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NC STATE UNIVERSITY. U.A.S.L.P. Process Integration for Environmental Control in Engineering Curricula. “AIR POLLUTION”. I. Q. Francisco Gómez Rivera. Universidad Autónoma de San Luis Potosí. Dr. John Heitmann Jr. North Carolina State University. Dr. Pedro Medellín Milán

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Air pollution

NC STATE

UNIVERSITY

U.A.S.L.P.

Process Integration for Environmental Control in Engineering Curricula

“AIR POLLUTION”

I. Q. Francisco Gómez Rivera

Universidad Autónoma de San Luis Potosí

Dr. John Heitmann Jr.

North Carolina State University

Dr. Pedro Medellín Milán

Universidad Autónoma de San Luis Potosí

January-May 2005


Air pollution

NATURAL RESOURCES

POLLUTION

INDUSTRIAL PLANTS

6.45 BILLION

9.22 BILLION

2005

2050

TRANSPORTATION

U.S. Census Bureau, International Data Base

Data updated 4-26-2005

http://www.census.gov/ipc/www/worldpop.html

WHY AIR POLLUTION?

  • CO2: Increasing 5% peryear

David T. Allen; David R. Shonnard

GREEN ENGINEERING. Environmentally Conscious Design of Chemical Processes

Pg: 11-12

destroys

precipitates

  • 1 CFC 10,000 O3 HCl

1 Kg Particles

2 Kg Sulfur dioxide

1 Kg Nitrogen oxides

  • 1 KWh Coal-burning industrial boiler

Richard P. Turco

EARTH UNDER SIEGE

Pg: 111


Air pollution

  • ENERGY PRODUCTION

  • CHEMICAL PROCESSES

  • TRANSPORTATION

MAIN SOURCES OF AIR POLLUTION

COMMON POLLUTANTS

  • Sulfur oxides

  • Nitrogen oxide

  • Carbon monoxide

  • Hydrocarbons

  • Particulate Material

  • Organic compounds

  • Chlorine and fluorine compounds


Air pollution

QUIZ

5 seconds left

5 seconds left

  • Main sources of air pollution:(10s)

Click

To

Start

  • Mention 3 common pollutants of the atmosphere: (10s)

Click

To

Start

Time Trial

  • Percentage that CO2 increases each year:

a) 5%

b) 10%

c) 15%

d) 20%

R= Energy Production

Chemical Processes

Transportation

R= Sulfur oxides

Nitrogen oxides

Carbon monoxide

Hydrocarbons

Organic compounds

Particle material

Chlorine and fluorine compounds


Air pollution

ENERGY PRODUCTION SITUATION


Air pollution

EMISSIONS

  • Carbon dioxide

  • Sulfur oxides

  • Mercury

  • Nitrogen oxides

WHERE DO THEY COME FROM?

Production of fossil fuels

Generation of electricity based on geothermal energy

Generation of electricity based on fossil fuels

Estudio Temático 3: La Electricidad en América del Norte

John Paul Moscarella y Edward Hoyt (EIC). Ralph Cavanagh (Consejo para la Defensa de los

Recursos Naturales). Dermot Foley (Asociación para el Avance de la Energía Sustentable). Rogelio Ramírez (O, de Ecanal, S.A. de C.V)

http://www.cec.org/programs_projects/law_policy/index.cfm?varlan=espanol


Air pollution

PERCENTAGE OF POLLUTANTS RELEASED BY THE PRODUCTION OF ENERGY (1995)

  • NOx

Mexico: 15%

United States: 33% = 6.4 millions tons

Canada: 10% = 186,000 tons

  • SO2

Mexico: 48%

United States: 70% = 10,519 tons

Canada: 22% = 524,000 tons

  • CO2

Mexico: 25% = 73 millions tons

North America = 33%

United States: 33% = 17 billions tons

Canada: 16.6% = 103 million tons

Comisión para la Cooperación Ambiental (1997), Continental Pollutant Pathways: An Agenda for Cooperation to Address Long-Range Transport of Air Pollution

in North America (Montreal: CEC).


Air pollution

Fossil Fuels: 66%

Mexico: 4%

Hydroelectric Energy: 18%

United States: 83%

Nuclear Energy: 13%

Canada: 13%

Renewable Energy: less than 2%

PRODUCTION OF ELECTRICITY IN NORTH AMERICA

CEA, EIA y CFE.

  • Canada

2%

1%

19%

16%

3%

554.2 Terawatt-hour (1994)

59%

CEA. 1997


Air pollution

  • United States

4%

14%

9%

59%

12%

2%

3%

1%

21%

3,473.6 Terawatt-hour (1994)

53%

14%

8%

  • Mexico

EIA, 1998.

147.9 Terawatt-hour (1994)

CFE, 1995.


Air pollution

GROWTH

The consumption of electricity is growing. Between 1997 and 2005 the growth in North America has been:

  • Mexico:

4.5% per year

  • United States:

1.7% per year

  • Canada:

1.6% per year

OTHER TECHNOLOGIES?

In order to supply the new necessities of electricity technologies based in natural gas and hydroelectric energy are the main sources


Air pollution

TECHNOLOGIES EMPLOYED FOR THE NEW DEMAND (1997-2006)

  • Mexico:

New capacity 10,000 MW

<1%

1%

2%

5%

10%

82 %

CFE, Documento de prospectiva, 1997.


Air pollution

  • United States:

1%

1%

3%

15%

11%

69%

Departamento de Energía de Estados Unidos, EIA.

  • Canada:

3%

22%

75%

8,212 MW in 2010

CEA, Electric Power in Canada, 1995.


Air pollution

REGULATIONS

  • Mexico:

Permissible emissions for NOx and SOx in point and mobile sources

NOM-ECOL-085-1994

NOM-ECOL-086-1994

NOM-ECOL-085-1994

Sources of more than 110,000 MJ/hour

MZMC: Metropolitan Zone, Mexico City

CZ: Critic Zone. Monterrey, Guadalajara, Ciudad Juarez

RC: Rest of the country


Air pollution

  • United States:

The Clean Air Act requires EPA to set National Ambient Air Quality Standards for pollutants considered harmful to public health and the environment.

National Ambient Air Quality Standards


Air pollution

QUIZ

5 seconds left

5 seconds left

  • Name one of the 2 technologies used to meet the new demand:(10s)

Click

To

Start

Time Trial

  • Principal emissions related to energy production :(10s)

R= Carbon dioxide

Sulfur oxides

Nitrogen oxides

Mercury

Click

To

Start

  • Percentage of CO2 generated by energy production in N.A.:

a) 20%

b) 10%

c) 40%

d) 30%

  • Percentage of fossil fuel in the energy production:

a) 60%

b) 62%

c) 64%

d) 66%

R= Hydroelectric energy

Natural Gas


Air pollution

GLOBAL ISSUE?

  • Air pollutants are not stationary

  • No borders, cross countries

  • Some of them can last several years in the atmosphere

WHO IS INVOLVED?

SOCIETY

GOVERMENTS

SCIENTISTS

INDUSTRY


Air pollution

“What to do?” EVOLUTION

  • Progress = Pollution (past)

  • End-of-the-pipe (70´s)

  • Recycle/reuse (80´s)

  • Plant design (90´s)

  • Process Integration ???

Atom Production ???

Progress = Pollution

Pollution Inevitable result of a chemical process

Wastes were released without treatment

Bad effects on human health and environment Strict Laws


Air pollution

END-OF-PIPE

Reduce/Eliminate Concentration/Toxicity

Transfer pollutant from one medium to other

Application

Pollution increasing

  • Good results

RECYCLE/ REUSE. Plant design

Raw materials

Atom production

High efficiency

Good results

Pollution decreasing

CONTROL vs PREVENTION

Treat, reduce or eliminate a pollutant

Avoid the creation of pollution


Air pollution

HIERARCHY

IN-PROCESS RECYCLE

ON-SITE RECYCLE

OFF-SITE RECYCLE

SOURCE REDUCTION

REDUCE / RECYCLE

WASTE TREATMENT

SAFE DISPOSAL


Air pollution

QUIZ

5 seconds left

5 seconds left

5 seconds left

5 seconds left

  • What is pollution control?:(10s)

  • What is pollution prevention?: (10s)

  • Name the hierarchy pyramid: (10s)

Click

To

Start

Click

To

Start

Click

To

Start

Time Trial

  • Name the “what to do?” evolution:(10s)

R= Progress = Pollution

End-of-pipe (70’s)

Recycle/Reuse (80’s) Process integration???

Plant design (90’s)

Click

To

Start

R= Treat, reduce or eliminate a pollutant

R= Avoid the creation of pollution

R= Source reduction

Reduce/recycle: in-process, on-site, off-site

Waste treatment

Safe disposal


Air pollution

PROCESS INTEGRATION

It was developed in the 1970’s

Thermodynamic approach (1980’s)

Linnhoff

Gundersen and Naess

Delaby and Smith

employed for heat exchanger networks

ENERGY INTEGRATION

Smith and Petelea

Reduction of wastes in a process

reduction of the utility demand and a reduction of utility waste

Source-Sink Mapping

determinates which waste streams can be used as feedstocks to other processes or equipments

Optimization Strategies

MASS INTEGRATION

when the process involves too many sources and sinks it is necessary to employ both mathematical optimization and simulation packages

Mass Exchange Network

reaches mass integration by a direct exchange between streams


Air pollution

Waste

Waste

Streams

Streams

(Lean)

(Rich)

Out

In

MASS EXCHANGE NETWORK

MSA’s (Lean Streams) In

MSA= Mass Separation Agent

MASS

EXCHANGE

NETWORK

(to Final Discharge

or Recycle to

Process Sinks)

MSA’s (Rich Streams) Out

  • Employs either MSA or lean phase

yi : solute in the rich phase

xj : solute in the lean phase

  • The MSA must be immiscible

  • Equilibrium controls the mass transfer: yi = mjxj* + bj

  • Gradient concentration = Driving force: xj* = (yi – bj)/mj


Air pollution

REGULATIONS

COMISSION FOR ENVIRONMENTAL COOPERATION

http://www.cec.org/programs_projects/law_policy/index.cfm?varlan=english

CANADA:

ENVIRONMENT CANADA

http://www.ec.gc.ca

UNITED STATES:

ENVIRONMENTAL PROTECTION AGENCY

http://www.epa.com

SECRETARIA DEL MEDIO AMBIENTE Y RECURSOS NATURALES

MEXICO:

http://www.semarnat.gob.mx


Air pollution

REGULATIONS

PROTOCOLS

Originally signed in 1987. and substantially amended in 1990 and 1992

MONTREAL PROTOCOL

Protect the Stratospheric Ozone Layer

Chlorofluorocarbons (CFCs), Halons, Carbon Tetrachloride, and Methyl Chloroform

http://www.ciesin.org/TG/PI/POLICY/montpro.html

RIO DECLARATION

Enforcing Adoption of Sustainable Development

June 1992. Reaffirming the Declaration of the United Nations Conference on the Human Environment(Stockholm 1972)

http://www.unep.org/Documents/?DocumentID=78&ArticleID=1163

OTHERS

Managerial procedures for the continuous minimization of pollutants. Enforce the concept of sustainable development

ISO 14000

http://www.iso14000.com/


Air pollution

QUIZ

5 seconds left

5 seconds left

5 seconds left

5 seconds left

  • Protocols that protect the environment:(10s)

  • Branches of Process Integration: (10s)

  • Principal driving force on mass exchange: (10s)

Click

To

Start

Click

To

Start

Click

To

Start

Time Trial

  • Governmental Offices in charge of environmental quality

  • on each country :(10s)

Click

To

Start

R= Canada: Environment Canada

United States: EPA

Mexico: Semarnat

R= Montreal Protocol

Rio de Janeiro Convention

R= Energy Integration

Mass Integration

R= Gradient of concentration


Air pollution

RECOVERY OF BENZENE FROM GASEOUS EMISSION OF A POLYMER PRODUCTION FACILITY

Inhibitors

+

Special Additives

Extending

Agent

Gaseous Waste

R1

S1

Catalytic

Solution

(S2)

Additives Mixing Column

(Benzene as primary pollutant)

Copolymer

(to Coagulation and

Finishing)

Monomers Mixing Tank

Monomers

First Stage Reactor

Second Stage Reactor

Separation

Solvent

Makeup

Recycled Solvent (Benzene)

Unreacted Monomers

Pollution Prevention Trhough Process Integration

Mahmound M. El-Halwagi

Pg: 53-62


Air pollution

Gaseous Waste

R1

Inhibitors

+

Special Additives

Extending

Agent

Catalytic

Solution

(S2)

Additives Mixing Column

(Benzene as primary pollutant)

S1

Copolymer

(to Coagulation and

Finishing)

Monomers

First Stage Reactor

Monomers Mixing Tank

Second Stage Reactor

Separation

Solvent

Makeup

Recycled Solvent (Benzene)

Unreacted Monomers

Additives

(Extending Agent, Inhibitors,

And Special Additives)

Oil

Makeup

Catalytic Solution

Benzene

Oil

S3

S2

S1

Benzene Recovery MEN

To

Atmosphere

Gaseous Waste

R1

Regeneration

Copolymer

(to Coagulation and Finishing)

Monomers

Monomers Mixing Tank

First Stage Reactor

Second Stage Reactor

Separation

Solvent

Makeup

Recycled Solvent (Benzene)

Unreacted Monomers

COMPARISON

“Problem”

“Possible solution”


Air pollution

POSSIBLE SOLUTION

Additives

(Extending Agent, Inhibitors,

And Special Additives)

Oil

Makeup

Catalytic Solution

Oil

Benzene

S3

S2

S1

Benzene Recovery MEN

Gaseous Waste

R1

To

Atmosphere

Regeneration

Copolymer

(to Coagulation and Finishing)

Monomers Mixing Tank

First Stage Reactor

Second Stage Reactor

Separation

Monomers

Solvent

Makeup

Recycled Solvent

Unreacted Monomers

TWO PROCESS MSA´s: S1 and S2

ONE EXTERNAL MSA´s: ORGANIC OIL (S3)


Air pollution

RICH COMPOSITE STREAM

Waste Stream

R1

3.8

Rich Composite Stream

Separation

0..0001

MRi = Gi*(yis – yit)

Mass Exchanged = (Gi)*(y)

MRi = Gi*(yis – yit)

Mass Exchanged = (Gi)*(y)


Air pollution

LEAN COMPOSITE STREAM

Inhibitors

+

Special Additives

Extending

Agent

S1

3.4

S2

2.4

S1

y

x1

Catalytic

Solution

(S2)

Additives Mixing Column

x2

First Stage Reactor

Second Stage Reactor

yi = Ljc (xj + ξj) + bj

yi = Ljc(xj + ξj) + bj

ξj = 0.001

ξj = 0.001

MSi = Ljc(xjt – xjs)

MSj = Ljc(xjt – xjs)


Air pollution

LEAN COMPOSITE STREAM

3.4

S2

2.4

S1

3.4

S2

y

Lean Composite Stream

2.4

x1

S1

x2

y

x1

x2

Superposition of the Streams


Air pollution

PINCH POINT

Rich Composite

Stream

3.8

3.4

S2

Lean Composite Stream

2.4

S1

y

0..0001

x1

x2

+


Air pollution

PINCH POINT

(y,x1,x2) = (0.0010,0.0030,0.0010)

Excess Capacity = 1.4 x 10-4 kgmol B/s

Process MSA´s = 2.0 x 10-4 kgmol B/s

External MSA’s = 1.8 x 10-4 kgmol B/s

Lean Composite Stream

5.2

Excess Capacity of Process MSA´s

1.4 x 10-4

4.2

3.8

Pinch Point

Load to be Removed by External MSA´s

Integrated Mass Exchange

1.8

Load to be Removed by External MSA´s

0.0001

y

x1

x2


Air pollution

SOLUTION

4.2

3.8

Pinch Point

S1

Integrated Mass Exchange

Rich Composite Stream

1.8

Load to be Removed by External MSA´s

y

x1

S1 = L1 (x1out – x1s)

L1 = S1 /(x1out – x1s)

x1out = 0.0055


Air pollution

SOLUTION

Regenerated Solvent, S3

L3=0.0234 Kgmol/s

x3s=0.0008

y1t=0.0001

Makeup

Regeneration

x3out=0.0085

ypinch=0.0010

Additives Mixture, S1

L1=0.08 Kgmol/s

x1s=0.0030

Gaseous Waste, R1

G1=0.2 kgmol/s

y1s=0.0020

x1out=0.0055

External Process MSA (S3)

Pinch Point

Flash Separation

Internal Process MSA (S1)


Air pollution

ξj

ξj

MINIMUM ALLOWABLE COMPOSITION

DIFFERENCE (ξJ)

Practical Feasibility Region

yi = mjx*j + bj

y

x*j = xj + ξj

Practical Feasibility Line

yi = mj * (xj + ξj) + b

Equilibrium Line

x*j= (y-bj)/mj

xj


Air pollution

(y,x1,x2) = (0.00125,0.0030,0.0015)

5.7

Lean Composite Stream

Excess Capacity = 1.9 x 10-4 kgmol Ben/s

Excess Capacity of Process MSAs

4.7

3.8

Process MSA´s = 1.5 x 10-4 kgmol Ben/s

Integrated Mass Exchange

2.3

External MSA’s = 2.3 x 10-4 kgmol Ben/s

Rich Composite Stream

Load to be Removed by External MSAs

Pinch Point

0.00125

y

0.0001

x1

0.0030

x2

yi = Ljc(xj + ξj) + bj

ξj = 0.002

MINIMUN ALLOWABLE COMPOSITION

DIFFERENCE (ξJ)


Air pollution

SUMMARY

Air pollution is a serious problem which will continue to become more critical in the future due to increasing

Population

Energy needs

Transportation needs

Industrial and chemical manufacturing

Efforts to reduce and control air pollution have evolved over time, but require further development to meet the increasing need.

Currently the best approach may be process integration to optimize plant design to minimize pollutants. “Atom production”, manufacturing with zero waste and byproducts, is a future goal not generally achieve now.

Process integration for plant design centers around pinch analysis of mass exchange network (MEN) to minimize waste streams, recycle them in the process, or recover them external to the process.


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