from energy to mass integration- industrial experiences ... · polymerandchemicaltechnologies,llc...
TRANSCRIPT
Polymer and Chemical Technologies, LLC
From Energy to Mass Integra:on: Industrial Experiences
Russell F. Dunn, Ph.D., P.E.
Gothenburg, Sweden March 18, 2013
Polymer and Chemical Technologies, LLC Professor of the Prac:ce Department of Chemical and Biomolecular Engineering President and Founder
Polymer and Chemical Technologies, LLC
• Background and Interest in Process Integra2on • Energy and Mass Integra.on Technology • Industrial Experiences
– Process integra.on – The Big Picture Perspec.ve • Unique Process Flow Diagram Development
– Condensate to Cooling Tower Design – Caus.c Makeup Design
• Site Material and Energy Balance Development – Heat Integra.on Designs
• Water U.lity Loop for Plas.c Resin Plants • Patented Heat Integra.on Design for Chlor-‐Alkali Plants
– Water Conserva.on Designs • Cascaded Blowdown Design • Deepwell Injec.on/River Water Discharge (Land Treatment Applica.ons, etc.)
• Current Process integra.on Ac.vi.es – Danish Hydraulic Ins.tute-‐Singapore Refining Company – Heat Integra.on and
Water Alloca.on Analysis – Heat Integra.on and Water Alloca.on SoSware Development – Southeastern US Chemical Plant – Heat Integra.on and Water Alloca.on Analysis
From Energy to Mass Integra:on: Industrial Experiences
Polymer and Chemical Technologies, LLC
Background and Interest in Process Integra:on
1. Teach Courses in Process Design at Vanderbilt University – Co-‐Teach with Professor Ken Debelak – Fall and Spring Semesters of Senior Year for Chemical Engineering Students – Text Used: Product and Process Design Principles, 3rd Edi.on, Warren D. Seider,
J. D. Seader, Daniel R. Lewin, Soemantri Widagdo – Separate Chapters on Heat Integra.on (Ch. 9) and Mass integra.on (Ch. 10)
2. Over Twenty-‐Five Years of Work on Issues of Industrial Sustainability Including: – Energy Conserva.on (Heat Integra.on) – Water Use Conserva.on/Wastewater Minimiza.on (Mass Integra.on) – Process and Product Safety
3. Prior Industrial and Consul.ng Experience Designing Heat Exchange Networks and
Water Recycle Networks – Applied heat integra.on and mass integra.on in industry for the past 21 years – Started a consul.ng company Polymer and Chemical Technologies, LLC in 2004 and worked full-‐.me at
building this company from 2004-‐2011 • 132 product and process design consul.ng projects to date • Approximately 25% of the company ac.vi.es have been heat integra.on and/or wastewater minimiza.on network design
Polymer and Chemical Technologies, LLC
Polymer and Chemical Technologies, LLC
Energy Consump:on
Polymer and Chemical Technologies, LLC
Water Consump:on
Polymer and Chemical Technologies, LLC
• Background and Interest in Process Integra.on • Energy and Mass Integra2on Technology • Industrial Experiences
– Process integra.on – The Big Picture Perspec.ve • Unique Process Flow Diagram Development
– Condensate to Cooling Tower Design – Caus.c Makeup Design
• Site Material and Energy Balance Development – Heat Integra.on Designs
• Water U.lity Loop for Plas.c Resin Plants • Patented Heat Integra.on Design for Chlor-‐Alkali Plants
– Water Conserva.on Designs • Cascaded Blowdown Design • Deepwell Injec.on/River Water Discharge (Land Treatment Applica.ons, etc.)
• Current Process integra.on Ac.vi.es – Danish Hydraulic Ins.tute-‐Singapore Refining Company – Heat Integra.on and
Water Alloca.on Analysis – Heat Integra.on and Water Alloca.on SoSware Development – Southeastern US Chemical Plant – Heat Integra.on and Water Alloca.on Analysis
From Energy to Mass Integra:on: Industrial Experiences
Polymer and Chemical Technologies, LLC
Heat Exchange Network (HEN)
Plant Unit Opera:ons Raw Materials
Products &
By-‐Products
Hot Streams In
Cold Streams In
Heat Exchanger Network
Cold Streams Out
Hot Streams Out
Hot and Cold U.li.es
A
(Linnhoff, Grossmannn et al. 1978-‐present)
Polymer and Chemical Technologies, LLC
Schema.c of a Single Mass-‐Exchanger for Environmental Process Design
Mass Exchanger (Direct-‐Contact
Counter-‐Current Unit)
Waste Stream Out Waste Stream In
Mass Separa.ng Agent Out Mass Separa.ng Agent In
Examples of Mass-‐Exchangers are Absorbers, Adsorbers, Ion-‐Exchange Units, Liquid-‐Liquid Extrac:on Units, etc.
(El-‐Halwagi and Manousiouthakis., 1989, 1990) (El-‐Halwagi and Srinivas, 1992) (Srinivas and El-‐Halwagi, 1994a) (Dunn and El-‐Halwagi, 1996)
Mass-‐Exchange Network Synthesis for Environmental Process Design
A Mass Exchange Network is a System of One or More Mass Exchangers
Process Equipment Raw Materials
Products &
By-‐Products
Environmentally Acceptable Gaseous Emissions
Environmentally Acceptable Aqueous Emissions
Reac2ve and Physical Mass Separa2ng Agents (MSAs) In
MEN, Synthesis
MEN, Synthesis
Mass Separa2ng Agents (MSAs) Out
Mass Separa2ng Agents (MSAs) Out
End-‐of-‐the-‐Pipe Design Tools (Mass-‐Exchange Networks)
Reac2ve and Physical Mass Separa2ng Agents (MSAs) In
Polymer and Chemical Technologies, LLC Opera.ng and Equilibrium Lines for Mass Transfer
ε
y=mx+b y=m(x+ε)+b
minimum composition driving force
Linearity exists for Many separations involving dilute streams
Polymer and Chemical Technologies, LLC
50
100
150
200
500 1000 1500 150 300 800
Mass Exchanged *10 -‐3 (kg/s)
y (ppm)
x 1 (ppm)
x 2 (ppm)
105
10
5
1300
170000
100000
MSA (Lean) Composite Stream
Wastewater (Rich) Composite Stream
Pinch y=800ppm
Load to Be Removed By External MSA’s
Excess Capacity of Process MSA’s
The Mass Exchange Pinch Diagram
Maximum Integrated Mass Exchange
Composi:on
Polymer and Chemical Technologies, LLC Mass Exchange Network (MEN) Solu.on Strategies
• Graphical Techniques – Composite Curves (a.k.a. Pinch Diagram): Rich Composite Curve, Lean Composite Curve, Minimum Composi.on Driving Force, Mass Pinch
– Overlap of Curves = Maximum Mass Integra.on Possible
• Targe.ng Approach (Mathema.cal Op.miza.on Formula.ons) – LP to Minimize Opera.ng Cost – MILP to Minimize the Number of Units
• Structural Approach
Polymer and Chemical Technologies, LLC
Water Pinch Diagram
0
100
200
300
400
500
600
700
800
900
0 10 20 30 40 50 Mass, (kg/hr)
Com
posi
tion
(ppm
)
Water Supply Line
Water Pinch Point
Limi:ng Composite Curve
Slope of the Water Supply Line = minimum amount of fresh water needed
(Wang & Smith. 1994)
Process Integra:on Design Methods for Water Conserva:on and Wastewater Reduc:on Industry
Polymer and Chemical Technologies, LLC
0
10
20
30
40
50
60
0 50 100 150 200 250 300
Load (x10-6 kg/hr)
Water Flow Rate (x10-3kg/hr)
Shifted Material Recycle Pinch Diagram
Source Composite Curve
Sink Composite Curve
Fresh Water
Waste Discharge
Recycle
(El-‐Halwagi. 1997)
Process Integra:on Design Methods for Water Conserva:on and Wastewater Reduc:on Industry
Polymer and Chemical Technologies, LLC
Mass Exchange Networks
Composi:on of Key Species
W3
W2
W1b W1a
W1c
S3
S2
W4
Mixing &Recycle
Direct Recycle
Intercep:on
S1
S4
S5 Source Streams (W) Sink Streams (S)
Mass Mapping Diagram (El-‐Halwagi. 1994) Water Load
Process Integra:on Design Methods for Water Conserva:on and Wastewater Reduc:on Industry
Polymer and Chemical Technologies, LLC
• Background and Interest in Process Integra.on • Energy and Mass Integra.on Technology • Industrial Experiences
– Process integra2on – The Big Picture Perspec2ve • Unique Process Flow Diagram Development
– Condensate to Cooling Tower Design – Caus2c Makeup Design
• Site Material and Energy Balance Development – Heat Integra.on Designs
• Water U.lity Loop for Plas.c Resin Plants • Patented Heat Integra.on Design for Chlor-‐Alkali Plants
– Water Conserva.on Designs • Cascaded Blowdown Design • Deepwell Injec.on/River Water Discharge (Land Treatment Applica.ons, etc.)
• Current Process integra.on Ac.vi.es – Danish Hydraulic Ins.tute-‐Singapore Refining Company – Heat Integra.on and
Water Alloca.on Analysis – Heat Integra.on and Water Alloca.on SoSware Development – Southeastern US Chemical Plant – Heat Integra.on and Water Alloca.on Analysis
From Energy to Mass Integra:on: Industrial Experiences
Polymer and Chemical Technologies, LLC
• Product Design [Molecular Modeling, Group Contribution Theory}
• Detailed Reactor Vessel Simulation [CFD: Hydraulics, Kinetics, Mass Transfer]
• Reaction Unit Flowsheet Simulation [Process Simulator: Product Recovery, Optimization]
• Integration of the Reactor Unit into the existing Plant [Process Integration (Pinch)]
Total H2O out2895 pph
1860 pph 1035 pph Steam
841 pph
235 psig
225.5 C in 235.25 245 C Polymer
22851 pph 21169 pph7.03 %H20 275 C 0.97 RV 10 psig
Qin 1 Qin 2 2974 MW 0.30 %H201.93 MBTU/hr 1.13 MBTU/hr 4.00 RV125 Uin 85 Uout 7073 MW
Total Qin 1.13 MBTU/hr
Total Qin 3.07 MBTU/hr
Stage #1 Stage #2
Reactor
Flasher
ChemicalPlant
(Enterprise)
Mass Mass
Feed Stock
Solvents
Catalysts
Material for Utilities(Water, Coal)
Products
By-Products
Effluents
Spent Materials
HeatingCooling
Power Pressure
HeatingCooling
Power Pressure
Energy
Energy
Process Integra:on Design Tools are at the Macro-‐Scale and Involve Large and Complex Problems
The scale of the problem that is being addressed
Polymer and Chemical Technologies, LLC
Indirect Steam Direct Steam Water Process Water Butane Methane Propane Ethylene Propylene Hydrogen Hydrogen Rich Fuel Gas Chlorine NaOH Fuel Oil Gasoline O2/Air EDC HCl VCM PVC
180# steam
30# steam
435# steam
NaOH
Process Water
H2SO4 Acid
PVC
EDC
Ethylene
Propane
Propylene
Methane
Butane
Fuel Oil
Hydrogen
Gasoline
O2/Air
NaCl
Cl2
Cooling Water
Soc Water
HCl Acid
Clarified Water VCM
Condensate
100# steam
Anhydrous HCl Vapor
Fuel Gas
Anhydrous HCl Liquid
Color-Coded PowerPoint Diagram Development
Polymer and Chemical Technologies, LLC
• Background and Interest in Process Integra.on • Energy and Mass Integra.on Technology • Industrial Experiences
– Process integra.on – The Big Picture Perspec.ve • Unique Process Flow Diagram Development
– Condensate to Cooling Tower Design – Caus.c Makeup Design
• Site Material and Energy Balance Development – Heat Integra2on Designs
• Water U2lity Loop for Plas2c Resin Plants • Patented Heat Integra2on Design for Chlor-‐Alkali Plants
– Water Conserva.on Designs • Cascaded Blowdown Design • Deepwell Injec.on/River Water Discharge (Land Treatment Applica.ons, etc.)
• Current Process integra.on Ac.vi.es – Danish Hydraulic Ins.tute-‐Singapore Refining Company – Heat Integra.on and
Water Alloca.on Analysis – Heat Integra.on and Water Alloca.on SoSware Development – Southeastern US Chemical Plant – Heat Integra.on and Water Alloca.on Analysis
From Energy to Mass Integra:on: Industrial Experiences
Polymer and Chemical Technologies, LLC
Polycarbonate Resin Plant Data
Polymer and Chemical Technologies, LLC
Water U2lity Loop Design
Polycarbonate Resin Plant Data
Polymer and Chemical Technologies, LLC
Westlake Calvert CityChlor-Alkali Plant Heat Pinch Curves
0
50
100
150
200
250
300
350
400
0 10 20 30 40 50 60 70 80 90 100
Heat Duty (MMBTU/hr)
Tem
pera
ture
(deg
F)
Hot Composite Curve
Cold Composite Curve
Minimum Hea.ng U.lity = 27.5 MM BTU/hr Minimum Cooling U.lity = 66.0 MM BTU/hr Poten.al for Heat Integra.on = 5.6 MM BTU/hr
PolymerChemTech
3/22/06
Polymer and Chemical Technologies, LLC [email protected]
Opportuni.es Existed for Addi.onal Hea.ng and Cooling
Chlor-Alkali Plant Data
Polymer and Chemical Technologies, LLC
• Background and Interest in Process Integra.on • Energy and Mass Integra.on Technology • Industrial Experiences
– Process integra.on – The Big Picture Perspec.ve • Unique Process Flow Diagram Development
– Condensate to Cooling Tower Design – Caus.c Makeup Design
• Site Material and Energy Balance Development – Heat Integra.on Designs
• Water U.lity Loop for Plas.c Resin Plants • Patented Heat Integra.on Design for Chlor-‐Alkali Plants
– Water Conserva2on Designs • Cascaded Blowdown Design • Deepwell Injec2on/River Water Discharge (Land Treatment Applica2ons, etc.)
• Current Process integra.on Ac.vi.es – Danish Hydraulic Ins.tute-‐Singapore Refining Company – Heat Integra.on and
Water Alloca.on Analysis – Heat Integra.on and Water Alloca.on SoSware Development – Southeastern US Chemical Plant – Heat Integra.on and Water Alloca.on Analysis
From Energy to Mass Integra:on: Industrial Experiences
Polymer and Chemical Technologies, LLC
Industrial Study Minimiza.on of Wastewater Discharge Using Slow Rate Irriga.on Land Treatment Technology and Other Water-‐Using Processes (Dunn et al. Monsanto Site Study, 1999; Denmark Course, 2001; Dunn et al., 2001)
Mathematical Optimization Program for Minimizing Wastewater Discharge in an Integrated Nylon Plant
Polymer and Chemical Technologies, LLC
Source'Stream''Designations!
Flow' TKN' SO48S' Cl8' Cu' Na+' Ca2+' Mg2+'liter/s( ppm( ppm( ppm( ppm( ppm( ppm( ppm(
CTB1'Stream' 17.350! 1.26! 116.01! 72.45! 0.14! 91.33! 7.96! 6.46!CTB4'Stream' 0.435! 1.11! 57.08! 134.38! 0.14! 94.33! 7.58! 5.72!CTB6'Stream' 2.524! 0.72! 96.67! 61.2! 0.14! 121! 10.84! 7.12!RX'Stream' 18.927! 0.82! 10.69! 2000! 0! 18.75! 209! nd!YP'Stream' 28.391! 220! 35.87! 32.18! 0.16! 49.74! 3.48! 2.48!CS'Stream' 37.854! 28! 178.39! 315.99! 4.90! 0.16! 0.82! nd!NZ'Stream' 14.511! 0.99! 3199.4! 169! 0! 1643! 23.67! 17!
Source Streams
Polymer and Chemical Technologies, LLC
Sink Streams Type 1 Land Constraints: • 283,290 m2 of type 1 land is available (NP) • Total flowrate of wastewater (liter/s) to the land < 1.091E-‐4/m2 • Total nitrogen (TKN) applied to the land per year ≤ 0.03062 kg/m2 • Total copper applied to the land per year ≤ 0.00334 kg/m2 • Total Cl-‐ (ppm) applied to the land ≤ (m2/(109.05*flowrate applied in liter/s))+250 • Total SO4-‐S (ppm) applied to the land ≤ (m2/(109.05*flowrate applied in liter/s))+250 • Sodium adsorp.on ra.o (SAR) applied to the land ≤ 6.0
Type 2 Land Constraints: • 404,700 m2 of type 2 land is available (P) • Total flowrate of wastewater (liter/s) to the land < 3.520E-‐5/m2 • Total nitrogen (TKN) applied to the land per year ≤ 0.03062 kg/m2 • Total copper applied to the land per year ≤ 0.00334 kg/m2 • Total Cl-‐ (ppm) applied to the land ≤ (m2/(109.05*flowrate applied in liter/s))+250 • Total SO4-‐S (ppm) applied to the land ≤ (m2/(109.05*flowrate applied in liter/s))+250 • Sodium adsorp.on ra.o (SAR) applied to the land ≤ 6.0
Process Unit 1 Sink Constraints: • Total flowrate of wastewater < 11.041 liter/s • Total nitrogen (TKN) ≤ 1 ppm • Total SO4-‐S ≤ 40 ppm • Total Cl-‐ ≤ 1000 ppm • Total Cu ≤ 0.1 ppm
Process Unit 2 Sink Constraints: • Total flowrate of wastewater < 15.773 liter/s • Total nitrogen (TKN) < 2 ppm • Total SO4-‐S ≤ 25 ppm • Total Cl-‐ ≤ 600 ppm • Total Cu ≤ 0.15 ppm
Polymer and Chemical Technologies, LLC
∑=
sources
iidischargeWastewater
1
min
subject to: Availability constraints for the sources
Overall Material Balances:
∑=
+=ssink
jiiji dischargeWastewaterlowFWastewater
1i = 1, 2, ...sources
Component Balances:
∑=
+=ssink
j
cii
ciij
cii xdischargeWastewaterxlowFxWastewater
1*** i = 1, 2, ...sources
c = 1, 2, ...components
Availability constraints for the sinks
Overall Material Balances:
j
sources
iij FlowsinklowF ≤∑
=1j = 1, 2, ...sinks
Mathema:cal Op:miza:on Program for Minimizing Wastewater Discharge in an Integrated Nylon Plant
Polymer and Chemical Technologies, LLC
Component constraints:
cj
j
sources
i
ciij
yFlowsink
xlowFmax
*1 ≤∑=
i = 1, 2, …sources c = 1, 2, ...components
Non-‐nega.vity constraints
jiallforlowF ij ,0≥
Intercep.on target constraint:
Flowij * xi
c
i=1
sources
∑Flowsink j
≤ ymax jc
where is a variable, not a constant, for the sink limi.ng component(s). xic
Mathema:cal Op:miza:on Program for Minimizing Wastewater Discharge in an Integrated Nylon Plant
Polymer and Chemical Technologies, LLC
CTB1 Stream
Sinks (Inlet Water Streams)
Land Type 1 Slow Rate Irriga:on
(70 acres)
Sources (Outlet Wastewater Streams)
Wastewater Discharge
CTB4 Stream
CTB6 Stream
RX Stream
Land Type 2 Slow Rate Irriga:on
(30 acres)
YP Stream
CS Stream
NZ Stream
Process Unit 1
Process Unit 2
17.350
1.262
2.164
0.360
4.360
1.047
1.432
12.088
0.432
0.202
27.766
5.596
2.631
29.627
0.707
0.278
13.527
30.599
4.158
3.054
83.002
TKN Cl Cu SAR
TKN Cl Cu SAR
TKN SO4 Cl
All values in liter/s
Scenario One: Iden.fica.on of Allocated Flows for Recycle and Reuse Only
Polymer and Chemical Technologies, LLC
Sinks (Inlet Water Streams)
Sources (Outlet Wastewater Streams)
CTB1 Stream Land Type 1 Slow Rate Irriga:on
(70 acres)
Wastewater Discharge
CTB4 Stream
CTB6 Stream
RX Stream
Land Type 2 Slow Rate Irriga:on
(30 acres)
YP Stream
CS Stream
NZ Stream
Process Unit 1
Process Unit 2
17.350
0.435
1.060
0.114
4.246
1.047
0.486
13.142
0.423
0.202
27.741
5.628
2.637
0.416
0.719
0.278
13.514
0.826
1.350
29.173
29.425
4.164
1.035
70.422
15.773
TKN Cl Cu SAR
TKN Cl Cu SAR
TKN SO4 Cl
Flow TKN SO4 Cl Cu
S/I = source reduc:on and/or intercep:on process All values in liter/s
2000 ppm Cl
705 ppm Cl S/I
Scenario Two: Iden.fica.on of Intercep.on Targets
Polymer and Chemical Technologies, LLC
• Background and Interest in Process Integra.on • Energy and Mass Integra.on Technology • Industrial Experiences
– Process integra.on – The Big Picture Perspec.ve • Unique Process Flow Diagram Development
– Condensate to Cooling Tower Design – Caus.c Makeup Design
• Site Material and Energy Balance Development – Heat Integra.on Designs
• Water U.lity Loop for Plas.c Resin Plants • Patented Heat Integra.on Design for Chlor-‐Alkali Plants
– Water Conserva.on Designs • Cascaded Blowdown Design • Deepwell Injec.on/River Water Discharge (Land Treatment Applica.ons, etc.)
• Current Process integra2on Ac2vi2es – Danish Hydraulic Ins2tute-‐Singapore Refining Company – Heat Integra2on and
Water Alloca2on Analysis – Heat Integra2on and Water Alloca2on Sobware Development – Southeastern US Chemical Plant – Heat Integra2on and Water Alloca2on
Analysis
From Energy to Mass Integra:on: Industrial Experiences
Polymer and Chemical Technologies, LLC
• Danish Hydraulic Ins.tute-‐Singapore Refining Company – Simultaneous Water Pinch and Heat Pinch Analysis – Water Treatment Pilot Plant Development
• Heat Integra.on and Water Alloca.on SoSware Development – DHI (Simultaneous Heat Integra.on and Water Alloca.on Design) – Vanderbilt University (Water Alloca.on Network Design)
• Southeastern US -‐ Chemical Plant – $400 million Site Expansion in Progress – Site Process Flow Diagram Development – Water Pinch and Heat Pinch Analysis
Current Process Integra:on Ac:vi:es
Polymer and Chemical Technologies, LLC
Excel/Graphical Approaches
Heat Duty Mapping Diagram
Temperature-‐Interval Diagram
Subnetwork Above the Pinch
Heat Pinch Composite Curves
Heat Exchange Network Design SoSware (Dunn, Debelak, Spelling, Jamiran, Musa and Thomas)
Polymer and Chemical Technologies, LLC
Heat Exchange Network Design SoSware (Dunn, Debelak, Spelling, Jamiran, Musa and Thomas)
Polymer and Chemical Technologies, LLC
Water Alloca:on Network Design: Excel/Graphical Approaches
Water Recycle Network Design Software (Dunn, Debelak, Perlmutter, Alahmad, and Mohd Fauzi)
Can handle large industrial problems
Polymer and Chemical Technologies, LLC
Concluding Observa:ons from Applying Process Integra:on in Industry Over the Past 20 Years
• Energy and Water Use are Key Concerns for Future Industrial Sustainability • Significant Opportuni.es Exist at Chemical Plant Sites for Energy Integra.on and
Wastewater Recycle Designs; however, Most Wastewater Recycle Designs are Driven by Environmental Regula.ons, not Economics
• Heat Pinch Analysis can OSen Provide the Economic Incen.ve for Water Use Reduc.ons
• Process Integra.on Analysis Effec.vely Reinforces “Big Picture” Mentality which OSen Leads to Other Ideas
• Data Collec.on and Reconcilia.on are Crucial • Process Integra.on Analysis oSen Iden.fies Non-‐Obvious Process Opportuni.es • Large Sites that are Evaluated for Process Integra.on Opportuni.es Require:
– Time – Technology – Tools – Technique