From Energy to Mass Integration- Industrial Experiences ... · PolymerandChemicalTechnologies,LLC • Background!and!Interestin!Process!Integraon! • Energy!and!Mass!Integraon!Technology!

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


•  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



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



Energy Consump:on


Water Consump:on


•  Background and Interest in Process Integra.on •  Energy and Mass Integra2on Technology •  Industrial Experiences










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)


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


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


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


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)



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



•  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








• 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


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





•  Site Material and Energy Balance Development –  Heat Integra2on Designs

•  Water U2lity Loop for Plas2c Resin Plants •  Patented Heat Integra2on Design for Chlor-‐Alkali Plants






Polycarbonate Resin Plant Data


Water U2lity Loop Design

Polycarbonate Resin Plant Data


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







–  Water Conserva2on Designs •  Cascaded Blowdown Design •  Deepwell Injec2on/River Water Discharge (Land Treatment Applica2ons, etc.)





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


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


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


∑=

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


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


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


(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


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


(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








•  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



•  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


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)


Heat Exchange Network Design SoSware (Dunn, Debelak, Spelling, Jamiran, Musa and Thomas)


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


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

Documents

From Energy to Mass Integration- Industrial Experiences ... · PolymerandChemicalTechnologies,LLC • Background!and!Interestin!Process!Integraon! • Energy!and!Mass!Integraon!Technology!