achieving more sustainable solutions through … · achieving more sustainable solutions through...

Achieving More Sustainable Solutions Through Process IntensificationThrough Process Intensification

Rafiqul Gani

CAPEC-PROCESS, Department of Chemical & Biochemical Engineering

Technical University of Denmark, DK-2800 Lyngby, Denmarkwww.capec.kt.dtu.dkwww.capec.kt.dtu.dk

[email protected]

Fertilizers ElectronicsNutrition

Communications,

Master of the universe – how did we get there? Positive contribution to the modern society

. . . . . . . .Fertilizers

Vitamins

Colorants andcoatings

Plastics

Fuel

Electronics

PharmaceuticalsDetergentsHealthcare

Mobility

Communications,Entertainment

13 MCCE, Barcelona, 30 September - 3 October 2014 2

coatings

Clothing Housing

Survival of the modern society depends on the products from ChE

Is our future sustainable? - growth

Process Industry Growth*

Region2000Prod

2000-25 GrowthNew Plant %Tot

2025-50 GrowthNew Plant %Tot

North America 1.0 0.6 5 0.8 5

Latin America 0.4 1.1 9 1.6 10

Europe 1.1 1.1 9 0.5 4

Africa 0.2 1.5 12 3.2 21

Asia 1.4 8.2 65 9.3 60


World 4.1 12.6 15.4

* Current North America = 1.0 Siirola, PSE-2012

Is our future sustainable? - needsMedium Term Economic Trends

• Much slower growth in the developed world; accelerating growth in the developing world

• World population stabilizing at 9-10 billion• World population stabilizing at 9-10 billion• 6-7 X world GDP growth over next 50 or so years (in

constant dollars)• 5-6 X existing production capacity for most

commodities (steel, chemicals, lumber, etc.)• 3.5 X increase in energy demand ( 7X increase in

electricity demand)


electricity demand)• Increase in water demand• Costs related to CO2 emissions ( 7 GTC/yr to 26 GTC/yr )

Siirola, PSE-2012

Is our future sustainable? - water


Is our future sustainable? - Environment


Is our future sustainable? - motivationThe challenges facing us

Resources-products

Energy, water, ….

Environmental Impacts (GWP, OD, HTTP, …)


OD, HTTP, …)

WasteOnly 25% converted; must be > 40% ( Driolli 2007 )

The synthesis/design problem

Establish

Chemical and bio-based industry faces enormous

challenges to achieve and/or respond to:

Survive

Needed: Innovative and more sustainable alternatives

Establish

sustainable

production

Adopt to

changing

markets

Demands for

innovative

products

Survive

global

competition

Process

Product(s)

Waste

Raw

Materials

Utilities

Needed: Innovative and more sustainable alternatives

That are economically feasible; has reduced waste; utility efficient; environmentally acceptable; safe; operable; ……. (order of magnitude better)


Should we change our focus?

Innovations – Unit operations

Is it possible to achieve more


Is it possible to achieve more improvements in design for these equipments?

Adapted from Stankiewicz, 2008

Process Intensification & Sustainability

PI is a process development/design option that focuses on improvements of a whole process by adding/enhancing of phenomena through:

• integration of unit • integration of unit operations

• integration of functions

• integration of phenomena and/or

• targeted enhancement of a


• targeted enhancement of a phenomenon within an operation

Examples of process intensification

13 MCCE, Barcelona, 30 September - 3 October 2014

11

Experiment based or model based?

REALITY

Experimenting

SystemSystemunder studyunder study

OptimisedOptimisedSystem ?System ?

Modelling

Implement

Simulate

REALITY

VIRTUAL

REALITY Modelling

ModelModelsystemsystem

Implement

Solution forSolution forthe systemthe system


How to perform useful virtual experiments to identify trully sustainable & innovative

solutions?

What? Why? How?

Product function

Product

What is the best way to identify, design,

Product function

Process functionMonomer A

Monomer B

Solvent (S)

Separatoreffluent

design, develop, .............

the chemicals based


Process

Solvent (S)

Initiator (I)

Transferagent (T)

Inhibitor (Z)

MIXER

REACTOR

SEPARATOR

Copolymerproduct

products & their processes?

Knowledge-data-models

Monomer A

Monomer BSeparatoreffluent

Log Pi = Ai + [Bi/(Ci + T)]Property models

Process modelsSolvent (S)

Initiator (I)

Transferagent (T)

Inhibitor (Z)

MIXER

REACTOR

SEPARATOR

Copolymerproduct

, , ( , , ) ; 1 ,ii n i o u t i

d mf f r m T P V i N C

d t= − − =

Mod

els

for

envi

ronm

enta

l im

pact

Models for

sustainability m

etrics

Process models

Operation models Formulation process model


Mod

els

for

envi

ronm

enta

l im

pact

Models for

sustainability m

etricsProperty-kinetics models

Process models

Cost models

model

Product evaluation model

General mathematical problem

Fobj = min {C Ty + f(x, y, u, d, θ ) + Se + Si + Ss + Hc + Hp}

Process-product model

P = P(f, x, y, d, u, θ)Problems:

LP, NLP, MILP, MINLP,process simulation, .....

Process-product

0 = h1(x, y)

Equipment-material

0 ≥≥≥≥ g1(x, u, d)

≥≥≥≥

process simulation, .....

Solution strategies : Direct,

Decomposition based

x: real-process variables; y

13 MCCE, Barcelona, 30 September - 3 October 2014

0 ≥≥≥≥ g2(x, y)

Flowhseet-chemical alternatives

B x + CTy ≥≥≥≥ D

15

integer-decision variables

A 3-stages framework for achieving sustainability


Molecular design vs flowsheet design

• Comparison to Computer-Aided Molecular Design (CAMD)

• Key concept: Operation at a lower level of aggregationlower level of aggregation

Molecules

MolecularGroups

Lower Level of Aggregation

Next Lower Level of

Tasks


AtomsC H O

Level of Aggregation

PhenomenaIdea l

Mix ingReaction

2 Phase Mix ing

Phase Contact

Phase Transition

Gani et al. (1994)Babi et al. (2014)

Flowsheet to phenomena: Both ways


Phenomena to tasks (SPB)

SPB Interconnection Phenomena In Out

SPB.1 M 1..n(L) 1(L)

SPB2 M=R 1..n(L) 1(L)

SPB.7 M=R=2phM=PC=PT(VL) 1..n(L,VL) 1(V/L)

SPB.8 M=R=2phM=PC=PT(VL)=PS(VL) 1..n(L,VL) 2(V;L)

SPB.9 M=R=2phM=PC=PT(PVL)=PS(VL) 1..n(L,VL) 2(V;L)

R, Ml, MT, MR MV, 2phM, PC(V-L), PT(V-L), PT(P:V-L), PS (V-L), D, H, C 13 in total SPB.9 M=R=2phM=PC=PT(PVL)=PS(VL) 1..n(L,VL) 2(V;L)

SPB.58 D 1(L;VL,V) 1..n(L;V; VL)


M=R=H=C 1..n(L) 1(L)


Reduced from 4017→58 using connectivity rules

Connectivity Rules:

1. H+C should not exist in the same SPB

2. PC phenomena exists


SPB.7 M=R=2phM=PC=PT(VL) 1..n(L,VL) 1(V/L)


SPB.8 M=R=2phM=PC=PT(VL)=PS(VL) 1..n(L,VL) 2(V;L)

SPB.9 M=R=2phM=PC=PT(PVL)=PS(VL) 1..n(L,VL) 2(V;L)

2. PC phenomena exists together with PT phenomena

3. SPB can contain simultaneous R and separation Lutze et al. (2013)

Combine phenomena: New operations

Not feasible*MeOH

HOAc

H2O

MeAC

Feasible*MeAC

H2O

MeOH

HOAc

HOAc

MeAC


MeOH

HOAc

H2O

* With respect to the target

Innovative solution

Non- reactive Zone

Reactive Zone


Non- reactive Zone

Conceptual framework


Example: Biodiesel production

• Two raw material sources (palm oil & waste (cooking) palm oil) having different compositions

• Flowsheet depnds on the conversion • Flowsheet depnds on the conversion technique employed (11 different catalysts found)

• Same product specifications


Mansouri et al. (2013)

Biodiesel production superstructure

Palm Oil

R1

Feedstock Pretreatment Reaction ProductsSeparation 1 Separation 2 Separation 3

R2 R3

DC

DC

Biodiesel

D DD

LLE

Water

RMeOH &

Waste oil

D

MeOH

DC

Glycerine

D DD

N

Acid

RMeOH & RWater

S S

F

LD

S

F

Catalyst

Co-solvent

S

NAlkali

S

Waste Oil

R

Vent gas

WC

Glycerol

S

S


Title: Superstructure biodiesel production Legend: R - ReactorD - DecanterS - SeparatorWC - Washing column

E - Esterification TankLLE - Liquid-liquid extractionDC - Distillation columnLD - Liquid dryer

LS - Liquid separatorF - Flash N - Neutralization tankLW - Liquid washing

LW

Water

Sep 1 - Methanol recoverySep 2 - Water washing and neutralizationSep 3 - Biodiesel and glycerine purificationDetails: Combination of flowsheets

S

LW LWLW

Water Water Water

Biodiesel production: Base case analysis

MIX-101

T-101

E-103RCY-1

V-101T-103

RCY-3

V-100

MIX-100

P-101

E-100

P-102

P-103

MIX-103

R-101

E-104

Cutter-1

Flash-2Cutter-2T-102

RCY-2

T-104

E-105

E-107OP 3

E-101

E-102

Flash-1

OP 4CP 2

Path MVA Probability Path TVA Probability


E-106

CP 2Path MVA Probability Path TVA Probability

OP3 –14174.30098 High OP3 –14898.0917 High

OP4 –2047.234859 High - - -

C 2 496.6545095 High C2 496.6545095 High


MIX-101

T-101

E-103RCY-1

V-101T-103

RCY-3

V-100

26%

35%

25%

30%

35%

40%

Pe

rce

nta

ge

of

tota

l uti

lity

co

st

MIX-100

P-101

E-100

P-102

P-103

MIX-103

R-101

E-104

Cutter-1


RCY-2

T-104

E-105

E-107OP 3

E-101

E-102

Flash-1

OP 4CP 2


5%

0% 0% 1%

4%

0% 0%

18%

1% 1%0% 0%

7%

1%

0%

5%

10%

15%

20%

Pe

rce

nta

ge

of

tota

l uti

lity

co

st


E-106


OP3 –14174.30098 High OP3 –14898.0917 High

OP4 –2047.234859 High - - -

C 2 496.6545095 High C2 496.6545095 High

Activity/Unit operation


MIX-101

T-101

E-103RCY-1

V-101T-103

RCY-3

V-100

26%

35%

25%

30%

35%

40%

Pe

rce

nta

ge

of

tota

l uti

lity

co

st

0,05

0,06

Equ

ival

ent

MIX-100

P-101

E-100

P-102

P-103

MIX-103

R-101

E-104

Cutter-1


RCY-2

T-104

E-105

E-107OP 3

E-101

E-102

Flash-1

OP 4CP 2


5%

0% 0% 1%

4%

0% 0%

18%

1% 1%0% 0%

7%

1%

0%

5%

10%

15%

20%

Pe

rce

nta

ge

of

tota

l uti

lity

co

st

0,01

0,02

0,03

0,04K

ilogr

ams

CO

2E

quiv

alen

t


E-106


OP3 –14174.30098 High OP3 –14898.0917 High

OP4 –2047.234859 High - - -

C 2 496.6545095 High C2 496.6545095 High

Activity/Unit operation0,00

Activity/Unit operation

Biodiesel production: Identify tasks

Separation TaskSeparation TaskSeparation Task

Methanol

Recycle

MixingMethanol

RecycleMethanol

Feed

Reaction Task Separation TaskSeparation Task

Water

Separation Task

Separation Task

Biodiesel

MixingWaste cooking oil

Feed


Separation Task

Separation TaskMethanol

Recycle

Water

Glycerol

Separation Task

Waste Oil

Base case analysis: Identify phenomena

M, C/H, PC(LL),

PS(LL)

M, C/H, PC(LL),

PS(LL)

M, 2phM, C/H,

PC(VL), PT(VL),

PS(VL)

Methanol

Recycle

M, PCMethanol

RecycleMethanol

Feed

M, 2phM, C/H, R

M, 2phM, C/H,

PC(VL), PT(VL),

PS(VL)

PS(VL)

M, C/H, PC(LL),

PS(LL)

Water

M, 2phM, C/H,

PC(VL), PT(VL),

PS(VL)

Methanol

Recycle

M, 2phM, C/H,

PC(VL), PT(VL),

PS(VL)

M, 2phM, C/H,

PC(VL), PT(VL),

PS(VL)

Biodiesel

M, PC

Feed

Waste cooking oil

Feed


M, 2phM, C/H,

PC(VL), PT(VL),

PS(VL)

PS(VL)

Water

Glycerol

Waste Oil

Mansouri et al. 2013

MIX-101

T-101

E-103RCY-1

V-101T-103

RCY-3

V-100

New more sustainable (PI) solution

MIX-100

P-101

E-100

P-102

P-103

MIX-103

R-101

E-104

Cutter-1


RCY-2

T-104

E-105

E-107OP 3

E-101

E-102

Flash-1

OP 4CP 2

E-106

CP 2



MIX-101

T-101

E-103RCY-1

V-101T-103

RCY-3

V-100


Water

Methanol

Recycle

Methanol

Recycle

MIX-100

P-101

E-100

P-102

P-103

MIX-103

R-101

E-104

Cutter-1


RCY-2

T-104

E-105

E-107OP 3

E-101

E-102

Flash-1

OP 4CP 2

Waste cooking

oil

MeOH

Tri-glycerides

Biodiesel

Waste

Oil

Reactive Distillation

ColumnFFA

E-106

CP 2


Glycerol

Water

Methanol

Recycle



Water

Methanol

Recycle

Methanol

Recycle Sustainability Metrics Base case

design Intensified alternative

%Improvement

Per

form

ance

met

rics

Total utility cost ($/year) 7,790,000 4,660,000 40.2

Total energy consumption (GJ/h) 119.163 73.104 38.6

product/raw material (kg/kg) 0.94 0.94 0

Energy/ products (GJ/kg) 0.0025 0.0017 32

Net water added to the system (m3) 0 0 0

Water for cooling/product (m3/kg) 0.017 0.017 0

Waste/raw material (kg/kg) 0.032 0.026 18.8

Waste cooking

oil

MeOH

Tri-glycerides

Biodiesel

Waste

Oil


ColumnFFA

Per

form

ance


Waste/products (kg/kg) 0.034 0.028 17.6

Hazardous raw material/product (kg/kg) 0 0 0

Number of unit operations 9 7 22

LC

A

Total carbon footprint (kg CO2 eq.) 0.183 0.143 21.8

HTPI - Human Toxicity Potential by Ingestion (1/LD50) 0.51811 0.51111 0

HTPE - Human Toxicity Potential by Exposure (mgemiaaion/m3) 0.03558 0.03564 0

GWP - Global Warming Potential (CO2 eq.) 0.55214 0.55241 0

ODP - Ozone Depletion Potential (CFC-11 eq.) 5.18E–09 5.18E–09 0

PCOP - Photochemical Oxidation Potential (C2H2 eq.) 0.04968 0.04976 0

AP - Acidification Potential (H+ eq.) 0.00010 0.00010 0

ATP - Aquatic Toxicity Potential (1/LC) 0.00366 0.00366 0


Glycerol

Water

Methanol

Recycle


ATP - Aquatic Toxicity Potential (1/LC50) 0.00366 0.00366 0

TTP - Terrestrial Toxicity Potential (1/LD50) 0.51811 0.51111 0

HTC (Benzene eq.) - human toxicity (carcinogenic impacts) 2062.7 1794.5 13

HTNC (Toluene eq.) - human toxicity (non-carcinogenic impacts) 1.3301 1.1795 11.3

ET (2, 4-D eq.) - Fresh water ecotoxicity 0.00525 0.00490 6.7

LC50 is lethal concentration (mgemission/kgfathead minnow) LD50 is one kg body weight of rat administered in milligrams of toxic chemical by mouth (mgemission/kgrat)


Water

Methanol

Recycle

Methanol

Recycle Sustainability Metrics Base case

design Intensified alternative

%Improvement

Per

form

ance

met

rics

Total utility cost ($/year) 7,790,000 4,660,000 40.2

Total energy consumption (GJ/h) 119.163 73.104 38.6

product/raw material (kg/kg) 0.94 0.94 0

Energy/ products (GJ/kg) 0.0025 0.0017 32

Net water added to the system (m3) 0 0 0

Water for cooling/product (m3/kg) 0.017 0.017 0

Waste/raw material (kg/kg) 0.032 0.026 18.8 60%

70%

80%

90%

100%

Operational Cost/kg Product

Utility Cost/kg ProductHTNC (kg C6H6 Eq.)

Waste cooking

oil

MeOH

Tri-glycerides

Biodiesel

Waste

Oil


ColumnFFA

Per

form

ance


Waste/products (kg/kg) 0.034 0.028 17.6

Hazardous raw material/product (kg/kg) 0 0 0

Number of unit operations 9 7 22

LC

A

Total carbon footprint (kg CO2 eq.) 0.183 0.143 21.8

HTPI - Human Toxicity Potential by Ingestion (1/LD50) 0.51811 0.51111 0

HTPE - Human Toxicity Potential by Exposure (mgemiaaion/m3) 0.03558 0.03564 0

GWP - Global Warming Potential (CO2 eq.) 0.55214 0.55241 0

ODP - Ozone Depletion Potential (CFC-11 eq.) 5.18E–09 5.18E–09 0

PCOP - Photochemical Oxidation Potential (C2H2 eq.) 0.04968 0.04976 0

AP - Acidification Potential (H+ eq.) 0.00010 0.00010 0

ATP - Aquatic Toxicity Potential (1/LC) 0.00366 0.00366 0

0%

10%

20%

30%

40%

50%

Energy usuage/kg ProductPCOP (C2H2 Eq.)


Glycerol

Water

Methanol

Recycle


ATP - Aquatic Toxicity Potential (1/LC50) 0.00366 0.00366 0

TTP - Terrestrial Toxicity Potential (1/LD50) 0.51811 0.51111 0

HTC (Benzene eq.) - human toxicity (carcinogenic impacts) 2062.7 1794.5 13

HTNC (Toluene eq.) - human toxicity (non-carcinogenic impacts) 1.3301 1.1795 11.3

ET (2, 4-D eq.) - Fresh water ecotoxicity 0.00525 0.00490 6.7

LC50 is lethal concentration (mgemission/kgfathead minnow) LD50 is one kg body weight of rat administered in milligrams of toxic chemical by mouth (mgemission/kgrat)

Raw Material cost/kg Product

Profit

Carbon Footprint (CO2 Eq)

Base Case Alt. 1 Alt. 2 Alt. 3 Alt. 4

Edible oil industry:Soybean Processing

Soybean (Glicine max):

native to East Asia, globally grown.

248 MMT global production*, steadily increasing

Goal:Goal:

Synthesis and Design of Optimal Soybean Processing Network

Maximize Net Present Value (NPV)

Robustness to Uncertainty

Models:

Generic Process Interval Model

Sources of uncertainty:

Commodity - price uncertainty

Natural product - raw material composition uncertaintyNatural product - raw material composition uncertainty

* FAO Food Outlook, 2007-2009

Raw Materials 2

Products 21

Processes 15

Proc. Intervals 42

Tot binary var. 65

Results - Topology

SELECTED INTERVALS

DET.

NPV (unit-cost)

106.6

Results 2 – Economics

Cost unitcost 364.92Raw Material cost unitcost 350.00

PRODUCTS AND WASTES YIELD

COST STRUCTURE OVERVIEW*

Utility cost unitcost 11.88(of which heat) unitcost (8.65)Transportation unitcost -Special Wastes Cost unitcost 3.04

Revenues unitcost 492.61Oil unitcost 158,26Byproducts unitcost 334.35 REVENUES BREAKDOWN

Gross Operating Margin unitcost 127.69

Input to Product ratio %mass 93.09%Input to Wastes ratio %mass 6.91%

*in scaled units, numbers refered to 100 unitmass of feed

Oil Refinery Wastewater Treatment

• World refinery capacity: 88.7·106 barrels of crude oil per day (2010)1

• Single refinery capacity:150-600,000 barrels of crude oil per day2

• Average freshwater consumption: 1.55-2.14 tons/m3 of crude oil3up to

30·106• Average freshwater consumption: 1.55-2.14 tons/m of crude oil

Average wastewater production: 0.48-0.95 tons/m3 of crude oil3

• Challenging case study:

• Intensive use of water

• Often located in water scarce countries

• Different configurations of water user

and producer processes

30·10ton/day!

and producer processes

• Highly variable amount and

contamination of wastewaters

1 OPEC, Annual Statistical Bulletin 2010/20112 J. Wong and Y. T. Hung, Handbook of Industrial and Hazardous Waste Treatment, 20043 Adapted from DOE, Energy and Environmental Profile of of the U.S. Petroleum RefineryIndustry, 2007

Superstructure

3 Wastewater Sources4 Water Sinks4 Water Sinks23 Treatment Units

Sinks

PreTreatment Primary

TreatmentSecondaryTreatment

TertiaryTreatmentH2S, NH4

+

SS, O&G, C NH4+ , Cr6

+, ions

Sources

C

Results 1- topology

Information obtained:

� Stream table

� Composition evolution

� Economic and performance metrics

CO2 Utilization

40

Production of block chemicals through CO2 conversion

Kongpanna et al. 2014

41

Roh et al. 2014

Production of block chemicals through CO2 conversion

42

Roh et al. 2014

Kongpanna et al. 2014

Are we dependent on others?

Why should Why should others make decisions for us? How do we become

decision makers?


makers?

What are the challenges?

Depletion of fossil fuels?


Grossmann, 2014

What are the challenges?

Growth in shale gas


Grossmann, 2014

How sure are we?

• Issues related to uncertainty of data & models are important and need to be considered

• Mutlidisciplinary nature of problems need to be handled


• Golden Era for Chemical Engineering (Westmoreland, 2014) – do something!

• Focused team-effort needed to meet the challenges

Chemical Engineering Education


Grossmann, 2014

Invitation to visit Denmark

Main Event of the EFCE


Call for abstracts is now open!

achieving more sustainable solutions through … · achieving more sustainable solutions through...

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