different

type of sites
AS+BS' CS'+DS'

(E) Reaction between an adsorbed molecule and a molecule in the gas

phase—Eley-Rideal mechanism
A S + B (g) C S + D (g)

CS
(3) Desorption
AS A+S

The products of the surface reaction adsorbed on the surface are

subsequently desorbed into the gas phase.
(4) Rate-Limiting Step (RLS)若能使此步驟快速進行，則整個程序必能加速。
＝ Rate-Controlling Step (RCS)
＝ Rate-Determining Step (RDS)

When heterogeneous reactions are carried out at steady state, the rates
of each the three reaction steps in series (adsorption, surface reaction, and
desorption) are equal to one another:
r’A= rAD = rs = rD

1011
However, one particular step in the series is usually found to be
rate-limiting or rate-controlling.

1012
3. Synthesizing a Rate Law (Rate Expression)
Example: Decomposition of cumene (異丙苯) to form benzene &
propylene
C6H5CH (CH3)2 C6H6 + C3H6
C B P

。Adsorption:

。Surface reaction:

1013
 。Benzene Desorption:

At Steady state,

We wish to determine which step is rate-limiting. We first assume one

of the steps to be rate-limiting and then formulate the reaction rate law
in terms of the partial pressures of the species. If the predicted rate
varies with pressure in the same manner as the rate observed
experimentally, the implication is that the assumed mechanism is
correct.

(1) If Adsorption of cumene is the RLS

Because we can not measure CV or CCS , we must replace these

variables with PC, PB and PP .

For adsorption-limited reaction, kA is small and kS and kD are

large. The ratios rS/kS and rD/kD are very small (0), whereas the ratio

1014
rAD/kA is relatively large.

Hint: Using rS/kS  0  rD/kD to find CBS and CCS in terms of partial
pressures.

After combining (10-33) and (10-35):

Replacing CCS in the (10-25) by (10-36):

Site balance:
Substituting (10-35) and (10-36) into (10-40):

Combining (10-41) and (10-37), assuming the adsorption of cumene is

RLS:

Sketch a plot of the initial rate as a function of the partial pressure of

1015
cumene, PC0. Initially, PP = PB = 0.

(2) If surface reaction is the RLS

Site balance: Substituting for CBS and CCS

The initial rate (PP = PB = 0) is

1016
 linearly

independent of PC0

(3) If the desorption is the RLS

Combining (10-28) and (10-47):

Site balance:

1017
Replacing CV in (10-48) by (10-49) and multiplying the numerator and
denominator by PP:

The initial rate (PP = PB = 0):

(4) Summary of the cumene decomposition

The experimental observation of r’C0 as a function of PC0:

The rate law derived by assuming the “surface reaction” is

rate-limiting agrees with the data.

1018
Rate limiting step Rate expression

Adsorption

Surface rxn

Desorption

As a function of PC0, the initial rate will be

Adsorption - rC0’ ≈ CtkAPC0

Surface rxn -rC0’ ≈ KCkSCtPC0 /(1 + KCPC0)

Desorption -rC0’ ≈ kDCt

(PC0 = yC Pt0)

※ Eqn 10-42 (adsorption of C is the RLS)

i. 分母中沒有出現 PC

※ Eqn 10-44 (Surface rxn is the RLS)

i. 分母中沒有出現 PP

※ Eqn 10-50 (desorption of B is the RLS)

i. 分母中沒有出現 PB

歸納 :
(1.) 如果 adsorption of A 為 RLS 則分母不會出現 PA

(2.) 如果 desorption of B 為 RLS 則分母不會出現 PB

(3.) 如果 surface rxn 為 RLS, 則分母不會出現與 surface rxn 相關

component 之 partial pressure

1019
 (4.) 不會被吸附之 component 其 partial pressure 不會在分母中出現
(page 689)

。The Plot of –rC0’ vs. PC0─Decomposition of Cumene

(Without inhibitors; initially no B and P)

1.Adsorption of cumene is the RLS 2.Surface rxn is the RLS

-rC0’ = CtkAPC0 -rC0’= KCkSCtPC0/(1 + KCPC0)

3. Desorption of benzene is the RLS ＊ Experimental observation

-rC0’ = kDCt

* Adsorption or desorption is not

the RLS
* The surface rxn is the RLS

1020
1021
(5) Rate laws derived from the Pseudo-Steady-State hypothesis
(PSSH) 假恆穩狀態推導速率定律
The PSSH, the net rate of formation of reactive intermediates was
assumed to be zero.
Each species adsorbed on the surface is a reactive intermediate.

Use the PSSH when:

1. Some steps are irreversible.
2. Two or more steps are rate-limiting.

The rate law for the irreversible surface rxn:

The net rate of the intermediate is zero:

Substituting for CNS in (10-55):

Site balance:
After substituting for CNS and CIS, solving for CV, which we then
substitute in the rate law:

1022
Take the surface rxn step to be rate-limiting; kS is much smaller than
kN.

(10-63) is identical to the one derived assuming that and

.
ps. this method also works well for a single RLS.
This technique is preferred if two or more steps are RLS or if some of
the steps are irreversible or if none of the steps are RLS.

1023
4. Heterogeneous Data Analysis for Reactor Design 分析實驗數據並由其
中找出速率定律
Deduce rate law; Find mechanism; Evaluate rate law; Design reactor

Hydrodemethylation of toluene 加氫脫甲烷

clinoptilolite
C6H5CH3＋H2 C6H6＋CH4
(crystalline silica-alumina)
T H2 B M

To design a packed-bed reactor and CSTR to process a feed consisting

of 30 T，45 H2，and 25 inert. T is fed at a rate of 50 mol min at
640C and 40 atm.

To design the reactors, we must first determine the rate expression

from the differential reactor (p. 281) data presented in Table 10-5

1024
。Deducing a rage law from the experimental data 分壓在分母出現代
表會被觸媒吸附
1
Dependence on M: if M were absorbed on the surface, PM would
appear in the denominator.

From run 1 and 2: 甲烷分壓提高4倍，對 −rT′ 的影響卻很小

Methane is not (or weakly) adsorbed (R1)
or goes directly into the gas phase similar to propylene in the
cumene decomposition. (R2)

2
Dependence on B:
From runs 3 and 4

(10-68) suggests that B is adsorbed on the catalyst surface.

3
Dependence on T: at low conc. of T (runs 10 and 11), the rate
increases with PT; while at high conc. (runs 14 and 15), the rate is
independent of PT.

Combine (10-68) and (10-69):

4 Dependence on H:
○
From runs 7, 8 and 9,

We conclude that the reaction is first order in H2. H2 is either not

adsorbed on the surface or its coverage of the surface is extremely low.
可說明氫不被吸附在表面上或其在表面的覆蓋面積非常低 (1 KH2PH2)
Combine (10-67) through (10-71):

。Finding a mechanism consistent with experimental observations 尋

1025
求符合實驗數據之機構

(1). From the above result, it is known that T and B are adsorbed
T＋S T．S
B．S B＋S
and both steps are not the RLS

(2). H2 is not adsorbed on the surface, then the surface rxn will be
T．S＋H2 (g) B．S＋M (g)

(3). Methane is not (or weakly) adsorbed, then the surface rxn will be
T．S＋H2 (g) B．S＋M (g)

Basing on the above discussions；we propose the following reaction

mechanism：

(Approximately 75 of all heterogeneous rxns are surface-rxn

limited) 非均勻反應之機構大約75% 為表面反應限制速率

Site balance:
1026
Substitute for CTS and CBS and then substitute for CV in (10-73):

Neglecting the reverse rxn:

。Evaluation of the Rate Expression Parameters 速率定律參數之計算

We wish to determine how best to analyze the data to evaluate the rate
law parameter, k, KT and KB. This analysis is referred to as parameter
estimation. (10-80) are divided by PH2 PT and the equation is then
inverted.

The regression techniques described in Chap. 5 could be used to

determine the rate law by using the equation.

Example 10-2 以 Polymath 做線性化的最小二乘方之分析，求得參數

k 、KT 與 KB 之初估值，再求非線性回歸之收歛值。

Example 10-3 設計能達到指定轉化率之觸媒反應器。

1027
5. Reaction Engineering in Microelectronic Fabrication 微電子製造
之反應工程: Chemical Vapor Deposition (CVD)
積體電路的製造需先製作電子路徑的網路，利用反應工程原理的製作步驟包
括 ： 在 表 面 上 沈 積 一 種 物 種 稱 為 基 質 (substrate) [ 例 如 使 用 化 學 氣 相 沈 積
(chemical vapor deposition)]，改變區域的電導度(conductivity)[如硼摻配(boron
doping) 或 離 子 移 植 (ion-implantation)] ； 以 及 移 除 不 要 的 物 質 [ 如 蝕 刻
(etching)]，經由系統化應用這三個步驟，即可在非常小的半導體晶片上製作微
小的電子電路。

The mechanisms by which CVD occurs are very similar to those of

heterogeneous catalysis.
The reactant adsorbs on the surface and then reacts on the surface
to form a new surface.
The growth of a germanium epitaxial film 鍺薄層 as an interlayer
between a gallium arsenide 砷化鎵 layer and a silicon layer and as a
contact layer. 在砷化鎵與矽層之間形成鍺薄層的中間層

Example: The growth of germanium films 鍺薄膜之成長

The surface rxn is RLS:

1028
Fractional area balance:
The rate of GeCl2 adsorption is

The dissociative adsorption of hydrogen on the Ge surface

Substitute for (10-85) and (10-87) in (10-82)

Fractional area balance

We find that

Lumping KA, KH and ks into k’, 得 Ge 之沈積速率

1029
6. Catalyst Deactivation 觸媒之失活
在多數工業觸媒的反應中，觸媒反應最棘手的問題之一就是觸媒發生反應時，會
失去活性。

Definition of the activity of the catalyst at time t, a(t):

 rA' (t  0) : fresh catalyst

 rA' (t ) : catalyst that has been used for a time t

The rate of disappearance of reactant A on a catalyst:

Where a(t) = catalytic activity, time-dependent

k(T) = specific reaction rate, temperature-dependent
Ci = gas-phase conc. of reactants, products or contaminant

Types of catalyst deactivation 觸媒失活的型式可分成三大類: sintering 燒

結 or aging 老化, fouling 污染 or coking 碳化, and poisoning.

(1) Structural Change (Aging/Sintering)

Causes for Aging: loss of activity due to a loss of active surface area
resulting from the prolonged exposure to high temp. 觸媒長期曝露在高溫
的氣相中，致活性表面受損所引起的活性衰退。
1
Through crystal agglomeration and growth, the internal
surface areas of catalysts and supports are reduced; 晶體的
聚集，與金屬在擔體的表面沈積
2
through the narrowing or closing of the catalyst pores. 觸媒
孔洞的堵塞
3
A change in the surface structure may also result from
either surface recrystallization or from the formation or
elimination of surface defects. 表面結構的改變可能由於表面
的再結晶或表面缺陷(活性部位)的生成或消除
2
Rate of deactivation: the most commonly used is second order.

1030
 Integrating, with a = 1 at t = 0, yield

圖10-23 高溫時由於觸媒擔體軟化後流動，使孔道封閉所引起的表面的消失。

圖10-24 由於原子的遷移以及沈積在表面的小金屬聚集成較大的部位，致使內部
的原子無法接近以產生反應。在溫度低於固體熔點的40% 時燒結通常可忽略不
計。

※ Sintering can be reduced by keeping the temp. below 0.3 to 0.4 times
the metal’s melting point.

‧ Example 10-5 (p.711) Calculating conversion with catalyst decay in

batch reactors
The first-order isomerization

is being carried out isothermally in a batch reactor on a catalyst that is

decaying as a result of aging. Derive an equation for conversion as a
function of time.

1. Design equation

2. Reaction rate law

1031
3. Decay law. For second-order decay by sintering

4. 代入 design eqn.

5.

6. 整理後可得

(2) Coking or Fouling 由於碳化或污染引起的衰退

It results from a carbonaceous (coke) material being deposited on
the surface of a catalyst.

The amount of coke deposited

C C ＝ At n
Cc is the conc. of carbon on the surface (g/cm2); n and A are fouling
parameters 污垢參數, which can be functions of the feed rate.

＊ Coking can be reduced by running at elevated pressure (2000 to

3000 KPa) and hydrogen-rich streams.

1032
 ＊ Catalyst deactivated by coking can usually be regenerated by
burning off the carbon.

(3) Poisoning 中毒引起的衰退

Causes for Poisoning:
The poisoning molecules become irreversibly chemisorbed to active site,
thereby reducing the number of sites available.
The poisoning molecule, P, may be a reactant or a product or an impurity.

A. Poison in the Feed. Many petroleum feed stocks contain trace

impurities such as sulfur, lead, which are too costly to remove. 雜質
移除的成本太高
Rate of deactivation
A. Poison (impurity) in the feed

Main reaction：
A＋S A．S
A．S B．S＋C (g)
B．S B＋S

Poisoning reaction：

Packed-Bed Reactors. 填充床反應器之中毒 The poison is removed

from the gas phase by being adsorbed on the catalytic site, the
deactivation process can move through the packed bed as a wave front.
開始時，只在接近反應器入口的部位衰退，這是因為毒物由氣相移除
後被觸媒吸附之故，因此遠離入口的觸媒部位並不受影響，但隨著時
間增長，接近入口端的部位之吸附已達飽和，故毒物不被吸附而繼續
向反應器的下游移動。

1033
B. Poisoning by either reactants or products. The main reactant also
acts as a poison.

可處理衰退觸媒的三種反應系統
We will consider 3 reaction systems that can be used to handle systems
with decaying catalyst. To offset the decline in chemical reactivity of
decaying catalysts in continuous flow reactors, the following methods are
commonly used: 在含衰退觸媒的連續式流動系統中，要消除化學活性的下降
1. Slow decay: Temperature-Time Trajectories (10.7.2)
2. Moderate decay: Moving-Bed Reactors (10.7.3)
3. Rapid decay: Straight-Through Transport Reactors (10.7.4)
(1) Temp. - time trajectories 溫度-時間之軌跡
在連續式的流動反應器中，轉化率通常必須為常數，以使後續的處理
步驟(如分離)不致混亂。在含有衰退性觸媒的填充床或流體化床中維
持常數轉化率的方法之一為恆穩的增加入料的溫度。

1034
 k (T )a(T , t )  k0
The goal is to find how the temp. should be increased with time to
maintain constant conversation. 使用 Arrhenius 方程式以活化能 EA 表示 k

解 1/T
The decay law also follows an Arrhenius-type temp dependence.

kd0: decay constant at temp. T0, s-1

EA: activation energy for the main reaction, kJ/mol
Ed: activation energy for catalyst decay 觸媒衰退的活化能, kJ/mol

Substituting (10-115) into (10-116) and rearranging yields

Integrating with a = 1 at t = 0,

Solving (10-114) for a and substituting in (10-118)

(10-119)
(10-119)說明觸媒反應器的溫度應如何隨溫度上昇，以使反應速率保持常數。

(2) Moving-Bed Reactors 移動床反應器

1035
‧Reaction systems with significant catalyst decay require the continual
regeneration and／or replacement of the catalyst
新鮮的再生觸媒由反應器的頂部加入，然後以緊密的填充床移動通過反應
器，當它移經反應器時，持續碳化直至反應器的出口進入混合窯中，窯中
以熱空氣燒掉碳，窯中的再生觸媒以氣流提升至分離器再回流到反應器
中。

圖 10-32 熱觸媒裂解

反應物A 在ΔW區間的莫耳均衡為：

Dividing by W, letting W0

dF A
   rA'
dW

dX
FA0   rA' (2-17)
dW

where  rA (t )  a(t )[rA (t  0)]

' '

 a(t )kf n (C A , C B ........)

W   b AC Z
＊ t：the time that the Consider the case with
catalyst has da
  kd a n the decay rate law
been in contact dt
with the gas (10-110)

1036
尋找接觸時間t與觸媒重量W的關係式，思考反應器中的任一點z，該點的氣體反
應物已以順流方向通過W重量的觸媒。由於固體觸媒係以Us 的速率 (質量/時間)
流經床體，當觸媒到達z點時，觸媒與氣體反應物接觸的時間為：
W dW
∵ t= ； dt  (10-123) combine (10-110) and (10-123)
US US
da k
∴  d an (10-124)
dW U S

Example 10-7 (p.725) Catalytic Cracking in a Moving-Bed Reactor

The catalytic cracking of a gas oil charge, A, to form C5+ (B) and to form
coke and dry gas (C) is to be carried out in a screw-type 螺旋運送的
conveyor moving-bed reactor at 900F:

This reaction can also be written as

Gas oil exhibits a wide spectrum of cracking rates gives rise to the fact
that the lumped cracking rate is well represented by a second-order rate
law:

The catalytic deactivation is independent of gas-phase conc. and follows

a first-order decay rate law, with a decay constant of 0.72 reciprocal
minutes. The feed stream is diluted with nitrogen so that as a first
approximation, volume moves through the reactor at a rate of 10 kg/min.
The gas oil is fed at a rate of 30 mol/min at a conc. of 0.075 mol/dm3.
Determine the conversion that can be achieved in this reactor.

First-order decay using (10-124)

Integrating ∵CA = CA0(1-X)

1037
Combining, we have
Separating and integrating yields

(3) Straight-Through Transport Reactors (STTR)直線通過的傳送反

應器
This reactor is used for reaction systems
in which the catalyst deactivates very
rapidly. Commercially, the STTR is used
in the production of gasoline from the
cracking of heavier petroleum fractions
where coking of the catalyst pellets
occurs very rapidly.
在 STTR 中 觸 媒 粒 子 與 反 應 物 一 起 入
料，且非常快速的流過反應器。在STTR
中觸媒粒子的整體密度明顯小於移動
床之整體密度，且粒子經常以同於氣流
之速度貫穿床體，在某些地方，STTR
也稱為循環式的流體化床(circulating
fluidized bed, CFB)。

A mole balance on the reactant A over the differential reactor volume

is

1038
 FA ( z )  FA ( z  z )  (  rA ) Ac z
Dividing by z and taking the limit as z0 and recalling that
rA = B rA’
dX dF
 FA0   A  (  rA ) Ac  (  rA' )  B Ac
dz dz
dX  B Ac
 [rA (t  0)]a (z/UP)
'

dz FA0
z
t：the time the catalyst pellet has been in the reactor =
UP

where

＊因應觸媒活性衰退的方法
1.為維持固定的轉化率
(1) 逐漸提高反應溫度，（進料或反應器溫度）
(2) 逐漸降低進料流率
2.採用流體化床或移動床
3.當轉化率鄰近 100或平衡轉化率時，可加長反應器長度
4.使用兩個反應器交互使用

＊提高反應溫度
(1)不能超過 max allowable temp.
(2)不能影響選擇率
(3)可能因出口溫度升高，必須加裝冷卻設備

＊降低進料流率
可能因此影響下游設備之操作

1039
補充教材:
Design of Reactors for Solid-Catalyzed Reactions

(1) Batch Reactor

dX d NA
NAO =- = (- rA) V = (-rA') W (1)
dt dt

-rA ﹝=﹞ moles of A / vol. of reactor ∙time

-rA’ ﹝=﹞ moles of A / wt. of catalyst ∙time

(3) Tubular Reactor / Packed-Bed Reactor

A. Tubular reactor:
i. FA(Z) - FA (Z+ Z) = (- rA) AC Z

1 d FA
- = ( - rA ) (2)
AC dZ

∵ FA = FA0 ( 1 – x )

d CA
or FA = u CA - DL ‧ Ac
dZ
convective flow diffusion / dispersion

FA0 dX
∴ = ( -r A ) (3)
AC dZ
d d
d CA (4)
or ( DL ) - ( u CA ) = ( - r A ) AC
dZ dZ dZ

ii. FA ( V ) – FA ( V + △V ) = ( - rA ) AC

1040
 dX d FA
FA0 = - = (- rA ) (5)
dV dV
dX
V = FA0 ∫ (6)
- rA

B. Packed-bed reactor:

除上列 Tubular reactor 的式子外,常用下列的式子

FA ( W ) – FA ( W + △W ) = ( - rA’ ) △W

dX d FA
FA =- = ( -r A' ) (7)
dW dW
dX
W = FA0 ∫ (8)
- r A'

第 8 式亦可由第 6 式左右兩邊各乘ρb 得到。(ρbV = W)

↑
bulk density of catalyst
(3) CSTR (CSTCR)
↑catalytic

FA0 – FA = ( - rA ) V = ( - rA’ ) W
FA0 - FA FA0 X
W= =
- rA ' - rA '

※ Note that the above equations are for the cases of negligible diffusion
(both internal and external ) resistance. In Chapter 11 and 12, we will
discuss the effect of diffusion.

(4) Differential Reactor

△ FA △ X FA0X
- rA = - ------ = FA0 ------ = ------
△W △ W W

1041