CN4248: Sustainable Process Development

S. Farooq Office: E5 02 26 Phone: 65166545 Email: chesf@nus.edu.sg

Module Outline

Introduction (4 h) Green chemistry and sustainable energy developments (8 h) Sustainability through engineering design (10 h) Product life cycle concepts (4 h)

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Sustainability through Engineering Design

Content
Methodology for environmentally benign process synthesis; design of unit operations and flow-sheet analysis for reducing environmental footprint; risk assessment in process design; environmental cost accounting; case studies.

Course materials
Text book: Green Engineering: Environmentally Conscious Design of Chemical Processes by David T Allen and David R Shonnard; Prentice Hall PTR, NJ, 2002. ISBN 0-13-061908-6 (Chapters 8-12). Journal papers

Assessment: Term test, project, report, presentation

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Sustainability through Engineering Design

Objectives
To introduce the concepts of sustainability and sustainable development, their engineering and social relevance. To introduce the progress that has taken place in developing scientific methodologies to minimize environmental footprint of chemical processes and products.

Learning outcomes
Understanding of the concepts, principles and methodologies. Apply the understanding in course projects. Communicate the findings through written reports and oral presentation to the entire class. Ability to think at the systems level that involves balancing multiple objectives occurring at different scales a much desired attribute necessary to succeed in the complex real world.

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Outline of Lectures 1 and 2

Sustainability
Examples of sustainability issues in engineering Product, process and system design Guiding principles and decision making A quick review of qualitative methodologies of green chemistry

Environmental performance evaluation during process synthesis

Tier 1 tools (Rapid screening of alternatives) Economic criteria Environmental criteria Toxicity criteria Tier 2 tools (Preliminary design of major eqpt) Release assessment Release quantification Assessing environmental performance

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What is Sustainable Development?

Sustainable development: to ensure that it meets the needs of the present without compromising the ability of future generations to meet their own needs.
Report of the 1987 World Commission on Environment and Development (The Brundtland Report)

An important theme in local, national and world politics. A central theme for engineering professions around the world. Engineering graduates must leave their courses with understanding of the concept of sustainable development, and relevant knowledge and skills applied in the engineering profession.
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Examples of Sustainability Issues in Engineering

(Royal Academy of Engineering, UK, 2005; Chapter 2)

Jubilee River
River instead of a traditional concrete flood channel Reduced flood risk Added wildlife and public amenity features Collaborative effort of engineers, planners, landscape architects and ecologists

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Examples of Sustainability Issues in Engineering

(Royal Academy of Engineering, UK, 2005; Chapter 2)

Laundry Cleaning Products

From bulk to concentrate Non-foaming, biodegradable Bleach technology Increased effectiveness at lower temperature Correct dosage Better washing machine design Life cycle analysis kept the manufacturers ahead of the consumers

Correct dosage for liquid concentrate?

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Examples of Sustainability Issues in Engineering

(Royal Academy of Engineering, UK, 2005; Chapter 2)

Catalytic Converter
End-of-the-pipe solution to air pollution from automobile exhaust About 3 g of Pt/Pd/Rh per converter Limited localized reserve at ppm level and formidable energy for purification Economic and social welfare of the miners?

Is this sustainable? sustainable What can be done?

Increased public transport network benefit on health Hydrogen economy Electric vehicles Efficient collection and recycling

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Examples of Sustainability Issues in Engineering

(Royal Academy of Engineering, UK, 2005; Chapter 2)

The Energy Challenge

Current use dominated by fossil fuel Demand is increasing (China, India) Inequitable per capita consumption IPCC: discernable global impact Oil and gas extraction rate peaking Higher CO2 emission rates for alternative fossil fuels Nuclear power has unresolved issues Proven technologies for energy from many renewable sources Falling conversion costs but issues of integration and intermittency remain

Several decades to evolve from fossil fuel to renewable system Immediate solution: carbon capture and storage With coordination among all stakeholders and political will it is possible to stabilize global CO2 emission by 2050

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Sustainable Engineering Development: Guiding Principles

(Royal Academy of Engineering, UK, 2005; Chapter 3)

Look beyond own locality and immediate future Innovate and be creative Seek a balanced solution Seek to engage all stakeholders Make sure you know the needs and wants Plan and manage effectively Give sustainability the benefit of any doubt If polluters must pollute, they must also pay Take a holistic cradle to grave approach Decide right, do right Do not sacrifice sustainability for cost cutting Practice what you preach

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Decision-making in Engineering
(Royal Academy of Engineering, UK, 2005; Chapter 4)

Decision-making in Engineering
Process design Product design Design of infrastructure Management of an enterprise

Many models for decisionmaking A 5-step model

Framing the requirements Scoping the decision Planning and design Implementation, delivery and operation End of usable life

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Applications of the Principles in Decisionmaking

(Royal Academy of Engineering, UK, 2005; Chapter 4)

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Green Chemistry: Qualitative Methodologies

(Text Book; Chapter 7)

Design of chemical products and processes to reduce or eliminate the use or generation of hazardous substances
Green solvents
Less hazardous Human health Environmental Global Local

Alternative feedstock
Innocuous Less waste Selective Efficient Renewable

Synthesis pathways
Reaction type Atom efficiency

Safer chemistry
Structure-activity relationship Eliminate toxic functional group Reduce bioavailability Easy degradability

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Green Chemistry: Selected Examples

(Text Book; Chapter 7)

Feedstock for adipic acid manufacture Traditional: nonrenewable and carcinogenic benzene Alternative: renewable and innocuous glucose Solvents Hazardous: halogenated solvents, CFCs, VOCs, etc Alternatives: supercritical CO2, water, HCFCs, etc. Synthesis pathways Friedel Crafts reaction: ~30% mass efficiency Recover and reuse AlCl3 catalyst or find alternative Safer chemistry Increase alkyl chain length, release functionality in-situ, etc
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Environmental Performance Evaluation During Process Synthesis

(Text Book; Chapter 8) Process design Raw material and chemical pathway selection Material balance Screening of process alternatives Preliminary design of major equipment including component material flows Detailed evaluation of alternatives Small scale pilot plant for an attractive process alternative Very detailed flow sheet of the full-scale process
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Environmental evaluation Traditional Proposed

Tier 1 tools (limited information) Rough emission estimates Tier 2 tools Tier 3 tools

After critical design decisions

Tier 1 Environmental Performance Tools

Evaluation method must be rapid and simple to handle large number of process alternatives Elementary data on raw materials, products and bi-products
Environmental criteria
Persistence (atmospheric half life)* Biodegradation index (aquatic half life) Bioconcentration factor

Economic criteria
Compares raw material cost per unit amount of product

Toxicity criteria
Inhalation exposure Threshold TLVs Permissible PELs Recommended RELs Toxicity weight Impact of inhalation and ingestion

* Reaction with atmospheric hydroxyl radicals (1.5x106 molecules/cc) and 12 hr sun light

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Economic Criteria

For each synthesis route calculate

x

( compound i fed or produced per unit mass of desired product ) ( unit cost of the compound i)

Limitations
Different processing cost for different pathways Equipment and energy cost depend on operating conditions Use of market price for unit cost

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Environmental Criteria

Persistence and Bioaccumulation

Calculated using EPISUITE software (http://www.epa.gov/oppt/exposure/pubs/episuitedl.htm) Uses group contribution method (GCM) (chapter 5)
Compound Atmospheric half life 52 days 1 year 17 days 2.5 hours 2.6 days Aquatic half life Weeks Weeks Days-weeks Weeks Days-weeks Bioconcentration factor 3.2 3.2 3.2 12.6 81

Acetone Hydrogen cyanide Methanol Isobutylene Pentane Sulfuric acid Methyl methacrylate
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GCM does not estimate; assumed short due to reaction with ammonia

7 hours

Weeks

2.3

Rating for Persistence and Bioaccumulation

Persistence Rapid Moderate Slow Very slow Bioaccumulation High potential Moderate potential Low potential 8.0>Log Kow>4.3 or BCF>1000 4.3>Log Kow>3.5 or 1000>BCF>250 3.5>Log Kow or 250>BCF Rating index = 3 Rating index = 2 Rating index = 1 >60% degradation over 1 week >30% degradation over 28 days <30% degradation over 28 days <30% degradation over >28 days Rating index = 0 Rating index = 1 Rating index = 2 Rating index = 3

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Toxicity Criteria Workplace Limits

Recommended Exposure Limits (RELs)

Based on toxicity research US National Institute of Safety and Health under Centers for Disease Control and Prevention

Threshold Limit Values (TLVs)

No adverse effect over lifetime for working 8-hour/day 40-hour/week American Conference of Governmental Industrial HygienistsNongovernmental organization (http://www.acgih.org)

Permissible Exposure Limits (PELs)

Occupational Safety and Health Administration (OSHA), MoL, US MoM, Singapore Legal authority to set workplace limits Outside USA most countries use TLVs as PELs

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Environmental Index Based on TLV

(compound i fed or produced per unit mass of desired product)/(TLV)i
Compound Acetaldehyde Acetic acid Acetone Butane Carbon monoxide Ethyl chloride Vinyl chliride TLV (ppm) 25 10 500 800 25 500 1 PEL (ppm) 200 10 1000 50 1000 1 REL (ppm) Potential carcinogen minimize exposure 10 250 800 35 Potential carcinogen minimize exposure Potential carcinogen minimize exposure

Environmental Index (TLV index) =

See Table 8.2-4 for more values

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Toxicity Weight
Toxic response

Limitation of the Environmental Index

A chemical with higher TLV may have faster toxic response beyond the threshold TLV values do not consider ingestion pathways

Toxicity Weights

Dose

US EPA Integrated Risk Assessment Information System Database Toxicity weights for 600 compounds using 3 information Inhalation reference concentration (related to TLV) Oral slope factor, SF (unit: risk per mg/kg-day) Inhalation unit risk factor, UR (unit: risk per mg/m3) Weights related to SF and UR A complete description of methodology and toxicity weighs at http://www.epa.gov/opptintr/rsei/
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Environmental Index Based on Toxicity Weight

Environmental Index (EPA index) = (compound i per unit mass of product) x (maximum of oral and inhalation weight)
Oral slope factor (SF) (risk per mg/kg-day) SF<0.005 0.005<SF<0.05 0.05<SF<0.5 0.5<SF<5 5<SF<50 SF>50 Unit risk factor (UR) (risk per mg/m3) UR<0.0014 0.0014<UR<0.014 0.014<UR<0.14 0.14<UR<1.4 1.4<UR<14 UR>14 Weight Known or probable Possible carcinogen carcinogen 10 100 1000 10,000 100,000 1,000,000 1 10 100 1000 10,000 100,000

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Examples of Toxicity Weights

Compound Acetaldehyde Acrolein Biphenyl Chlorine Chloroform Methyl ethyl ketone Vinyl chloride Inhalation toxicity factor 1000 100000 100 10 1000 10 10000 Oral toxicity factor 1000 100000 100 10 100 1 10000

See Table 8.2-6 for more values

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Class Discussion

Comparing alternatives using Tier 1 economic and environmental performance criteria.

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Tier 2 Environmental Performance Tools

A part of screening design alternatives

Preliminary process flow sheet available Storage, reactors, separators identified Stream flow rates known More information for environmental evaluation

Also called environmental performance of flow sheet

Release quantification
Measured data Data for a surrogate chemical Emission factors Residual losses from cleaning Secondary emissions Modeled estimates

Release assessment
What constitutes release? Information gathering Process analysis

Assessing environmental performance

Based on treatability or cost of treatment of waste stream Based on material, water and energy consumptions and pollutant generation

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Process Flowsheets

CO2 capture from flue gas

Urea manufacture

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Release Assessment

What constitutes release to environment?

Chemicals other than the saleable product(s) entering air, water or land

Process analysis
Flow sheets of alternative processes Identify on-site releases Releases missing in a flow sheet Routine Fugitive emissions (leaking
valves, pump seals, flanges, etc)

Information gathering
Purpose: screening level risk assessment vs. detailed risk assessment Process flow diagram Waste and emission streams Best way to quantify each release Data/information available Additional data Release rate and frequency

Venting (vents of reactors,

separators, tanks, etc)

Periodic cleaning Container residuals Incomplete separation Non-routine Spills

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Release Quantification

Measured release data

Applicable for existing processes

Release data of a surrogate chemical

Applicable for existing processes

Emission factors
Unit or source specific Several databases
US EPA: Air Pollution Emission Factors (AP 42) Database; Factor Information Retrieval (FIRE) System (http://www.epa.gov/ttn/chief/efpac/index.html) National Atmospheric Emissions Inventory, UK (http://www.naei.org.uk/emissions/index.php) Canadian GHG Inventory Methodologies (http://www.ec.gc.ca/pdb/ghg/guidance/calcu_pro_e.cfm)

Losses of residuals from cleaning Modeled release estimates

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Emission Factors for Process Units

E

E = mVOC EFav M

mVOC EFav M

Rate of emission, mass/time mass fraction of the VOC in a stream or process unit Average emission factor, kg emitted/kg throughput mass flow rate, mass/time
(kg/103 EFav kg throughput) 1.50 0.10 2.20 0.20 0.02 0.70 0.10

Process Unit Reactor vents Distillation column vents Absorber units Strippers Decanters Dryers Cooling towers

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Emission Factors for Fugitive Sources

Source Service Emission Factor (kg/hr/source) SOCMI Valves Hydrocarbon gas Light liquid Heavy liquid Hydrogen gas All Pump seals Light liquid Heavy liquid Liquid Pressure relief valves Hydrocarbon gas Liquid All Sampling connections All 0.104 0.007 0.16 0.007 0.188 0.0199 0.00862 0.011 0.021 0.063 0.00597 0.00403 0.00023 Refinery 0.027 0.011 0.0002 0.0083 0.02 Gas plant

See Table 8.3-3 for more values and other details

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Losses of Residuals from Cleaning

Unloading method Vessel type Weight % based on pilot scale study Surfactant solution 3.06 NA 0.485 0.089 0.048 0.058 0.040 Water 2.29 3.28 0.403 0.034 0.019 0.034 0.033 Kerosene 2.48 2.61 0.404 0.054 0.033 0.038 0.040 Motor oil 2.06 2.3 0.737 0.35 0.111 0.161 0.127 Viscosity >200 cp 3 4 1 0.5 0.1 0.2 0.2

Pumping Pumping Pouring Pouring Gravity drain Gravity drain Gravity drain

Steel drum Plastic drum Bung-top steel drum Open-top steel drum Slope-bottom steel tank Dish-bottom steel tank Dish-bottom glass lined tank

Surfactant: viscosity = 3 cp, surface tension = 31.4 dynes/cm2 Water: viscosity = 1 cp, surface tension = 77.3 dynes/cm2 Kerosene: viscosity = 5 cp, surface tension = 29.3 dynes/cm2 Motor oil: viscosity = 97 cp, surface tension = 34.5 dynes/cm2 Best engineering judgment for viscosity>200 cp

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Secondary Emissions from Utilities

Oil/gas combustion for energy supply

E(kg/unit/yr) = (ED)(EF)(FV)-1 (BE)-1
ED EF FV BE Energy demand of the process unit (energy demand /unit/yr) Emission factor for the fuel type (kg/volume of fuel combusted) Fuel value (energy/volume fuel combusted) Boiler efficiency (unit less; 0.75 0.90)
kg/103 L SO2 19S 19S 19S 18S SO3 0.069S 0.069S 0.069S 0.069S NOx 8 5 8 8 CO FPM TOC CO2 3,025 3,025

Source Classification (oil-fired boilers) Utility boilers No. 6 oil-fired, normal firing No. 6 oil-fired, tangential firing No.5 oil-fired, normal firing No.4 oil-fired, normal firing

0.6 0.6 0.6 0.6

1.12S+0.37 1.12S+0.37 1.2 0.84

0.125 0.125 0.125 0.125

S is %wt of sulfur in the oil

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Secondary Emissions from Utilities

Source Classification (oil-fired boilers) Industrial boilers No. 6 oil-fired Distillate oil-fired Commercial combustors No.6 oil-fired Residential furnaces 19S 17S 0.24S 0.24S 6.6 2.2 0.6 0.6 1.12S+0.37 0.3 0.193 0.299 3,025 19S 17S 0.24S 0.24S 6.6 2.4 0.6 0.6 1.12S+0.37 0. 0.154 0.154 3,025 kg/103 L SO2 SO3 NOx CO FPM TOC CO2

See Tables 8.3-5 and 8.3-7 for more details

Natural Gas Combustor Type SO2 Utility/Large industrial boilers Uncontrolled (UC) Controlled low NOx burners Controlled flue gas recirculation Small industrial boilers Commercial boilers 35 CN4248/S FAROOQ Residential furnaces See Table 8.3-6 for details 9.6 9.6 9.6 3040 2240 1600 1344 1344 1344 1.9x106 1.9x106 1.9x106 kg/106 m3 NOx CO CO2

Secondary Emissions from Utilities

Electricity for energy supply

E(kg/unit/yr) = (ED)(EF)(ME)-1
ED Electricity demand of the process unit (energy demand /unit/yr) EF Emission factor for the fuel type (short ton emitted/KW hr) ME Efficiency of the device

How can you estimate EF from the following data?

Emission (103 short tons) Carbon dioxide Sulfur dioxide Nitrogen oxides Power generation (billion kW hr) Coal fired 1,499,131 14,126 6,879 1,551 Petroleum fired 87,698 637 208 111 Gas fired 156,748 1 599 264 Total 1,747,418 14,766 7,690 2,796

1 short ton = 2000 lb = 0.8929 metric ton

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Modeled Release Estimates

We have discussed data-based release estimates from

Process units Fugitive sources Cleaning Utilities

AP 42 proposes model based release estimates from

Loading transport containers Evaporative losses from static liquid pool Storage tank working and breathing losses

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Release from Loading Transport Containers

Vapor in empty cargo tank is displaced by the liquid loaded

Evaporation of residual liquid Evaporation of the liquid being loaded Transferred in vapor balancing system

Splash loading

Release quantity depends on

Loading history Physical/chemical properties of old/new cargo Method of loading/unloading

Submerged pipe

Vapor balancing

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Loading Loss Calculation

LL = 12.46 x SMP/T (P<35 torr or 0.68 psia)

LL S P M T Loading loss in lb/103 gal of liquid loaded Saturation factor True vapor pressure of the liquid loaded at T(psia) Molecular weight of the vapor (lb/lb mole) Temperature of the liquid loaded (R = oF + 460)

What if the liquid being loaded is a mixture?

G = SMVrP/(3600RT)
G Vapor generation rate in g/s V Container volume in cc r Fill rate in containers/hr R Universal gas constant (82.05 atm-cc/gmol K) P in atm, M in g/gmol and T in K

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Saturation Factor and Fill Rate

Mode of Operation Saturation factor, S Submerged Clean cargo vessel Normal dedicated service Dedicated vapor balance Drums and small containers 0.5 0.6 1.0 0.5 Splash 1.45 1.45 1.0 1.0

Vessels

Fill rate, r (containers/hr) CC TC 20 20 2 1

Fill rate gal/min CC 27.5 2.5 167 333 TC 18.3 1.7 167 333

Volume, V (cc) CC 2.1x105 1.9x104 1.9x107 7.6x107 TC 2.1x105 1.9x104 1.9x107 7.6x107 CC 1.0 1.0 1.0 1.0

S TC 0.5 0.5 1.0 1.0

Drumming (55 gals) Cans/Bottles (5 gals) Tank Truck (5000 gals) Tank Car (20,000 gals)

30 30 2 1

CC: Conservative case; TC: Typical case

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Release from a Static Liquid Pool

Evaporative loss from open surface operations

Open vats or tanks Solvent dip tank Dip coating Open roller coatings Unintentional spills

Empirical correlation from experiments with 16 pure chemicals

G = 13.32MPAT-1(Dabvzz-1)0.5
G Generation rate, lb/hr A Area, ft2 Dab Diffusion coefficient of a in b (air), ft2/s vz Air velocity, ft/min z Pool length along flow direction, ft P in in. Hg, M in lb/lb mole, T in K

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Storage Tank Working and Breathing Losses

(Text Book; Appendix C)

4 types of storage tanks

Fixed roof (high FP) Floating roof Only floating roof (medium FP) Internal floating roof (low FP) Variable vapor space Pressurized

2 types of losses
Working loss
Movement of liquid level

Standing loss

Ambient temperature change

Loss calculation
Table C-1 for fixed roof tanks Table C-2 for floating roof tanks TANKS software from US EPA
(http://www.epa.gov/ttnchie1/software/tanks/index.html)

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Class Discussion

Release quantification using Tier 2 tools

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Assessing Environmental Performance

At this point, we have estimates for

Material flows Energy requirements Wastes Emissions

Evaluate environmental performance of the flow sheet

Cost of treatment of the waste streams Determine a set of indicators (Canadian National Roundtable for the Environment and the Economy, 1999) (per unit product output) Energy consumed from all sources (converted to equivalent fuel) Total mass of materials used directly in the product minus the mass of the product Emissions of targeted pollutants Total pollutants

Cost and indicators together provide additional guidance on flow sheet performance

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