Module 6.

Detailed design: Evaluation of maleic

anhydride flowsheets
Green Engineering Short Course
Center for Environmentally Beneficially Catalysis
University of Kansas, Lawrence, KS
June 21-22 , 2004
David R. Shonnard
Associate Professor
Department of Chemical Engineering
Michigan Technological University
Michigan Technological University - - US EPA
University of Texas at Austin

Presentation Outline
The last step for improving the environmental performance of a chemical
process design is a detailed environmental impact assessment of a
process flowsheet

Pedagogical Approach - flowsheet Tier 3 assessment

How to formulate environmental impact indicators
How to draw the boundaries around the assessment - what
to leave in - what to leave out
A methodology to integrate emissions estimation,
environmental fate and transport, and relative risk
assessment
Example application maleic anhydride production
comparison of benzene versus n-butane

Michigan Technological University - - US EPA

University of Texas at Austin

Educational goals and topics

covered in the module
Participants will:
!

learn to apply a hierarchical approach to evaluate

and improve the design of chemical processes

use process diagnostic summary tables to identify

pollution prevention opportunities

Michigan Technological University - - US EPA

University of Texas at Austin

SCENE: A Software to integrate

environmental and economic
criteria with decision analysis

Chen, H. and Shonnard, D.R. Industrial and Engineering Chemistry Research, 43, 535-552, 2004

Michigan Technological University - - US EPA

University of Texas at Austin

Early versus detailed design tasks

Chen, H., Rogers, T.N., Barna, B.A., Shonnard, D.R., Environmental Progress, 22(3), 147-160, 2003.

Initial design task

Process synthesis and base case

flowsheet development
1.
2.
3.
4.

Iterate

Process
Diagnostic
Summary
Tables

Reaction pathway evaluation

Solvent selection
Technology selection
Equipment selection

Equipment sizing
Economic assessment
Environmental assessment

Scaled gradient analysis

Process
simulation

Multi-objective
optimization

PDS

Life cycle assessment

Improved base
case flowsheet

Optimum

(DUO\'HVLJQ

Michigan Technological University - - US EPA

University of Texas at Austin

'HWDLOHG'HVLJQ

Case study: MA production

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)ORZVKHHW6\QWKHVLVDQG(YDOXDWLRQ
)ORZVKHHW6\QWKHVLVDQG(YDOXDWLRQ
7LHU(QYLURQPHQWDO,PSDFW$QDO\VLV
!

Based on an initial process flowsheet created using

traditional economic-based design heuristics.

tier 3 assessment
Emissions estimation from units and fugitive sources
Environmental fate and transport calculation
Toxicity, other impact potentials, environmental fate and
transport, and pollution control.

Michigan Technological University - - US EPA

University of Texas at Austin

Absorber mass separating agent

(MSA) for MA from n-C4
Vent

Vent

MA Data
b.p. 202C

Crude MA

Reactor
off-gas

Absorber

MSA
b.p. >222C
m.p. < 35C

Distillation
Column

Make-up
solvent

Recycle solvent

HYSYS
99% MA recovery in Absorber, 99.9% recovery of MA in distillation,
98% purity of MA.
7

Michigan Technological University - - US EPA

University of Texas at Austin

Absorber mass separating agent

(MSA) for MA from n-C4

Dibutyl phthalate
Dibutyl terephthalate
Dimethyl phthalate
Diisopropyl phthalate

Benzene process
TAC ($/yr)
IPC
AHP score
2.41E+06 6.59E-05
0.2319
2.71E+06 1.41E-05
0.1636
2.12E+06 1.44E-05
0.5679
3.00E+06 4.33E-04
0.0367

n-Butane process
TAC ($/yr)
IPC
AHP score
2.80E+06 8.35E-05
0.4755
3.12E+06 1.66E-05
0.1540
2.89E+06 2.13E-05
0.3244
3.23E+06 5.08E-04
0.0461

Chen, H., Environmental and Economic Assessments Applied to the Design and Optimization of
Chemical Processes, Ph.D. Dissertation, MTU, 2002.
Michigan Technological University - - US EPA
University of Texas at Austin

Simulation of Reactor temperature

for MA from n-C4
1000
900
800
700
600
500
400
300
200
100
0
380

Butane cost
Total cost
utility cost

390

400

410

420

430

440

450

Temperature (C)
Chen, H., Environmental and Economic Assessments Applied to the Design and Optimization of
Chemical Processes, Ph.D. Dissertation, MTU, 2002.
9

Michigan Technological University - - US EPA

University of Texas at Austin

IPC

Simulation of Reactor temperature

for MA from n-C4
2.0E-04
1.8E-04
1.6E-04
1.4E-04
1.2E-04
1.0E-04
8.0E-05
6.0E-05
4.0E-05
2.0E-05
0.0E+00
380

400

420

440

460

Temperature (C)
Chen, H., Environmental and Economic Assessments Applied to the Design and Optimization of
Chemical Processes, Ph.D. Dissertation, MTU, 2002.
Michigan Technological University - - US EPA
University of Texas at Austin

10

Initial flowsheet for MA from n-C4

Reactors
Compressor
Air

Pump
n-Butane
Vaporizer

Off-gas
Off-gas
MA

Distillation
column

Absorber

Solvent

11

Michigan Technological University - - US EPA

University of Texas at Austin

Process diagnostic summary tables:

Energy input/output for nC4 process
Stream

Air
n-Butane
Make-up solvent
Solvent pump
Air compressor
n-Butane vaporizer
Reactor feed heater
Reboiler
Total
Absorber off-gas
Distillation off-gas
Crude MA
Reactor 1
Reactor 2
Reactor 3
Reactor off-gas cooler
Solvent subcooler
Condenser
Total

Available
temperature
(In,Out)(?F)
77
50
95
472.87~472.96
77~167.18
50~50.004
160.62~770
472.87

120.53
95.043
95.043
770
770
770
770~230
234.95~95
95.043

Available
Energy flow
Pressure
(MM Btu/hr)
(In,Out)(psia)
Input
14.696
0.0000
22.278
-0.0424
18.13
0.0004
1.2505~18.13
0.0107
14.696~22.278
3.9588
22.278
1.0059
22.278
29.8800
1.2505
5.0774
39.8908
Output
18.275
2.0033
0.3897
0.0002
0.3897
0.0368
23.6340
23.6340
23.6340
18.943
26.8940
18.13
7.1588
0.3897
4.0202
111.0153

Michigan Technological University - - US EPA

University of Texas at Austin

% of total
energy
0.00%
-0.11%
0.00%
0.03%
9.92%
2.52%
74.90%
12.73%
100.00%
1.80%
0.00%
0.03%
21.29%
21.29%
21.29%
24.23%
6.45%
3.62%
100.00%

12

Process diagnostic summary tables:

Manufacturing profit and loss, nC4
Name

Total ($/yr)

% of total cost

Revenue
Maleic anhydride
Total Sales Revenue

21,258,236
21,258,836

100.00%
100.00%

4,760,866
81,343

55.80%
0.95%

159,913
679,014
58,014
580,303
2,212,796
8,532,249

1.87%
7.96%
0.68%
6.80%
25.93%
100.00%

Manufacturing Expenses
Raw Materials
n-Butane cost
Make-up solvent
Utilities
Cooling water (tower)
Electricity (on site)
Steam (50 psig)
Steam (600 psig)
Natural gas
Total Manufacturing Expenses

13

Michigan Technological University - - US EPA

University of Texas at Austin

Process diagnostic summary tables:

Environmental impacts, nC4
I
INk = k
Ik

Normalization
Chemical
Sulfur dioxide
TOC
Carbon dioxide
Carbon monoxide
Dibutyl phthalate
Maleic Anhydride
n-Butane
Nitrogen dioxide
Totals
Contribution to IPC
IPC

IFT
0.00E+00
1.36E-02
4.36E+02
1.90E-01
7.70E+01
5.10E+02
6.98E-02
2.10E-01
1.02E+03
1.55%

IING
0.00E+00
1.49E-02
0.00E+00
0.00E+00
1.00E+02
7.27E+05
0.00E+00
0.00E+00
7.27E+05
0.34%

IINH
1.49E+01
6.62E+01
8.91E+01
1.65E+07
3.01E+00
0.00E+00
2.38E+05
2.89E+03
1.67E+07
86.63%

ICING

ICINH

0.00E+00
0.00E+00
0.00E+00
0.00E+00
0.00E+00
0.00E+00
0.00E+00
0.00E+00
0.00E+00
0.00%

0.00E+00
0.00E+00
0.00E+00
0.00E+00
0.00E+00
0.00E+00
0.00E+00
0.00E+00
0.00E+00
0.00%

6.13E-04

Process Index
National Index
IOD

IGW

0.00E+00
0.00E+00
0.00E+00
0.00E+00
0.00E+00
0.00E+00
0.00E+00
0.00E+00
0.00E+00
0.00%

0.00E+00
4.11E+03
6.09E+07
2.33E+05
2.56E+02
3.49E+04
6.97E+04
4.09E+06
6.54E+07
4.85%

ISF
0.00E+00
4.24E+02
0.00E+00
2.03E+03
0.00E+00
0.00E+00
0.00E+00
0.00E+00
2.46E+03
0.14%

IAR
1.35E+02
0.00E+00
0.00E+00
0.00E+00
0.00E+00
0.00E+00
0.00E+00
7.16E+04
7.17E+04
6.50%

Weighting Factors

Process composite index

IPC = (I Wk )
k
N

k
Source: Eco-Indicator 95 framework for life cycle assessment,
Pre Consultants, http://www.pre.nl

Michigan Technological University - - US EPA

University of Texas at Austin

global warming
ozone depletion
smog formation
acid rain
carcinogenic
noncarcinogenic
ecotoxicity

2.5
100
2.5
10
5
5
14
10

Process diagnostic summary tables:

Environmental impacts, nC4
By Emission Sources

Chen, H. and Shonnard, D.R. Industrial and Engineering Chemistry Research, 43, 535-552, 2004

Michigan Technological University - - US EPA

University of Texas at Austin

15

Process diagnostic summary tables:

Environmental impacts, nC4
By Emission Sources (cont. from previous slide)

Chen, H. and Shonnard, D.R. Industrial and Engineering Chemistry Research, 43, 535-552, 2004

Michigan Technological University - - US EPA

University of Texas at Austin

16

Flowsheet for MA production from

n-C4: with heat integration.
Reactors

Compressor
Air

n-Butane

Pump

Vaporizer
Off-gas
Off-gas

MA

Distillation
column

Absorber

Solvent

17

Michigan Technological University - - US EPA

University of Texas at Austin

Flowsheet for MA production from

n-C4: with heat integration.
Economic
performance

Environmental
performance

NPV
CI
OC
RC

Unit
$
$
$/yr
$/yr

IFT
IINH
IING
ICINH
ICING
IGW
IAR
ISF
IOD
IPC

kg/yr
kg/yr
kg/yr
kg/yr
kg/yr
kg/yr
kg/yr
kg/yr
kg/yr
unitless

n-Butane
3,044,252
19,472,756
13,049,907
5,274,830
Value
Contribution
to IPC
9.05E+02
1.554%
1.59E+07
93.933%
7.53E+05
0.404%
0.00E+00
0.000%
0.00E+00
0.000%
4.08E+07
3.438%
5.28E+03
0.543%
2.03E+03
0.127%
0.00E+00
0.000%
5.40E-04

Benzene
2,561,415
16,081,942
14,211,938
6,809,811
Value
Contribution
to IPC
1.80E+03
0.016%
4.26E+06
0.133%
7.94E+06
0.002%
4.27E+04
49.912%
4.27E+04
49.912%
4.61E+07
0.021%
3.77E+03
0.002%
6.37E+03
0.002%
0.00E+00
0.000%
1.02E-01

Chen, H. and Shonnard, D.R. Industrial and Engineering Chemistry Research, 43, 535-552, 2004

Michigan Technological University - - US EPA

University of Texas at Austin

18

Recap
!

Pedagogical Approach - flowsheet Tier 3

assessment
How to formulate environmental impact indicators
How to draw the boundaries around the assessment what to leave in - what to leave out
A methodology to integrate emission estimation,
environmental fate and transport, and relative risk
assessment
The Tutorial on the Short Course CD contains detailed
instructions on how to combine HYSYS and SCENE to
generate the results shown here.

Michigan Technological University - - US EPA

University of Texas at Austin

19