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
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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:

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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. Reaction pathway evaluation Solvent selection Technology selection Equipment selection Process simulation

Equipment sizing Economic assessment Environmental assessment

Scaled gradient analysis

Iterate

Multi-objective optimization

PDS

Life cycle assessment

Process Diagnostic Summary Tables

Improved base case flowsheet

Optimum

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Case study: MA production

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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.

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Absorber mass separating agent (MSA) for MA from n-C4

Vent

Vent Crude MA

MA Data b.p. 202C

Reactor off-gas

Absorber Make-up solvent

Distillation Column Recycle solvent

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

HYSYS 99% MA recovery in Absorber, 99.9% recovery of MA in distillation, 98% purity of MA.
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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.
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Simulation of Reactor temperature for MA from n-C4

1000 900 800 700 600 500 400 300 200 100 0 380 390 400 410 420 430 440 450

Butane cost Total cost utility cost

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

IPC

Temperature (C)
Chen, H., Environmental and Economic Assessments Applied to the Design and Optimization of Chemical Processes, Ph.D. Dissertation, MTU, 2002.
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Initial flowsheet for MA from n-C4

Reactors Compressor Air

Pump n-Butane Vaporizer

Off-gas Off-gas MA

Absorber

Distillation column

Solvent

Michigan Technological University - - US EPA University of Texas at Austin

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Process diagnostic summary tables: Energy input/output for nC4 process

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

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

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

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Process diagnostic summary tables: Manufacturing profit and loss, nC4

Name Total ($/yr) 21,258,236 21,258,836 % of total cost 100.00% 100.00%

Revenue
Maleic anhydride Total Sales Revenue

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 4,760,866 81,343 159,913 679,014 58,014 580,303 2,212,796 8,532,249 55.80% 0.95% 1.87% 7.96% 0.68% 6.80% 25.93% 100.00%
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Michigan Technological University - - US EPA University of Texas at Austin

Process diagnostic summary tables: Environmental impacts, nC4

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% 6.13E-04

I k IN = k Ik
ICING
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%

Process Index National Index

IOD
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%

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%

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%

IGW
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
global warming ozone depletion smog formation acid rain carcinogenic noncarcinogenic ecotoxicity 2.5 100 2.5 10 5 5 14 10

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

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
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Michigan Technological University - - US EPA University of Texas at Austin

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

Absorber

Distillation column

Solvent

Michigan Technological University - - US EPA University of Texas at Austin

17

Flowsheet for MA production from n-C4: with heat integration.

Economic performance NPV CI OC RC Unit $ $ $/yr $/yr 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

Environmental performance

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

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
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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

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