Fundamentos de Ingeniería Verde

Ingeniería Química Industrial

9° semestre
Dr. Julio C. Sacramento Rivero
Universidad Autónoma de Yucatán
Dr. David Shonnard
Michigan Technological University
1
 Unidad IV

Unidad IV. Análisis de diagramas de flujo de proceso para

prevención de impactos ambientales

Shonnard, D. R. (2002) Chapter 8. Evaluating

environmental performance during process synthesis.
Shonnard, D. R. (2002) Chapter 9. Unit operations and
pollution prevention.
Shonnard, D. R. (2002) Chapter 11. Evaluating the
environmental performance of a flowsheet.

En Allen, D. T. y Shonnard, D. R., Green Engineering:

Environmentally Conscious Design of Chemical Processes.
Nueva Jersey: Prentice Hall PTR

2
 Competencia de la Unidad IV

Identifica las áreas de oportunidad para prevenir emisiones en

los principales equipos de proceso de una planta química y
según las corrientes de residuos declaradas en el diagrama de
flujo de proceso, de manera sistemática.

3
 Evaluating environmental
performance during process
synthesis

Chapter 8, Section 8.3

4
 ¿Qué aprenderemos a hacer?

In the process of flowsheet design, after screening out a number of

environmentally and economically inferior reaction pathways and
raw materials, the design engineer begins to identify unit
operations in a relatively small number of flowsheets. An
environmental evaluation should again be considered using
emission estimation.

Students will:
• estimate air emissions and other releases from process units after
developing a preliminary process flowsheet, using software and hand
calculations
• have a better understanding of the mechanisms for pollutant generation
and release from process units

5
 Contenido (sección 8.3)

1. Identify waste release sources in process flowsheets and

mechanisms for unit operations
2. Methods for estimating air emissions from chemical
processes
3. Case study - Benzene to Maleic Anhydride process evaluation

6
 Typical waste emission sources
from chemical processes

1. Waste streams from process units

2. Major equipment - vents on reactors, column separators, storage tanks,
vacuum systems, ..
3. Fugitive sources - large number of small releases from pumps, valves,
fittings, flanges, open pipes, ..
4. Loading/unloading operations
5. Vessel clean out, residuals in drums and tanks
6. Secondary sources - emissions from wastewater treatment, other waste
treatment operations, on-site land applications of waste, ...
7. Spent catalyst residues, column residues and tars, sludges from tanks,
columns, and wastewater treatment, …
8. Energy consumption - criteria air pollutants, traces of hazardous air
pollutants, global warming gases, …

7
 Process waste release estimation methods

1. Actual measurements of process waste stream contents and flow rates

or indirectly estimated based on mass balance and stoichiometry. (most
preferred but not always available at the design stage)

2. Release data for a surrogate chemical or process or emission factors

based on measured data

3. Mathematical models of emissions (emission correlations, mass

transfer theory, process design software, etc.)

4. Estimates based on best engineering judgment or rules of thumb

8
 Emission estimation methods:
based on surrogate processes

1. Waste stream summaries based on past experience

Hedley, W.H. et al. 1975, “Potential Pollutants from
Petrochemical Processes”, Technomics, Westport, CT

2. AP-42 Document, WebFIRE, https://www.epa.gov/chief

3. Other sources
Kirk-Othmer Encyclopedia of Chemical Technology, 1991-
Hydrocarbon Processing, “Petrochemical Processes ‘99”,
March 1999.

9
 Distillation column emission and
solid waste generation mechanisms

Inert gas for safety

N2
Vent air
emissions
Feed Condenser
Tank
Distillate
Feed
Distillation
Column

Bottoms
Reboiler

Still
Bottoms
High temperature degradation reactions Waste
(sludges)

10
 Distillation column emission mechanisms

3. Inert gas dissolves into 4. Vapor of condensed liquid

condenser liquid is emitted with inert gas

N2
Vent air
1. Inert gas emissions
dissolves in Condenser
liquid feed Feed
Tank Distillate
Feed D, xD, xD,I
Distillation
F, xF, xF,I
Column

Bottoms
Reboiler B, xB, xB,I = 0

2. Inert gas is stripped

from the liquid in the
reboiler
11
 Distillation column emissions:
Vent air emissions - N2 mass balance

F: Moles of feed.
xF: Mole fraction of ethanol in the feed.
xF,I: Mole fraction nitrogen in the feed.
D: Moles of overhead product.
xD: Mole fraction of ethanol in the overheads product.
xD,I: Mole fraction of nitrogen in the overheads product.
B: Moles of bottoms product.
xB: Mole fraction of ethanol in the bottoms product.
xB,I: Mole fraction of nitrogen in the bottoms product = 0
xF − xB
Moles N2 = F x F, I − D x D, I − B xB ,I D = F( )
xD − xB
−1
x F, I =0.98{exp[ x F ln(HE tOH ) +(1− x F )ln(HH2 O )]}
−1
x D,I = 0.98{exp[ x D ln(HE tOH ) +(1− x D )ln( HH2 O )]} Vapor pressure
of EtOH at
Vent emissions of EtOH = (Moles N2)(VPEtOH/1 atm) condenser
Temp.
12
 Liquid storage tank air emissions and
waste generation mechanisms
Vertical Fixed Roof Storage Tank

Vent air
emissions

Tank Bottoms Waste (sludges)

13
 Liquid storage tank air emissions and
Vent air emissions waste generation mechanisms

Domed External Roof

Storage Tank

Tank Bottoms
Waste (sludges)

14
 Mechanisms of air emissions from storage tanks

Emission Mechanisms; Fixed Roof Tank

LTOTAL = LSTANDING + LWORKING

Vent

Vapor pressure of liquid drives emissions

∆T - Weather, paint color/quality

∆P - Weather

Liquid - liquid throughput, volume of

Roof Column Level tank

15
 Module 4: Storage tank comparison -
TANKS 4.0 Software

Toluene Storage Tank Calculation

• Toluene emissions only
• 516,600 gal/yr flowrate of toluene
• 15,228.5 gallon tank for each comparison

Storage Tank Type Vertical Internal Domed External

Fixed Roof Floating Roof Floating Roof

Annual Emissions (lb)

White Paint 337.6 66.2 42.8

Grey (Medium) Paint 489.1 85.1 52.4

Heated (White) 313.5

Poor (Grey/Medium) 509.7 81.0 51.5

TANKS 4.0 is based on measurements from the American Petroleum Institute

https://www3.epa.gov/ttn/chief/software/tanks/index.html

16
 Wastewater generation and
RCRA sludges
1. Dissolved
solids build
Petroleum refinery up
water processes

Prevent
Pollution

Reverse
Osmosis 2. Dissolved solids
Device mix with oily water

1. Dissolved
solids build
up

3. 10 kg sludge/kg dissolved
solids : RCRA waste

17
 Emission Factors -
major equipment

Table 8.3.2 Average Emission Factors for Chemical Process Units

Calculated from the US EPA L&E Database

Process Unit EFav ; (kg emitted/103 kg throughput)

Reactor Vents 1.50
Distillation Columns Vents 0.70
Absorber Units 2.20
Strippers 0.20
Sumps/Decanters 0.02
Dryers 0.70
Cooling Towers 0.10

Equation 8-4 is valid only for the factors in Table 8.3.2

Estimates Only: Accuracy is only order-of-magnitude

18
 Emission factors -
fugitive sources; minor equipment

Mass fraction
of species i

Emission factor
Number of
sources
Ei (kg i / yr) = mi  EFav  N s  24  365

19
 Example 8.3-3 - fugitive emissions
from a chemical mfg. facility

1,400 valves (168 in gas service), 3,048 flanges/connectors, 27

pumps in liquid service, 20 pressure relief valves, 20 sampling
valves
valves in gas service
kg VOC   lb   hr   days
(168 valves) 0.00597
lb VOC
  2.2   24   365  = 19,300
hr - valve   kg   day   yr  yr

valves in liquid service

kg VOC   lb   hr   days
(1400 -168 valves) 0.00403
lb VOC
  2.2   24   365  = 95,700
hr - valve   kg   day   yr  yr

20
 Example 8.3-3 - Summary table
fugitive emissions from a facility

Equipment type Emissions, lb/yr % of emissions by

equipment type
Valves 115,000 41

Flanges 108,000 38

Pumps 10,300 3.7

Pressure relief va lves 40,200 14

Open-ended lines 700 .3

Sample connections 5,700 3

Total 276,000 100

21
 Emission factors - criteria pollutants
from energy consumption

Emission factor EFav (lb i / 10 3 gal)  ED(Btu / yr) Annual demand

Ei (lb i / yr) = 3
Fuel heating value HV(Btu / 10 gal)  BE Boiler efficiency

AP-42, Chapter 1, section 1.3, Air CHIEF CD, www.epa.gov/ttn/chief/airchief.htm

22
 Emission factors -
CO2 from energy consumption

EFav (lb i / 10 3 gal)  ED(Btu / yr)

Ei (lb i / yr) = 3
HV(Btu / 10 gal)  BE
AP-42, Chapter 1, section 1.3, Air CHIEF CD, www.epa.gov/ttn/chief/airchief.htm
23 https://www.gob.mx/semarnat/acciones-y-programas/registro-nacional-de-emisiones-rene
 CO2 Emissions from energy
consumption for steam

Calculation Data
Low S No. 6 Oil
Annual ED of 1011 Btu/yr
HV of 150,000,000 Btu/103 gal
BE of 0.90

24
 Emission correlations/models -
storage tanks and waste treatment

Software Tools

Storage tanks
TANKS 4.0 - program from EPA -
www.epa.gov/ttn/chief/tanks.html

Wastewater treatment
WATER8 - on Air CHIEF CD -
www.epa.gov/ttn/chief/airchief.html
EPI Suite - Epiwin

Treatment storage and disposal facility (TSDF) processes

CHEMDAT8 - on Air CHIEF CD

25
 Benzene to MA process
V2O5
2 C6H6 + 9 O2 ----------> 2 C4H2O3 + H2O + 4 CO2
MoO3

AP-42, Chapter 6, section 6.14, Air CHIEF CD, www.epa.gov/ttn/chief/airchief.htm

26
 Identify air emission and releases
sources: Benzene to MA process

Source Identification by unit process and by component

1.
2.
3.
4.
5.
6.
7.
8.

27
 Typical waste emission sources
from chemical processes

1. Waste streams from process units

2. Major equipment - vents on reactors, column separators, storage tanks,
vacuum systems, ..
3. Fugitive sources - large number of small releases from pumps, valves,
fittings, flanges, open pipes, ..
4. Loading/unloading operations
5. Vessel clean out, residuals in drums and tanks
6. Secondary sources - emissions from wastewater treatment, other waste
treatment operations, on-site land applications of waste, ...
7. Spent catalyst residues, column residues and tars, sludges from tanks,
columns, and wastewater treatment, …
8. Energy consumption - criteria air pollutants, traces of hazardous air
pollutants, global warming gases, …

28
 Benzene to MA process
V2O5
2 C6H6 + 9 O2 ----------> 2 C4H2O3 + H2O + 4 CO2
MoO3

Benzene storage
1. n.a.
2. Venteo (C6H6)
3. n.a.
4. Carga del tanque (C6H6)
5. Limpieza del tanque (C6H6)
6. n.a.
7. n.a.
8. n.a.

29
 Benzene to MA process
V2O5
2 C6H6 + 9 O2 ----------> 2 C4H2O3 + H2O + 4 CO2
MoO3

AP-42, Chapter 6, section 6.14, Air CHIEF CD, www.epa.gov/ttn/chief/airchief.htm

30
 Benzene to MA process
V2O5
2 C6H6 + 9 O2 ----------> 2 C4H2O3 + H2O + 4 CO2
MoO3

31
 Summary/Conclusions

Methodologies/software tools - process synthesis:

• emission factors
• surrogate process information from historical
sources
• emission estimation software: TANKS 4.0, AirCHIEF,
process simulator packages,

32
 Unidad IV

Unidad IV. Análisis de diagramas de flujo de proceso para

prevención de impactos ambientales

Shonnard, D. R. (2002) Chapter 8. Evaluating

environmental performance during process synthesis.
Shonnard, D. R. (2002) Chapter 9. Unit operations and
pollution prevention.
Shonnard, D. R. (2002) Chapter 11. Evaluating the
environmental performance of a flowsheet.

En Allen, D. T. y Shonnard, D. R., Green Engineering:

Environmentally Conscious Design of Chemical Processes.
Nueva Jersey: Prentice Hall PTR

33
Unit operations and pollution
prevention

Chapter 9

34