WASTE MANAGEMENT, Vol. 13, pp. 3-14, 1993 0956-053X/93 $6.00 + .

00
Printed in the U.S.A. All rights reserved. Copyright ~c~1993 Pergamon Press Ltd.

ORIGINAL CONTRIBUTION

W A S T E M I N I M I Z A T I O N BY
PROCESS MODIFICATION

J. R. Hopper,* C. L. Yaws, T. C. Ho, and M. Vichailak

Lamar University, Department i f Chemical Engineering, Beaumont, Texas 77710, U.S.A.

ABSTRACT. A simulation of the Sohio process for the production of acrylonitrile from the catalytic ammoxidation of
propylene has been performed, using published kinetic and thermodynamic data to illustrate the concepts of pollution pre-
vention by process modification. The study has determined the reaction parameters which will minimize the production of
by-products while maintaining the conversion ofpropylene above 80%. The reaction parameters studied were reactor type
(plug flow reactor [PFR], continuous stirred tank reactor [CSTR], and fluidized bed reactor [FBR]), reaction temperature,
residence time, and entering feed temperature. The minimum byproducts were produced in an FBR operating at 450°C at
a residence time of 7 seconds for a conversion of 81%.

INTRODUCTION aged. Under the category o f source reduction, there

are two subcategories: source control and product
Waste minimization means the reduction, to the ex-
substitution. Source control can be accomplished by
tent feasible, of hazardous waste that is generated
(a) good housekeeping practices, (b) input material
prior to treatment, storage, or disposal o f the waste.
modification, and (c) technology modification. EPA
The terms "waste minimization" and "pollution pre-
has reported that, generally, technology modifica-
vention" are becoming key initiatives of the United
tions have been found to be the most effective means
States Environmental Protection Agency (U.S.EPA),
o f reducing waste generation (4). Technology modi-
and the terms are being used increasingly in all areas
fications have been categorized as follows:
o f current applied research and development (1).
Waste minimization has been defined as consisting
• Process Modifications
o f two basic techniques: source reduction and recy-
• Improved Controls
cling (2; see Fig. 1). Source reduction, or avoiding
• Equipment Changes
waste generation, is the most desirable goal and
• Energy Conservation
should be explored first (3). In the waste management
• Water Conservation
hierarchy, source reduction is followed in order by re-
cycling, treatment, and, finally, disposal. Although
such processes as incineration, stabilization, a n d / o r The need for waste minimization studies has be-
storage are clearly preferable to land disposal, they are come apparent to the Chemical Processing Industries
not included in the definition of waste minimization. (CPI). Congress initially declared waste minimization
The total concept of pollution prevention is that it is to be the national policy o f the United States. This
m u c h more desirable not to produce waste, rather policy dictates that, wherever feasible, the generation
than to implement extensive treatment schemes to o f hazardous waste is to be reduced or eliminated as
insure that the quality of the environment is not dam- expeditiously as possible (5). The Clean Air Act
A m e n d m e n t s of 1990 (CAA) and the Superfund
A m e n d m e n t s Reauthorization Act, of which Title
313 includes the Toxic Releases Inventory (TRI) list,
RECEIVED 31 JULY 1992; ACCEPTED 30 AUGUST 1992.
Presented at the 1992 Spring National Meeting, March 29-April 2, will clearly impact the drive to implement this con-
1992, Hyatt Regency, New Orleans, LA, U.S.A. cept, which has been given a high priority by Con-
*To w h o m correspondence m a y be addressed. gress.
Acknowledgement--This project has been funded in part with
federal f u n d s as part o f the program o f the G u l f Coast Hazardous The objective o f this project is to develop examples
Substance Research Center, which is supported u n d e r cooperative of waste minimization by process modifications that
agreement R815197 with the U.S.EPA. T h e contents do not nec- can be achieved by modification of chemical process
essarily reflect the views a n d policies o f the U.S.EPA nor does the
m e n t i o n of trade n a m e s or commercial products constitute en- reaction and separation parameters. These examples
d o r s e m e n t or r e c o m m e n d a t i o n for use. can be used as guidelines for process and environ-
4 J.R. HOPPERE T A L .
WASTE MINIMIZATION TECHNIQUES

RECYCLING SOURCE~,REDUCTI
~ ~C-~_]ONu i

USE/ REUSE i
f
ONSITE/ OFFSITE

L ]

RECLAIM
i
- Process to recover
- I n g r e d i e n t in a process usable product
- Effective substitute - Regeneration

SOURCECONTROL

GOODPRACTICES
HOUSEKEEPING INPUT
IIBII

MATERIAL
MODIFICATION
I
I
i I SUBSTITUTION
PRODUCT i

TECHNOLOGY
MODIFICATION
- W a s t e stream segregation - Input purification - Improved Control
- I n v e n t o r y control - Input substitution - Process Modification
- E m p l o y e e training - Equipment Changes
- S p i l l / l e a k prevention - Energy Conservation
- Scheduling improvement - Water Conservation

FIGURE1.Wasteminimizaliontechniquesdiagram.

mental engineers to follow in suggesting process mod- sure, catalyst, mixing conditions, ratio of feed con-
ifications that will minimize waste generation. centrations and conditions, reaction type, and reactor
design options. Although catalyst changes are, with-
out a doubt, the most effective method of changing a
PROCESS MODIFICATION CONCEPTS
reaction selectively ( 11, 12), catalyst changes are very
Process modifications or changes mean: (a) the use of specific for each process and are in most cases highly
alternative low-waste process pathways to obtain the proprietary. However, changes in the other reaction
same product, and (b) modification of reaction or parameters have more general applications for many
separation parameters. processes and can have an impact far greater than any
Multiple chemical reactions can be classified into of our previous expectations ( 13, 14).
three general reaction types (6-10): (a) series, (b) par- This work has evaluated some of the conditions for
allel, and (c) combinations of series and parallel re- the modification of the reaction parameters for the
actions. It is the many possible reactions that generate acrylonitrile process.
many of our waste products. Generally, we have de-
sirable products and undesirable products. The un-
CASE STUDY ON ACRYLONITRILE
desirable products may become waste streams. The
PROCESS
ratio of the desirable products to the undesirable
products is generally defined as the selectivity of the General studies of process modifications have been
reaction. This selectivity can be influenced by the made in the past (15-17), and an earlier report was
choice of catalysts, reaction parameters, or by modi- presented for the allyl chloride process on our pre-
fication of these reaction parameters. liminary results (18, 19). Recently, two specific
Waste minimization by modification of reaction cases have been reported for the effect of modifica-
parameters is defined as changing the selectivity of the tion of reaction parameters for industrial processes
reaction so that undesirable reactions that produce (13, 14).
waste products are minimized, while at the same time This case study is an example of how alteration of
producing the desirable products. This selectivity reactor design and distillation parameter selection
may be affected by all of the reaction conditions. can reduce waste generation for the acrylonitrile pro-
These reaction conditions include temperature, pres- cess.
WASTE MINIMIZATION BY PROCESS MODIFICATION 5

PROCESS DESCRIPTION products, which are fractionated to remove pure

HCN and then sent to the main purification section.
Since the commercialization of the Sohio process in
A main fractionator yields an overhead consisting of
the early 1960s, all acrylonitrile plants built in the
wet acrylonitrile, which is dried and purified by azeo-
world have been based on the reaction between pro-
tropic and conventional distillation. The bottoms wet
pylene, ammonia, and air (4, 20-25). Acrylonitrile is
acetonitrile is similarly concentrated, dried, and con-
the product from the gas phase catalytic air oxidation
verted to high purity product (4, 24).
of propylene and ammonia. The reaction chemistry
Acrolein, acetonitrile (ACE), and HCN are by-
for the ammoxidation is
products and potential wastes. This study has evalu-
ated the reaction parameters shown in Table 1 to de-
Propylene Ammonia Oxygen Acrylonitrile termine the conditions that will minimize the
CH2=CH-CH3 + NH 3 + 3/2 02 ---" C H 2 = C H - C N production of byproducts while maintaining the pro-
Water duction of acrylonitrile.
+ 3H20, [1]
Reaction System Analysis
with the combination of five other possible side re- The rate equation for the ammoxidation ofpropylene
actions: over Bi-Mo-O has a first-order dependence with re-
spect to propylene and a zero-order dependence for
Acrolein both oxygen and a m m o n i a when they are supplied in
CHz=CH-CH3 + 02 --~ C H 2 = C H - C H O at least stoichiometric amounts (26-32). The rate
+ H20 , [2] equations are

Aeetonitrile

CH2=CH-CH3 + NH3 + 9/402 ~ CH3-CN (-r.) = k.Cc3H6 [7]

+ 1/2 CO2 + 1/2 CO + 3H20, [3] (-r_,) = k_,C~.~ [8]

C H 2 = C H - C H O + NH3 (-- r3) = k3CcsH6 [91

+ 1/2 02 ---" C H 2 = C H - C N + 2H20, [41
( - r4) = kaCcH2CHCHO [ 101

C H 2 = C H - C N + 20_, ~ CO, (-- rs) = ksCcH2CHCN [ 11 ]

Hydrocyanic acid
+ CO + HCN + U20 , [5]
( - r6) = k6CcH3CN [ 12]
CH3-CN + 3/2 02 --" CO2 + H C N + H20. [6]
where the rate constants are expressed in the Arrhe-
The catalyst used for the reaction in the early pro- nius form by
cess version was Bi-Mo-O (4). The current commer-
E i 1 1
cial catalyst is of unknown composition with anti- k,.r, = k,.r2e ~71t¢~,) ~)1. [13]
mony-tellurium catalyst, manufactured by Nitto
Corporation, being one possible catalyst. The flow di-
agram for this process is shown in Fig. 2. Approxi- From Callahan's studies (26, 27, 33), the activa-
mately stoichiometric quantities of propylene, am- tion energies for Eqs. [1], [2], [3], and [5] were esti-
monia, and oxygen (as air) are introduced to a mated to be
fluidized-bed catalytic reactor at 15 psig and a contact
time in the range of several seconds, and a tempera- E~ = 19,000 cal/g mol
ture of 350-600°C. The use of polymerization-grade E2 = 19,000 cal/g mol
propylene is unnecessary. Once-through-flow is used E3 = 7000 cal/g mol
because conversion of propylene is practically com- E5 = 19,800 cal/g mol
plete. The reaction is exothermic, so heat removal
must be provided. The reactor effluent is neutralized The activation energy for Eqs. [4] and [6] is estimated
to remove unconverted ammonia. It is next washed to be 7000 cal/g mol.
with water to yield an unabsorbed stream of inert The rate constants for each reaction were achieved
gases and the solution of acetonitrile, acrylonitrile, by applying Callahan's rate constant, Cathala's rate
and HCN. This solution is stripped of the dissolved constant ratios (28), and the Arrhenius equation. The
 I
I

6
WASTE MINIMIZATION BY PROCESS MODIFICATION 7

TABLE 1 The values for the constants are given in Table 2

Reaction Parameters Studied (35).
Reactor Type PFR / CSTR / FBR
Reactor Condition Temperature Residence Time Stoichiometric Equation
Feed Condition Entering Feed Temperature
The stoichiometric equation for each o f the speciesj
Kinetic Model Six Reactions
for the n independent reactions is

= Fj0 + F,0 ~ v,fl(,, [161

rate constants at 470°C were estimated to be i=1

k~ = 0.40556 sec -~
k 2 = 0.00973 sec -~ where v o is the stoichiometric coefficient for compo-
k 3 = 0.01744 sec-
nent j in reaction i. Fj0, ~ , and F40 are the molar
k4 = 6.81341 sec -~ flowrates for c o m p o n e n t j initially and at any point in
k5 = 0.16222 sec- time and the primary reactant A.
AT,.is the extent of conversion for reaction i and is
k6 = 0.07300 sec
defined as
The heats o f reaction at 298°K (34) are
X, - Ni, - Ni0 _ ANj, [17]
AH~ = --515,610 J/g mol voN.lo v,jN~o '
AH2 = -- 333,350 J/g mol
AH3 = --864,990 J/g mol
5//4 = -- 182,260 J/g mol where AN, i is moles o f s p e c i e s j consumed (formed) in
AH5 = -- 800,900 J/g mol reaction i.
AH6 = --593,120 J/g mol
Component Mass Balance
where the heat of reaction at other temperatures can The steady state c o m p o n e n t mass balance for the
be obtained from PFR and the CSTR is

A H r , ( T ) = AHr,(298°K) + ~2T (ACp), d T . [14] F,o - F, +

~0 ~
r, d V = O. [18]
98°K

For q simultaneous reactions, n o f which are indepen-

The heat capacity values for each o f the speciesj is
dent, r i is defined as
given by
q
rs = - ~ vijro, [ 19]
Cpi = o~, + 3 i T + % T 2 + z j T 3. [15] i=1

TABLE 2
Heat Capacities Constants

c~i 3, % z~

1. Nitrogen, N2 30.78 -- 1.178E-02 2.390E-05 - 1.000E-08

2. Carbon Monoxide, CO 30.87 -- 1.285E-02 2.789E-05 - 1.272E-08
3. Oxygen, 02 28.11 --3.680E-06 1.746E-05 - 1.065E-08
4. Carbon Dioxide, CO2 19.80 7.344E-02 -- 5.602E-05 1.715E-08
5. Propylene, C3H6 3.710 2.345 E-01 - 1.160E-04 2.205 E-08
6. A m m o n i a , NH3 27.31 2.383E-02 1.707E-05 -- 1.185E-08
7. Hydrogen Cyanide, HCN 21.86 6.062E-02 --4.961E-05 1.815E-08
8. Acrolein, C3H40 11.97 2.106E-01 - 1.071E-04 1.906E-08
9. Acrylonitrile, C3HsN 10.69 2.208E-01 -- 1.565E-04 4.601E-08
10. Acetonitrile, C2HsN 20.48 1.196E-01 --4.492E-05 3.203E-09
1 I. Water, H20 32.24 1.924E-03 1.055E-05 - 3.596E-09

Ce =- Joule/g mole K
T---K
8 J.R. HOPPER ETAL.

where r~j is the rate of formation of species j in reac- where 0i = Fjo/F4o: ratio of the initial molar feed rate
tion i. The bubbling bed model (36) has been used for for each specie j to the initial molar feed rate of pri-
the FBR. This model has a rising bubble surrounded mary reactant.
by a cloud-wake and enclosed by an emulsion catalyst For the PFR, the total energy balance for n inde-
bed. Mass transfer and reaction proceeds in each of pendent multiple reactions involvingj species is
these phases according to the following component
mass balance relations for reactant A:
F,o OjCe, + X~ ACei
i=l
dCA dC~
- ~ = uh dl - VbKrC'lb -- £r, AHr,(f) = Q- W,., [24]
t'=f

+ (Kh,.)b(C~h -- CA,), [201

where Q = UA(T, - T) and T, = temperature of the
surroundings.
(K~,)h(CA~ - CA,) -~ %KrCA,,
These models have been used to evaluate waste
+ (K,.,,)h(CA,.- C~,,), [21] minimization by reaction parameter modifications
for this process.

(K,.,,)h(C4,.- Ge) -~ % KrG,.. [221

DISCUSSION AND RESULTS
These parameters have been estimated (36).
The major wastes considered for the acrylonitrile pro-
cess are ACE and HCN, because the production of
Total Energy Balance acrolein is very much less than the production of ei-
For the CSTR and for the FBR, the total energy bal- ther ACE or HCN. An analysis of the reactor type,
ance for n independent multiple reactions involvingj temperature, and residence time has been done to es-
species is tablish the reaction conditions that will minimize the
production of these byproducts and maintain the pro-
le~ T m
duction of acrylonitrile (ACN).
Q - W~ - - FAO Jj To ~ Oicej a T Plots of the mole fraction for each of the reactants
and products versus residence time at 4000C and 2
-- Fao £ AHr,(T)X, = O, [23] atm for the PFR, CSTR, and FBR are shown in Figs.
i=1 3, 4, and 5 respectively. In Fig. 3, showing the plot for

PLOT OF MOLE FRACTION VERSUS RESIDENCE TIME

OPERATING CONDITION : ISOTHERMAL, 400 °C, 2 a t m
REACTOR TYPE : PLUG FLOW

0.25

0.20

Z
O
0.15

gr.,,

o 0.10
sr~r~r~ PROPYLENE
~,~:,.~, AMMONIA
v. v.v.v.v. OXYGEN
;, ;, ;, ;, ;, A C R Y L O N I T R I L E
0.05 II I I I W A T E R
ACROLEIN
~. ¢ • ~. ~ A C E T O N I T R I L E
~=~" A C0a
"~"--""--""~'"~ CO
~',,-%%%% H C N
0.00
0.00 5.00 10.00 15.00 20.00 25.00
RESIDENCE TIME (S)

F I G U R E 3. Acrylonitrile synthesis.
W A S T E M I N I M I Z A T I O N BY P R O C E S S M O D I F I C A T I O N 9

PLOT OF MOLE FRACTION VERSUS RESIDENCE TIME

OPERATING CONDITION : ISOTHERMAL, 400 °C, 2 atrn
REACTOR TYPE : CONTINUOUS STIRRED TANK

0.20

0.15
z
o

i0.10
o

u u u u u PROPYLENE
====,~ AMMONIA
0.05 0¢¢¢0 OXYGEN
ACRYLONITRILE
~tt i ~ WATER
;.";: × × × ACROLEIN
* * * * ACETONITEILE
-~=-~- ~- CO~
',-t'--t"-,~',-"-,t CO
##~.'. H C N
0.00 ,r ......... 'r ......... ? ......... ~ ......... ~ ......... ,
0.00 5.00 10.00 15.00 20.00 25.00
RESIDENCE TIME (S)

FIGURE 4. A c r y l o n i t r i l e s y n t h e s i s .

the PFR, the reactant oxygen decreases from 18% in idence time. A similar profile of reactants and prod-
the feed to 3% after a residence time of 20 sec, while ucts is shown for the CSTR and FBR in Figs. 4 and 5
the reactants ammonia and propylene decrease from respectively. Similar plots can be generated at various
7% in the feed to 1% after a residence time of 20 sec. temperatures.
Water is a significant product and reaches a value of A comparison of waste generation with the varia-
21 mole%, while ACN reaches 3.7%, ACE 0.5%, tion in temperature and residence time can be ob-
HCN 2.2%, CO_, 2.5% and CO 2.5% for this same res- tained from the cross section of Figs. 3, 4, or 5 at var-

PLOT OF MOLE FRACTION VERSUS RESIDENCE TIME

OPERATING CONDITION : ISOTHERMAL, 400 °C, 2 a t m
REACTOR TYPE : FLUIDIZED BED

0.25 -

0.20

Z
o
~< 0.15

,...1
O 0.10

~uuu~ P R O P Y L E N E
:~=~ AMMONIA
¢¢¢¢¢ O X Y G E N
ACRYLONITRILE
0.05 p in ~B W A T E R
×××:~x ACROLEIN
~ ** ¢ ¢ * ACETONITRILE
===== COz
~ CO
.'~.~ HCN
0.00 I I I ~ I I I I I I

0.00 5.00 10.00 15.00 20.00 25.00

RESIDENCE TIME (S)

FIGURE 5. A c r y l o n i t r i l e s y n t h e s i s .
10 J.R. HOPPER ETAL.

Mole ratio of ACE/ACN versus Temperature (C)

for Fluidized Bed Reactor
4.5

4.0

3.5

3.0

2.5

2.0

1.5

1.0

0.5

0.0 i
200 260 360 360 4()0 450 500
TEMPERATURE C

[- I - 2 5 E C --I'-- 5SEC -)K- 10SEC I

FIGURE 6. Acrylonitrile synthesis.

ious times and temperatures by plotting the ratio of change in residence time has no significant effect on
HCN/ACN, ACE/ACN, and the combination of this ratio. A similar profile of the plot shown in Fig. 6
both ([HCN + ACE]/ACN) with respect to the tem- can be obtained for the PFR and the CSTR.
perature and residence time for each of the reactor A plot of the mole ratio of HCN/ACN as a func-
types. tion of temperature for the PFR is shown in Fig. 7.
A plot of the mole ratio of ACE/ACN as a function This plot shows that the ratio HCN/ACN increases as
of temperature for the FBR is shown in Fig. 6. This the temperature and residence time increase. In Fig.
plot shows that the ratio of ACE/ACN decreases as 7, the minimum ratio occurs at a temperature of
the temperature and residence time increase. The about 300°C; however, the conversion ofpropylene at

Mole ratio of HCN/ACN versus Temperature (C)

for Plug Flow Reactor
1.4-

1.2

1.0

z< 0.8

o= 0.6

0.4

0.2-
- - - - - - - - - - q" ±
0.0"r ',"p
200 25o 3oo 3Eo 460 460 500
TEMPERATURE C

1' - 1 - 2 S E C "-I'-- 5SEC --)K-- 10SEC I

FIGURE 7. Acrylonitrile synthesis.

WASTE MINIMIZATION BY PROCESS MODIFICATION 11

Mole ratio of [HCN+ACE]/ACN versus Temperature (C)

for Plug Flow Reactor
4.5
4.0
3.5
z
L)
3.0
<c

E 2.5
O
+
Z
2.0
L)
z
1.5
1.0 S
0.5
0.0
200 2,50 3()0 3~i0 460 450 500
TEMPERATURE C

I "IB- 2SEC --t-- 5SEC ~ IOSEC }

FIGURE8. Acrylonitrilesynthesis.

this temperature is only 12.6% at a residence time of ture for minimizing the waste and that it is in the
10 sec. This indicates that a higher temperature and/ range of 400-480°C for each type of reactor. For this
or residence time may be necessary. A similar profile temperature range, a high conversion can be obtained
of a plot of this ratio shown in Fig. 7 can be obtained by selecting the correct residence time. A higher con-
for the CSTR and the FBR. version can be obtained by choosing a longer resi-
A plot of total waste ([HCN + ACE]/ACN) versus dence time, but the ratio of waste to acrylonitrile pro-
temperature and residence time is shown in Figs. 8, 9, duced will also increase marginally.
and 10 for the PFR, CSTR, and FBR, respectively. An exact comparison of the waste generation for
These plots show that there is an optimum tempera- each type of reactor can be made by comparing the

Mole ratio of [HCN+ACE]/ACN versus Temperature (C)

for Continuous Stirred Tank Reactor
4.5
4.0
3.5
z0 3.0
2.5
+ 2.0
Z

=-" 1.5

0.5 " ~
0.0 ,

200 250 300 350 400 450 500

TEMPERATURE C

I-IB-2SEC -+-5SEC -'~:- 10SEC I

FIGURE9. Acrylonitrilesynthesis.
12 J.R. HOPPER E T A L .

Mole ratio of [HCN +ACE]/ACN versus Temperature (C)

for Fluidized Bed Reactor
4.5
4.0
3.5
z 3.0
o<

~, 2.5
(3
<

z
0
÷ 2.0
=-" 1.5
/
1.0
/
0.5

0.0
200 250 360 350 4()0 450 500
TEMPERATURE C

I-I-2SEC --I--5SEC ~IOSEC I

FIGURE 10. Acrylonitrile synthesis.

mole ratio of undesired product to the acrylonitrile Table 4 shows the ratio of HCN/ACN and ACE/
(HCN/ACN, ACE/ACN) at the same residence time ACN at three different conversions for three reactors.
(as shown in Table 3) and also at the same conversion The residence time used for each reactor varies with
of propylene (as shown in Table 4). These two com- the type of the reactor. The FBR again generates less
parisons were made at an operating temperature of waste than the other two reactors.
400°C and pressure of 2 atm.
A comparison of the mole ratio of HCN/ACN and
CONCLUSION
the mole ratio of ACE/ACN for each of the reactors
at constant residence times of 2, 10, and 15 sec in To minimize the byproducts in the production ofac-
Table 3 shows that the FBR has the lowest values. The rylonitrile by modification of the reaction parameters
greatest difference in these ratios is for HCN/ACN. in the process, the following conditions would be rec-
The highest ratio of HCN/ACN occurs in the CSTR ommended:
which also has the lowest conversion. The mole ratios
of both HCN/ACN and ACE/ACN are higher with Reactor Type: Fluidized Bed Reactor
the PFR than the FBR but the conversion in the PFR Temperature: 400-480°C
is also higher. Residence Time: 2-10 sec.

TABLE 3 TABLE 4
Reactor Comparison for Waste Generation (400°C, 2 atm) Reactor Comparison for Waste Generation (400°C, 2 atm)

Mole Ratio Mole Ratio

Reactor Residence % Reactor Residence %
Type Time (s) Conversion HCN/ACN ACE/ACN Type Time (s) Conversion HCN/ACN ACE/ACN

2.00 19.97 0.04356 0.09767 0.90 10 0.02050 0.09820

PFR 10.00 66.88 0.26389 0.09565 PFR 4.25 40 0.10647 0.09695
15.00 80.72 0.44471 0.09442 9.90 70 0.29294 0.09544

2.00 19.29 0.08907 0.09728 0.95 10 0.04234 0.09789

CSTR 10.00 54.43 0.44404 0.09491 CSTR 5.60 40 0.24901 0.09599
15.00 64.18 0.66527 0.09400 19.60 70 0.86948 0.09336

2.00 17.14 0.03600 0.09647 1.15 10 0.02016 0.09723

FBR 10.00 60.69 0.21180 0.09086 FBR 5.51 40 0.10590 0.09398
15.00 75.11 0.34930 0.08744 12.99 70 0.29020 0.08880
WASTE MINIMIZATION BY P R O C E S S M O D I F I C A T I O N 13

The reactor effluent from the operation of the re- 15. Basta, N., Vagi, D., Ushio, S., Hunter, D., and Johnson, E.
actor at 450°C and the residence time of 7 seconds is Waste: A n ounce of prevention. Chem. Eng. 95(I !): 34 (1988).
16. Overcash, M. Techniquesfor Industrial Pollution Prevention.
Lewis Publishing Co., Chelsea, MI (1986),
Component Mole% 17. Tavlerides, L. L. Process modification for industrial pollution
source reduction. In: Industrial Waste Management Series,
Propylene 1.4 Patterson, J. W., Ed. Lewis Publishing Co., Chelsea, MI
Ammonia 1.4 (1985).
Oxygen 5.5 18. Hopper, J. R. and Muninnimit, A. Waste minimization by
Acrylonitrile 3.6 process modification. Proceedings of the National AIChE
Water 18.1 Conference, Washington, D.C., December (1989).
Acrolein 0.0 19. Hopper, J. R., Yaws, C. L., Ho, T. C., Vichailak, M., and Mu-
Acetonitrile 0.2 ninnimit, A. Waste minimization by modification of process
Carbon dioxide 1.8 parameters. IUCCP Symposium: Industrial Environmental
Carbon monoxide 1.7 Chemistry: Waste Minimization in Industrial Processes and
Hydrogen cyanide 1.6 Remediation of Hazardous Waste, Texas A&M University,
College Station, TX March 23-26, 1992.
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14 J . R . HOPPER ET A L .

NOMENCLATURE cal reaction based on volume of

solid
A Heat transfer area N~, = Moles o f c o m p o n e n t j i n reaction i
C4 Molar concentration of c o m p o n e n t Q -- Rate o f flow o f heat to the system
A from the surroundings
C,~, G , . , G,, = Concentration of A in the gas bub- (-r,) = Reaction rate o f disappearance of
ble, in the cloud-wake region, and in reaction i
the emulsion phase, respectively T = Temperature
ACei = Overall heat capacity difference of U = Heat transfer coefficient
reaction i per mole of A reacted V = Volume o f reactor
Heat capacity value of c o m p o n e n t j W~ = Work which is necessary to get the
E, = Activation energy of reaction i mass into or out o f the system
F, = Molar flowrate of c o m p o n e n t j Xi = Extent o f conversion
AHri = Heat o f reaction i aj, flj, %, zj = Heat capacity constants of compo-
(Kh,.)h = Coefficient o f gas interchange be- nentj
tween bubble and cloud-wake re- 7h, %., 7,, = Ratio of solids dispersed in bubbles,
gion based on volume of bubbles cloud-wake region, and emulsion to
(K,,,),, = Coefficient of gas interchange be- volume o f bubbles, respectively.
tween cloud-wake region and emul- v,j = Stoichiometric coefficient for com-
sion phase based on volume of bub- ponent j in reaction i
bles 0/ = Mole ratio of c o m p o n e n t j to the
ki Reaction rate constant of reaction i primary reactant in feed
K~ = Rate constant for first order chemi-

Open for discussion until 30 April 1993.