SUSTAINABLE PROCESS DESIGN IN THE …cepac.cheme.cmu.edu/pasi2011/library/araujo/Ofelia_Araujo_PASI...SUSTAINABLE PROCESS DESIGN IN THE CONTEXT OF ... explore the problem thoroughly

SUSTAINABLE PROCESS DESIGN IN THE CONTEXT OF

SYNTHETIC FUELS AND CO2 EMISSIONS

Ofélia Q. F. AraujoFederal University of Rio de Janeiro

Electricity Consumption (kwh per Capita) (2004)

Brazil: 2340

http://hdr.undp.org

http://hdr.undp.org/



CO2 Emissions (t) (2004)

Brazil: 331.6

http://hdr.undp.org




CO2 Emissions(t/$ PIB) (2004)

Brazil: 0.24

http://hdr.undp.org




R. G. Watts, Engineering Response

to Global Climate Change, Lewis

Publishers, New York, 1997.100

500

1000

5000

10,000

$ 20,000

50,000

$ 200

2000

0.01 0.10 1.0 10 100

GIP

per

capit

a (

$/y

ear)

U.S.A.

Canada

Bangladesh

China

MexicoPoland

South CoreaRussia

France

Japan

U.K.

kW per capita

Brazil (2010)

Energy(CO2), a By-product of Economic Development

6

2E

2P

Economy x Environment

NOT EVIL JUST WRONG

“The True Cost of Global Warming

Hysteria” “(…) warns Americans that their jobs, modest

lifestyles and dreams for their children are at

stake.”

www.noteviljustwrong.com

Phelim McAleer & Ann McElhinney

2E

http://www.noteviljustwrong.com/

World Sellers of Carbon Credits

Source: World Bank, 2010http://siteresources.worldbank.org/INTCARBONFINANCE/Resources/State_and_Trends_of_the_Carbon_Market_2010_low_res.pdf

http://siteresources.worldbank.org/INTCARBONFINANCE/Resources/State_and_Trends_of_the_Carbon_Market_2010_low_res.pdf











Economy x Environment

Source: World Bank

Source: World Bank

2E

Sustainability Reduced CO2 Emissions + Energy(Depletion of Carbon Resources?)

PH

OTO

SYN

TH

ESIS

CO2

GLUCOSE

CO

MBU

STIO

N

COXIDIZED

CREDUCED

ELECTRONS PHOTONS

PHOTOBIOREACTOR

Aquatic Species Program (DOE)

• 1978 - 1996

• Initial aim: CO2 sequestration

• Evolution: biodiesel production

• Goals: high oil content, desirable fatty acids, fast growth, resistent to other species and environmental conditions.

• Other Products: H2, HC, vitamins, alcohols, CH, CH4 and syngas

Photosynthesis Now?

DOE

“Aquatic Species Program”

Microalgae Tomorrow?

U.S. Energy Prices from 1986 to 2008[1]. Source: Hubbad, 2009

Relatively stable in the late 1980s and through much of the 1990sDOE Aquatic Species Program

Economy x Process Engineering

Since 2000, the volatility in oil prices has been extremely high

Processes should be designed for flexibility

Raw material

Capacity


• Process (bio)chemistry INTEGRATED to screening of process alternatives

• Predict PRODUCTS and EMISSIONS, and identify synergies: INDUSTRIAL ECOLOGY

• Process intensification (reduced inventories)

• Develop metrics applied to environmental impacts

• Inherent safety allied to inherent resilience and controllability

CAPEX & OPEX

OPTION A

CAPEX e OPEX

OPTION B

Econom

ic e

valu

ati

on

CAPEX + OPEX + HES

OPTION A

CAPEX + OPEX + HES

OPTION B

Sust

ain

abil

ity a

naly

sis

SAFETY

SAFETY


18

Problem Solving Hints and Wisdom

19

1. Take time to examine and explore the problem thoroughly before setting out in search of a solution.

Often, to understand the problem is to solve it.

2. Breaking the problem into smaller parts will often make solving it much easier. Solve each part separately.

3. The resources for problem solving are immense and ubiquitous.

4. You can always do something.

5. A problem is not a punishment; it is an opportunity to increase the happiness of the world, an opportunity to

show how powerful you really are.

6. The formulation of a problem determines the range of choices: the questions you ask determine the answers

you receive.

7. Be careful not to look for a solution until you understand the problem, and be careful not to select a solution

until you have a whole range of choices.

8. The initial statement of a problem often reflects a preconceived solution.

9. A wide range of choices (ideas, possible solutions) allows you to choose the best from among many. A choice

of one is not a choice.

10. People work to implement their own ideas and solutions much more energetically than they work to

implement others' ideas and solutions.

11. Remember the critical importance of acceptance in solving problems. A solution that is technologically

brilliant but sociologically stupid is not a good solution.

12. When the goal state is clear but the present state is ambiguous, try working backwards.

13. Procrastinators finish last.

14. Denying a problem perpetuates it.

15. Solve the problem that really exists, not just the symptoms of a problem, not the problem you already

have a solution for, not the problem you wish existed, and not the problem someone else thinks exists.

16. A maker follows a plan; a creator produces a plan.

17. Creativity is the construction of something new out of something old, through effort and imagination.

Problem Solving Hints and Wisdom

20

1. Take time to examine and explore the problem thoroughly before setting out in search of a solution.

Often, to understand the problem is to solve it.

2. Breaking the problem into smaller parts will often make solving it much easier. Solve each part separately.

3. The resources for problem solving are immense and ubiquitous.

4. You can always do something.

5. A problem is not a punishment; it is an opportunity to increase the happiness of the world, an opportunity to

show how powerful you really are.

6. The formulation of a problem determines the range of choices: the questions you ask determine the answers

you receive.

7. Be careful not to look for a solution until you understand the problem, and be careful not to select a solution

until you have a whole range of choices.

8. The initial statement of a problem often reflects a preconceived solution.

9. A wide range of choices (ideas, possible solutions) allows you to choose the best from among many. A choice

of one is not a choice.

10. People work to implement their own ideas and solutions much more energetically than they work to

implement others' ideas and solutions.

11. Remember the critical importance of acceptance in solving problems. A solution that is technologically

brilliant but sociologically stupid is not a good solution.

12. When the goal state is clear but the present state is ambiguous, try working backwards.

13. Procrastinators finish last.

14. Denying a problem perpetuates it.

15. Solve the problem that really exists, not just the symptoms of a problem, not the problem you already

have a solution for, not the problem you wish existed, and not the problem someone else thinks exists.

16. A maker follows a plan; a creator produces a plan.

17. Creativity is the construction of something new out of something old, through effort and imagination.

Best Process Configuration (Design)

Challenge in designing green processes

is on building an adequate design

objective function

Process Model

(Product Description)

Operations Model (Processing

Requirements)

Financial Model

(Resource Requirements)

PRODUCTION COST

An Introduction to Environmental Accounting as a Business Management Tool: Key Concepts and Terms. EPA 742-R-95-001

Conventional Costs (Easier to Measure)

Potentially Hidden and Contingent Cost

Societal Costs

(More Difficult to Measure)

ENVIRONMENTAL COST

Process Cost Modeling: StrategicEngineering and Economic Evaluation ofMaterials Technologies .Frank Field, Randolph Kirchain, and Richard Roth

22

CAPEX, OPEX

23

24

Elements of Economic Evaluation

(2000)

Process Engineering Index, CPE Index

25

Coulson & Richardson

Estimation of Fixed Capital Cost

26


Equipment Cost

27


28

Metrics of Environmental Risks

•Global Warming

•Stratospheric ozone depletion

•Acid deposition

•Smog formation

Abiotic Indexes

•Inhalation toxicity

•Ingestion toxicity

•Inhalation carcinogenicity

•Ingestion carcinogenicity

Health-Related Indexes

•Fish aquatic toxicityEcotoxicity Indexes

Sustainability

MetricsPercent yield

Water Consumption

(Volume of fresh water/Output)

Material Efficiency

(unit consumptions)

Percent Atomic Efficiency

Material Intensity

“Emergy” (embodied energy ratio)

BTU/pound

Minimum practical energy use

Total Energy Used

(Energy used/output)

Energy Intensity

Greenhouse Gases, Ozone Depletion,

Acidification, Eutrophication

Incidents

(Frequency, Severity, Worst-

case Scenario)

Waste

(mass /output)

Toxic Dispersion (Airborne toxics,

Carcinogens, VOC, Particulates, Acid gases,

aquatic toxicity, etc)

Environ-

mental

Forestation

(Total C offset, monetized eutrophication reductions,

etc)

Ecological footprint (ha/output)

Ratio of Highest/Lowest

Salary

Employee turnover, age of death of employees, etc

Societal

Sustainability Metrics – Weighting Factors

Weighting Factors

Input (50%)

Energy Consumption (25%)

Raw Material Consumption (25%)

Undesired Output (50%)

Risk Potential (10%)

Emissions (20%)

Atmospheric (50%)

Global Warming Potential (50%)

Ozone Depletion Potential (20%)

Photochemical Ozone Creation Potential (20%)

Acidification Potential (10%)

Water (35%)

Waste (15%)Toxicity Potential

(20%)

32

Safety

33

• Continual effort to analyze, reduce and control risks to the lowest levels

practical, while balancing other business objectives.

• Safety = tolerable risks in comparison to the benefit of the activity.

• Hazard = situation with the potential for harm

• Risk = the likelihood that a defined consequence (harm) will occur.

• Risk = f(hazard, frequency).

Reducing Risk Frequency or Consequences of Potential Accidents

34

• Inherent

Eliminating the hazard at process design: hazard reduction

or elimination is permanent and inseparable

• Passive

Minimizing the hazard through process and equipment design features;

• Active

Using controls, alarms, safety instrumented systems, and mitigation systems to

detect and respond to process deviation from normal operation

• Procedural

Using policies, operating procedures, training, administrative checks, emergency

response, and other management approaches to prevent incidents, or to minimize

the effects of an incident

Inherently

safer

35

Reducing Risk Frequency or Consequences of Potential Accidents

Inherent Safety: Layers of Protection

36

Strategies for Inherently Safer Design

37


38

Reduce the quantity of material or energy

The dimensions of process

equipments should be

specified as large enough

to accomplish its intended

purpose, and no larger.

However, surge

capacity should

be preserved

Minimize CAPEX meets

MINIMIZE STRATEGY for

inherently safer design

Smaller is safer

innovative process intensification

39

Replacement of a

material or process

equipment to reduce

or eliminate hazard

Substituting raw materials and

intermediates after the process has

been built, while possible in some

cases, is usually very difficult

PEI metrics can be adapted

and expanded to explicitly

include hazard


40

Also called attenuation, means using materials under less hazardous conditions. Inherently

Robust Process

Equipment

• synthesis routes

• catalysis for milder conditions

• less reactive reagent, or bio-synthesis

• reduction of hazardous solvents

• volatile solvents to boil, removing the heat of reaction

• immobilization of hazardous reagents and catalysts

• dilution of reagents

• reactions in water

• elimination of hazardous unit operations

• near-critical and super-critical processing

• replacement of batch reaction processes with semi-batch or continuous processes

reducing the quantity of reactant present

• use of processes less sensitive to operating parameter variations


Weighted Score Decision

41

Measuring Inherent Safety

42

Dow Fire and Explosion Index: [Unit Hazard Factor] x [Material Factor].

Quantifies the amount of energy released (e.g., exothermic chemical reactions).

Dow Chemical Exposure Index: relative acute health hazard potential of a

chemical release to workers and the neighboring community

Mond Index (ICI): The Dow Index expanded to a wider range of processes and

storage installations; processing of chemicals having explosive properties;

improved hazard consideration for hydrogen; additional special process hazards;

and, inclusion of toxicity in assessment.

Most

hazardous

substance

Worst case

scenario

Other Inherent Safety Indices

43

Integrated Inherent Safety Index (I2SI): economic evaluation and hazard potential

identification within the process life cycle. I2SI is comprised of sub-indices, with

main sub-indices being a hazard index and an inherent safety potential index.

Prototype Index of Inherent Safety (PIIS): is based on a chemical score (inventory, flammability, explosiveness and toxicity) and a process score (T, P). The chemical

score takes into consideration. Judgment and experience are used in weighting of

those factors.

Inherent Safety Index: used to classify process alternatives during the process

synthesis phase. This method assigns scores to chemical factors (heat of main and

side reactions, flammability, explosiveness, toxicity, corrosiveness, chemical

interaction) and process factors (inventory, process temperature and pressure,

equipment safety, safety of process structure). The final index is a summation of

the chemical and process factors.

44

12 Principles of Green Chemistry

1. Prevention

2. Atom economy

3. Less hazardous chemical

synthesis

4. Design safer chemicals

5. Safety solvents and auxiliaries

6. Design for energy efficiency

7. Use renewable feedstocks

8. Reduce derivatives

9. Catalysis

10. Design for degradation

11. Real-time analysis for pollution

prevention

12. Inherently safer chemistry for

accident prevention

a. Green Chemistry is the application of P2 principles to the chemistry discipline;

b. Emphasis of Green Chemistry tends to be on synthesis routes and solvent

selection, ignoring the role of equipment engineering

12 Principles of Green Engineering

1. All material and energy inputs and

outputs are as inherently non-

hazardous as possible

2. Prevention Instead of Treatment

3. Design for Separation and

Purification

4. Maximize efficiencies (Le

Chatelier’s Principle)

5. Output-Pulled Versus Input Pushed

6. Conserve Complexity

7. Durability Rather than

Immortality

8. Meet Need, Minimize Excess

9. Minimize Material Diversity

10. Integrate Material and Energy

Flows

11. Design for Commercial

“Afterlife”

12. Renewable Rather than

Depleting

Anastas, P.T., and Zimmerman, J.B., "Design through the Twelve Principles, Principles of Green Engineering", Env. Sci. and Tech., 37, 5, 95 -101, 2003.

Process Alternatives under GC and GE Perspectives

• Increase the integration of process chemistry into the generation of design

alternatives.

• Predict by-products and emissions.

• Recognize opportunities to match waste streams with feed streams.

• Link process and environmental models (environmental databanks and process

simulators).

J. A. Cano-Ruiz and G. J. McRae, ENVIRONMENTALLY CONSCIOUS CHEMICAL PROCESS DESIGN, Annu. Rev. Energy Environ. 1998. 23:499–536

Process Alternatives Under GC and GE Perspectives

• Detail used in process models should match the accuracy needed to make

decisions.

• Allocate environmental impacts to specific processes and products in plants.

• Develop environmental impact metrics.

• Define preferences needed to weight multi-objective optimization.

• Sensitivity analysis and identification of the features that drive environmental

impact.

J. A. Cano-Ruiz and G. J. McRae, ENVIRONMENTALLY CONSCIOUS CHEMICAL PROCESS DESIGN, Annu. Rev. Energy Environ. 1998. 23:499–536

Green PSE

The “ How tos” of Systematic Generation Approaches

• How to select among alternative along the algorithm

• How to generate an initial superstructure containing the “greenest” solution;

• How to solve the resulting large optimization problem

• How to integrate process chemistry and process engineering.

• How to efficiently cope with multiple objectives: green chemistry principles,

pollution prevention, social aspects (labor utilization), inherent safety, profit…

49

Adapted from Siirola, 1995

Green PSE

Evaluation of Pareto sets

• The synthesis system generates families of designs, involving different chemistries. Each may

need to be evaluated from distinct points of view, or with yet-to-be-developed optimization

objectives that somehow incorporate social criteria (Siirola, 1995)

50

51

CO2

CO2 Capture from Power Plants

POWER PLANT

HY

DR

OC

AR

BO

N

CO

2

POWER PLANT

WATER CONDENSATION

POWER PLANT

CO2

CAPTURE

REFORMING/GASIFICATION

WGS

AIR

ASUAIR

O2

O2

H2

POWER EQUIPMENT

FUEL CELL

OXY-COMBUSTION

AIR

H2O H2O

CO2

H2

CO2

CAPTURE

H2O

POWER PLANT

HY

DR

OC

AR

BO

N

CO

2

CO2

CAPTURE

AIR

Technology CO2 Emissions (kg/MWh)PC-fired—subcritical 850

PC-fired—supercritical 800

IGCC 670

NGCC 370

Nuclear 0

CO2 Capture from Power Plants

CCGS

CostUS$ / kwh

Poor Gas

Rich Gas

RevenueUS$ / kwh

CCIS

CCGS (Cost of kwh) x CCIS (Cost of kwh)

Production Volume X Added Value

POTENTIAL MARKET

m3/yearPRICES

US$/t

Pharmaceuticals

Chemicals

Food

Biofuels

CCIS

Combustor

HRSG

Flue Gas10-15% CO2

Low T

Water Recycle

Gas Turbine

Vapor Vapor Turbine

Energy

Energy

NG Air

CCIS

Combustor

HRSG

Flue Gas10-15% CO2

Low T

Water Recycle

Gas Turbine

Vapor Vapor Turbine

Energy

Energy

NG Air

Chemical Absorption

Flue as<1% CO2

Low T

>90% CO2

Low T

CCIS

Combustor

HRSG

Flue Gas10-15% CO2

Low T

Water Recycle

Gas Turbine

Vapor Vapor Turbine

Energy

Energy

NG Air

Chemical Absorption

Flue as<1% CO2

Low T

>90% CO2

Low T

CCIS

Combustor

HRSG

Flue Gas10-15% CO2

Low T

Water Recycle

Gas Turbine

Vapor Vapor Turbine

Energy

Energy

NG Air

Chemical Absorption

Flue as<1% CO2

Low T

>90% CO2

Low T

Microalgae Culture

O2

CCIS

Combustor

HRSG

Flue Gas10-15% CO2

Low T

Water Recycle

Gas Turbine

Vapor Vapor Turbine

Energy

Energy

NG Air

Chemical Absorption

Flue as<1% CO2

Low T

>90% CO2

Low T

Microalgae Culture

O2

Drying

LPS

BM Suspension

CCIS

Combustor

HRSG

Flue Gas10-15% CO2

Low T

Water Recycle

Gas Turbine

Vapor Vapor Turbine

Energy

Energy

NG Air

Chemical Absorption

Flue as<1% CO2

Low T

>90% CO2

Low T

Microalgae Culture

O2

Drying

LPS

BM Suspension

Dry BM

Syngas

BM seca

Syngas

Humid Gasification

CCIS

Combustor

HRSG

Flue Gas10-15% CO2

Low T

Water Recycle

Gas Turbine

Vapor Vapor Turbine

Energy

Energy

NG Air

Chemical Absorption

Flue as<1% CO2

Low T

>90% CO2

Low T

Microalgae Culture

O2

Drying

LPS

BM Suspension

Dry BM

Humid Gasification

Syngas

Dry BM

Syngas

Separation H2

Reaction Methanol

Fischer Tropsch

Green DieselGasoline

CCIS

Combustor

HRSG

Flue Gas10-15% CO2

Low T

Water Recycle

Gas Turbine

Vapor Vapor Turbine

Energy

Energy

NG Air

Chemical Absorption

Flue as<1% CO2

Low T

>90% CO2

Low T

Microalgae Culture

O2

Drying

LPS

BM Suspension

Dry BM

Syngas

BM seca

Syngas

Separation H2

Reaction Methanol

Fischer Tropsch


Extraction

Bioproducts ($$)

Residual Biomass

Dielectric Oil

Fatty Acids

Biodiesel

Glycerol

Glycerol Methanol

Humid Gasification

Trans-esterification

CCIS

Combustor

HRSG

Water Recycle

Gas Turbine

Vapor Vapor Turbine

Energy

Energy

NG Air

>90% CO2

Low T

Microalgae Culture

O2

Drying

LPS

BM Suspension

Dry BM

Syngas

BM seca

Syngas

Separation H2

Reaction Methanol

Fischer Tropsch


Extraction

Bioproducts ($$)

Residual Biomass

Dielectric Oil

Fatty Acids

Trans-esterification

Biodiesel

Glycerol

Glycerol Methanol

Humid Gasification

NGCC

NGCC

NGCC

NGCC and in situ Biomass Production

NGCCCULTIVO DE BIOMASSA

CAPTURA DE CO2CO2 Capture

Biomass Production

NGCC

69

Carbon Sequestering Industrial Complex

MinP(x,y) = - y P(i(x))PEI(x,y) = y P(i(x))

Stci(x) = 0c(x) > 0Ai x = biA x ≤ bli ≤ x ≤ ls

BIOREACTIONOXIDATION C2= EO

PRODUCTION DME DMC

MTO

PROD. NH3

PROD UREA

PROD DMC UREA

GLYCEROL CARBONATE

TRANSESTERI-FICATION

BIODIESEL

OIL EXTRACTION

GASIFICATION

SDTO

PRODUCTIONMETHANOL

FISCHER TROPSCH RXN

WATER GAS SHIFT REACTION

ETHYLENE

NH3

SYNGAS

RESIDUALBIOMASS

GLYCEROL

GLYCEROL CARBONATE

OILCAROTENE

1,2PROPANEDIOLHYDRO-

GENOLYSIS

UREA

“C

CIS

”

PROCESS REFERENCE REACTANTS PRODUCTS

Production of D. salina Chisti (2007) CO2, nutrients biomass, beta-carotene, O2

Biomass Gasification Olofsson et al. (2005) biomass, O2 SYNGAS, N2, CO2, vapor

Production of

Biodiesel Georgogianni et al. (2009) biomass, MeOH

Residual Biomass, biodiesel,

glycerol

Production of 1,2-PD Dasaria et al. (2006) glycerol, H2 1,2-PD, H2O

Production of H2 Monteiro et al. (2009) SYNGAS H2, CO2

Production of MeOH Nouri e Tillman (2005) SYNGAS MeOH

Production of NH3 Monteiro et al. (2009) H2 , N2 NH3

Production of Urea Baal e Lemmen (2003) NH3 , CO2 Urea

MTO Wei Wang et al. (2005) MeOH Methane, Ethane, ethylene,

propane, propylene,

butanes, butenes, C5+, H2O,

CO2

SDTO Cai et al. (1995) SYNGAS

FTCai et al. (1995) SYNGAS

Production of EO Coombs et al. (1997) Ethylene, O2 EO

Production of DMC via

EO Cui et al. (2004) EO, CO2, MeOH DMC, EG

Production of DMC via

Urea Cui et al. (2004) urea, MeOH DMC, NH3

Production of CG Rokicki et al. (2005) DMC, glycerol Glycerol carbonate

Complex Summary

72

Process Flow Diagram

Problem Dimension

15 processes

228 process streams

115 process equipaments

15 recycle streams

29 components

Computational Effort

Process Simulation Simplifications

Methodology

MASS ENERGY

FEEDSTOCKPRODUCTS

SUSTAINABILITY

FUNCTION PARETO FRONTIER

S=WEIEI + WPP

EI

P

PROCESS

i

k

i

k

i

k vpp 11 i

k

g

k

i

k

i

k

i

k

i

k pmrandcpmrandcvwv 22111

Position: Velocity:

c1 = 2

c2 = 2

w = 0,1

Optimization of S-CCIS Modules

Hybrid Algorithm (Leotitsis, 2009):

1 – set search region;

2 – locate initial particles;

3 – relocate particles according to objective function values,

generation of a new population;

4 – Pareto Frontier from memory of positions.

Avaliation of Optimal Solutions

Weights Weights Objectives

wP wEI P (1012 $/year) EI (108 PEI/year)

I 0.5 0.5 7.06 2.36

II 0.75 0.25 11.33 5.85

III 0.25 0.75 4.51 0.96

CCIS Results

I (wP = wEI)

II (wP > wEI)

III (wP < wEI)

http://www.therefinishingtouch.com/blog/uploaded_images/GreenTech_Dec-31-715625.jpg

CCIS

I II III

CO2 (t/h)

Consummed 1.83e5 8.85e3 1.32e5

Emitted 1.39e4 735 1.38e4

Net Capture (t/h) 1.69e5 8.12e3 1.18e5

PRODUCTS (t/h)

EO - 2.73 5.3

H2 - 0.6 0.13

Urea 0.44 1.58 0.17

DMC 1.32 - 4.9

1,2- Propanediol 0.084 0.08 -

Glycerol Carbonate 0.0321 - -

Glycerol 0.017 0.26 -

1

2

3

1 2 3

81

00,10,20,30,40,50,60,70,80,9

1

30 35 40 45 50

EI

(PE

I·t-1

)

Profit (USD·t-1)

Fronteira de Pareto

IA min

L max

Soluções intermediárias

L (USD/t de CO2)

IA (P

EI/t

de

CO

2)

00,10,20,30,40,50,60,70,80,9

1

30 35 40 45 50

EI (

PEI

·t-1

)

Profit (USD·t-1)

Fronteira de Pareto

S max(ωL /ωIA = 10)


L (USD/t de CO2)

IA (P

EI/t

de

CO

2)


P MAX

Pareto Frontier

Intermediate Solutions EIMIN

Pareto Frontier

SMAXSMAX

P (US$/t CO2)

P (US$/t CO2)

EI(

PE

I/t

CO

2)

EI(

PE

I/t

CO

2)

Pareto Frontier

Environmental Impact, Inherent Safety and Profitability

82

Alternative Routes

83

ROUTE 1

ROUTE 2

ROUTE 3

ROUTE 4

ROUTE 5

NFPA 704 (Hommel Fire Diagram)

84

http://en.wikipedia.org/wiki/File:NFPA_704.svg

Intrinsic Safety

85

PRINCIPLES PARAMETERS

(Kletz, 1991) (Edwards and Lawrence, 1993) (Heikkilä et al., 1996)

Intensification

- Inventory

- Reaction Volume

Inventory

Reaction fieldInventory

Substitution

- Safer materials

Flammability,

Toxicity, Explosivity

Flammability, Explosivity,

Toxicity, Chemical interaction

Attenuation

- Low T, Low P T, P T, P

Limitation of Effects

- safer technical alternatives

- safer reaction conditions

T, P

Equipment safety, Safety of

process structure, T, P

Chemical interaction

Simplification

- Simplifly process environment -Safety of process structure

Impossible incorrect assimilation

- Selection of equipments, tubes and

connections -

Equipment safety

Safety of process structure

Tolerance

- Resistance to bad operation -

Equipment safety, Safety of

process structure, Corrosion

Easy to control-

Heat of reaction

Safety of process structure

Intrinsic Safety Metrics

86

CHEMICAL INDEXES (ICI) PROCESS INDEXES (IPI)

Sub-indexes for reaction dangers Sub-indexes for process conditions

Heat of main reaction(IRM)MAX Inventory (II)

Heat of secondary reactions (IRS)MAX Process Temperature (IT)MAX

Chemical interactions (IINT)MAX Process Pressure (IP)MAX

Sub-indexes for dangerous substances Sub-indexes for process system

Flammabilility (IFL)MAXEquipment (IEQ)MAX

Explosivity (IEX)MAX

Toxicity (ITOX) MAXProcess structure (IST)MAX

87

Heikkilä et al. (1996)

PICITI III

max,maxmax,max,max, )( CORTOXEXFLINTRSRMCI IIIIIIII

max,max,max,max, STEQPTIPI IIIIII

worst case scenario

chemical

process


88


PICITI III



Heat of Reaction (IRM,max and IRS,max ) Value

Neutral ≤ 200 J/g 0

Average Exothermicity < 600 J/g 1

Moderate Exothermicity < 1200 J/g 2

High Exothermicity < 3000 J/g 3

Extremely High Exothermicity ≥ 3000 J/g 4


89


PICITI III



Chemical Interaction (IINT,max) Value

Heat of Formation 1;2;3

Fire 4

Formation of non-dangerous substances or non-flammable gases 1

Formation of toxic gases 2;3

Formation of flammable gases 2;3

Explosion 4

Rapid polimerization 2;3

Toxic chemical substances 1


90


PICITI III



Flammability (IFL) Value

Non-flammable 0

Combustible (flash point > 55oC) 1

Flammable (flash point ≤ 55oC) 2

Easily flammable (flash point < 21oC) 3

Highly flammable (flash point < 0oC and boiling point ≤ 35o C) 4


91


PICITI III



Explosivity (IEX , HEV-LEV) Value

Non-explosive 0

0 - 20 1

20 - 45 2

45 - 70 3

70 - 100 4


92


PICITI III



Toxicity (ITOX , ppm) Value

TLV > 10000 0

TLV ≤ 10000 1

TLV ≤ 1000 2

TLV ≤ 100 3

TLV ≤ 10 4

TLV ≤ 1 5

TLV ≤ 0.1 6

Threshold Limit Values (TLV).


93


PICITI III



Corrosivity (ICOR,max) Value

Carbon steel 0

Stainless steel 1

Superior material needed 2


94


PICITI III



Inventory (II,max)

ValueISBL OSBL

0 - 1 t 0–10 t 0

1–10 t 10–100 t 1

10–50 t 100–500 t 2

50–200 t 500–2000 t 3

200–500 t 2000–5000 t 4

500–1000 t 5000–10000 t 5

OSBL based on Mond Index (ICI,1985). ISBL based on flow rate and residence time of 1h for each vessel


95


PICITI III



Process Temperature (IT,max) Value

< 0 °C 1

0–70 °C 0

70–150 °C 1

150–300 °C 2

300–600 °C 3

> 600 °C 4

OSBL based on Mond Index (ICI,1985). ISBL based on flow rate and residence time of 1h for each vessel


96


PICITI III



Process Pressure (IP,max) Value

0.5–5 bar 0

0–0.5 ou 5–25 bar 1

25–50 bar 2

50–200 bar 3

200–1000 bar 4

Index Dow E&F (DOW, 1987).


97


PICITI III



Equipment Type (ISBL IEQ,max) Value

Equipaments with non-flammable and non-toxical chemicals 0

Heat exchangers, pumps, towers, vessels 1

Air coolers, reactors, high risk pumps 2

Compressors, high risk reactors 3

Furnaces and heaters 4


98


PICITI III



Equipment Type (OSBL IEQ,max) Value

Equipaments with non-flammable and non-toxical chemicals 0

Atmospheric reservoir tanks, pumps 1

Tcooling towers, compressors, blowdown systems, pressurized or

refrigerated reservoir tanks 2

Flares, burners, furnaces 3


99


PICITI III



Levels of Process Structures (IST,max) Values

Recomended 0

Practice of Engineers 1

Neutral or without available data 2

Probably unsafe 3

Small accidents 4

Great accidents 5


Profitability Potential

100

Profitability Potential– MeOH Routes

n

i jijij PvPP1 1PP

PPPI

jj

Profitability

Potential

Price ($/mol) of

Component i in

ROUTE j

StoichiometricCoefficient ofComponent i in ROUTE j

Potential

Profitability

Index of

ROUTE j

Profitability Potential – MeOH Routes

101

COMPONENT PRICES (US$/mol)1 2 3 4 5

Stoichiometric Coefficients

HCl 0.00342 1

H2SO4 0.01201 1

H2O 1 -1 -1

CH3HSO4 0.02922 -1

CH3Cl 0.01401 -1

CO2 -1

H2 0.00159 -2 -3

CH4 0.00275 -1

CH3OH 0.04417 1 1 1 1 1

CO 0.01400 -1

O2 0.00477 -0,5

Profitability Potential – MeOH Routes

102

ROUTE 1 ROUTE 2 ROUTE 3 ROUTE 4 ROUTE 5

ROUTE 1

ROUTE 2

ROUTE 3

ROUTE 4

ROUTE 5

Environmental Ranking– MeOH Routes

103


IMPACT CATEGORIES

PE

I/h

ÎÎÎ genoutint

I sistema

ÎÎÎ genoutin0

ki

sComponente

k kj

Correntes

j inj

Categorias

i iin xMÎ ,

scorescore

k i

ki

ki

Hommel Diagram

104

PRODUTOS

DIAGRAMA DE HOMMEL PARA AS SUBSTÂNCIAS

CO H2 CH3OH

REAGENTES

CH3OH

CO2 H2 CH3OH H2O

CH4

N.A.

CH3Cl H2O CH3OH HCl

N.A.

N.A.

N.A.N.A.

O2

N.A.

H2O CH3OH H2SO4CH3OSO3H

ROTA 5

ROTA 4

ROTA 3

ROTA 2

ROTA 1ROUTE 1

ROUTE 2

ROUTE 3

ROUTE 4

ROUTE 5

REACTANTS PRODUCTS

Toxicity Ranking – MeOH Routes

105

Simple addition of indexes of risk to health, flammability and reactivity of reactants and products in each route


Health Risk


Flammability Risk


Reactivity Risk

3

MeOH Process Simulation – Route 3

106

CO2 + H2 → HCOOH Eq.(1)

HCOOH + C2H5OH → HCOOC2H5 + H2O Eq.(2)

HCOOC2H5 + 2H2 → CH3OH + C2H5OH Eq.(3)

Fan et al. (1998).

MeOH Process Simulation – Route 3

107

Evaluation of Intrinsic Safety – Route 3

108

-504.7734819 J/g

14.26 t/h

200 C

30 bar

Substância Explosividade (IEX )

H2 4

H2O 0

CO2 0

Metanol 2

Etanol 1

E-Formato 01

SUBSTÂNCIAS PERIGOSAS

Inflamabilidade (IFL)

Não determinado

0

0

1

2

IEQ = 2Reatores

Valor EncontradoPERIGOS DE REAÇÃO - reação principal

INTERAÇÃO QUÍMICA Valor Encontrado

IT = 2

PRESSÃO Valor Encontrado

IP = 2

TIPO DE EQUIPAMENTO (ISBL) Valor Encontrado

Valor Encontrado

II = 2

INVENTÁRIO

TEMPERATURA Valor Encontrado

Hidrogênio - Explosivo IINT, M ax = 4

SUBÍNDICES

IRM , M ax = 1

REACTION RISK – Main Reaction CALCULATED VALUE

CHEMICAL INTERACTION Hydrogen - explosive

CALCULATED VALUE

CALCULATED VALUE

CALCULATED VALUE

CALCULATED VALUE CALCULATED VALUE

CALCULATED VALUE

DANGEROUS SUBSTANCES

PRESSURE

TEMPERATURE

INVENTORY

EQUIPMENT TYPE (ISBL)

Reactors

Substance Flammability Explosivity

Not Determined

METHANOL

ETHANOL

E-FORMATE

ICI = 1 + 4 + (1 + 2 + 1 + 4 + 2 + 1) = 16IPI = 2 + 2 + 2 + 2 = 8ITI = 24

Reference

109

Reference

110

Reference

111

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