SustainableProcess Synthesis- Intensification › ... › iets-expert-workshop-rgani.pdf · 2018-04-11 · SPEED SustainableProcess Synthesis-Intensification Rafiqul Gani. Department

SPEED

Sustainable Process Synthesis-Intensification

Rafiqul GaniDepartment of Chemical & Biochemical Engineering

Technical University of DenmarkDK-2800 Lyngby, Denmark

[email protected]

1IETS Experts Workshop, Berlin, 4-5 April 2017

mailto:[email protected]

SPEED

IETS Experts Workshop, Berlin, 4-5 April 2017 2

Processes need to be:

Sustainable (Economically feasible; Reduced waste; Utility efficient; Environmentally acceptable); Safe; Operable; …….

Establish sustainable production

Adopt to changing markets

Chemical and bio-based industry faces enormous challenges to achieve and/or respond to:

Demands for innovative products

Survive global

competition

Process

Product(s)

Waste

Raw Materials

Utilities

SPEED


Target: Intensify (reduce number of operations) as well as operational costs

Methyl acetate in multifunctional reactor (Eastman Chemicals)

Find innovative solutions

SPEED


Industrial example of process intensification

Deordorization Plant – Alfa Laval, Copenhagen

SPEED


Concept of 3-stages synthesis-design approachDecompose the problem into stages to manage the complexity

Stage 1Synthesis

Stage 2Design

Stage 3Innovation

Given: set of feedstock & productsFind: processing route

Given: processing route Find: feasible design

Given: feasible design (base case)Find: alternative more sustainable design

Define problem

Generate superstructure

Mathematical formulation

Solve optimization problem

Generate sustainable intensified alternatives

Detailed analyses to identify process bottlenecks

Quaglia et al. (2012)

Carvalho et al. (2013)

Babi et al. (2015)

SPEED


Raw material

Synthesis stage: find the optimal processing route

Sustainable Product-Process Development

SPEED


Synthesis problem solution: Biorefinery network

Lipids

Sugar productionSugarcane Sugar

Molasses Citric acid fermentation Citric acid

Lactic acid fermentation Lactic acid

L-lysine fermentation L-lysine acid

Hardwood chips

Switchgrass

Wheat straw

Cassava rhizome

Corn stover

Sugarcane bagasse

Dilute acid pretreatment

Lime pretreatment

Controlled pH pretreatment

ARP pretreatment

AFEX pretreatment

STEX pretreatment Int2

NREL hydrolysis

Conc. acid hydrolysis

Dilute acid hydrolysis

Int3 Ethanol fermentation Int4Ethanol

purification Ethanol

Lignocellulose

Size reduction

Gasification

Int5 Reforming Int6 LT Fischer-Tropsch

HT Fischer-Tropsch

Methanol synthesis Int7

Methanol purification Methanol

Methanol (int) Methanol to gasoline

Gasoline-diesel mix

Gasoline-diesel sep. Gasoline

Diesel

Virgin palm oil

WC palm oil

Microalgae

Alkali-cat. transesterif.

Acid-cat. esterification

Triglycerides Int8

Acid-cat. transesterif.

-

SFEC transesterif.

CSEC transesterif.

Phase separation Organic phase

Aqueous phase

FAME purification

Glycerol purification

Diesel

Glycerol

Open pond cultivation

PBR cultivation

Int9 Flocculation polyelectrolyt.

Flocculation NaOH

Flocculation PGA

Flocculation chitosan

Bio-flocculation

Centri-fugation

Autofloccula-tion (high pH)

Microfilt. + centrifugat.

Microalgae (int)

DR+US

DR+GR+ MW+US

Drying

Int10 GR-assisted LE

US-assisted LE by IL

US+MW- assisted LE

Wet LE

SE (Bligh-Dyer method)

SE (modifed Bligh-Dyer)

Supercritical fluid extract.

Extraction IL mixture

Extraction IL [Bmim][MeSo5]

Alkaline insitu transesterif.

Acidic insitu transesterif.

Enzym. insitu transesterif.-

Dry micro-algae (int)

Residue Enzymatic hydrolysis Int15 Fast pyrolysis

Ethanol fermentation

Anaerobic digestion

GR in liquid nitrogen

Int11

Int12

Int14

- Int13

Bio-oil

Ethanol

Biogas

Oil palm fruit Oil extraction

SPEED

8

Stage-2: Design Stage – CO2 conversion

CO2 Conversion Network

Mixing 1 Intermediate Production Mixing 2 Product 1 Conversion Purification Product 2 Conversion Purification 2 ProductsCapture Step 1Capture MixingFeedstock Capture Step 2 Mixing 3Splitter

Mixing Intermediate

Intermediate Production 2

M3

M1

M3

M1

M2

meohdirsyn

comref meohsynsyn

comref

meohdirsyn

meohsynsyn

dryref meohsyn2syn

dmesyn

S1

dmedirsyn

H2

H2

CH4, H2O

CH4, H2O

CH4

H2O

CO2

MeOH

DME

S2

Purge

Purge

S1

S2

Purge

Purge

S4

S5Purge

Purge

M5

M6

M7

NH3

C2H4O

C3H6O

ureasyn

ecsyn

pcsyn

DMCDirSyn

DMCUreaSyn

DMCECSyn

DMCPCSyn

S6

Purge

S7

Purge

S8

Purge

S9

Purge

NH3

PG

EG

DMC

CapM1 CapABS1 Splitter

M8

coalCO2_1

M2 dryref meohsyn2syn

CH4

M2 dryref

CH4

S3

Purge

M9

M10

M11

M4

H2

S3

Purge

M4

H2

MEA, H2O

Flue gas

MEA, H2O

CapDES1

M3

M1

meohdirsyn

comref meohsynsyn

S1

H2

CH4, H2O

S2

Purge

Purge

M2 dryref meohsyn2syn

CH4

S3

Purge

M4

H2

dryref*

dryref*

dryref*

dryref*

meohsynsyn*

meohsynsyn*

dmedirsyn* dmedirsyn**

meohsynsyn*

BP

BP

BP

Model and Solver

Number of equations 450663

Number of variables 444505

Discrete variables 176

Problem type MIP

Solver CPLEX

Superstructure for stage -1

IETS Experts Workshop, Berlin, 4-5 April 2017

SPEED



Design targets:more profit; lessenergy consumption; less waste; lowerenvironmental impact; …..

SPEED Biodiesel production: 2-stage analysis


MIX-100

P-101

E-100

MIX-101

P-102

P-103

MIX-103

R-101

T-101

E-103RCY-1

E-104

Cutter-1

V-101

Flash-2Cutter-2

E-106

T-102

RCY-2

T-103

T-104

RCY-3

E-105

E-107OP 3

E-101

E-102

Flash-1

V-100

OP 4CP 2

Path 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

SPEED

11

Stage-2: Design analysis

Absorber Desorber

Flue gas

MEA

F-EO

F-CO2

R-EC synthesisV-101

R-GAS

F-EC

F-MEOH

R-DMC synthesisEC route V-202

V-203

V-204

V-201

CAPTURE STEP 1

CAPTURE STEP 2

INTERMEDIATE PRODUCTION

MIXING 1

MIXING 3

PRODUCT 2 CONVERSION

PURIFICATION 2

F-MIX 2 PROD-1

PROD-2 P-DMC

Excess Feed

P-EGEG

PURGE

RECYCLE

Clean flue gas

CO2

H-101

E-101

C-102

R-103

E-103

Natural gas

HP steam

HP steam

C-101

T-101 T-102

Water

F-101

Dry syngas

E-102Air

Flue gas

Fuel gas

R-101 R-102

Purge

F-102

C-103

Recycle

Off-gas

P-101

P-102

E-104

Bottleneck: energy intensive separation

Parameter Value Unit

CAPEX 20.39 Million $

OPEX 13.41 Million $/year

Net CO2 4.97 kgCO2/kgDMC

Indirect CO2 (energy) 4.76 kgCO2/kgDMC

CO2 utilized 1.79 kgCO2/kgDMC

CO2 direct 2.00 kgCO2/kgDMC

IETS Experts Workshop, Berlin, 4-5 April 2017

SPEED


Innovative, sustainable & intensfied designs for stage 3

Note: for existing process, stage-1 is not necessary and we start with stage-2 to define the targets for

sustainable & innovative design

SPEED



Design targets:more profit; lessenergy consumption; less waste; lowerenvironmental impact; …..

SPEED Tasks to Phenomena (SPB)


SPB Interconnection Phenomena In OutSPB.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)

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

SPB Interconnection Phenomena In OutM=R=H=C 1..n(L) 1(L)

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

SPB Interconnection Phenomena In OutSPB.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)

Reduced from 4017→58 using connectivity rules

Connectivity Rules:1. H+C should not exist in

the same SPB2. PC phenomena exists

together with PT phenomena

3. SPB can contain simultaneous R and separation

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

Lutze et al. (2013)

Table 3

ϕ/ϑLoStOpPc

Reaction Present*

Reaction is inside the 1st unit operation (Unit-Op)*

The product purity is defined so in the base case design the reactor effluent is connected to a separation sequence*

EFFiciencyDo not integrate phenomena which inhibit each other’s performance*

Add phenomena and stages in the flowsheet in which it has the highest efficiency*

EnergyDo not connect phenomena to a series with alternating heat addition and heat removal*

Remove options in which phenomena are heated/cooled leading to a decrease of the efficiency*

Flowsheet SimplificationRemove options with redundant stages*

Do not use recycle streams if not necessary*

WasteDo not use two different solvents in one process*

$ DMC/ton DMCAllow a fixed number of Unit-Ops. Maximum number of Unit-Ops=2*

Ensure that phenomena are connected to ensure the best use or recycle of raw materials*

Raw materials are pure*

Yield ≥90%*

PI screening criteria: Novel equipment*

Analysis of split factors

CompoundMolar flow in ηi,in [mol/s]Molar flow out, ηi,out [mol/s]Split factor σsep,i

PCa6.5

MeOH13

DMC-

PDi-

Identification of Phenomena

Unit OperationPhenomena

ReactorR (V), M (V), C (V)

Distillation columnM (V-L), PC (V-L), PT (V/L), PS (V/L)

Liquid-Liquid SeparatorM (L), PC (L-L), PS (L/L)

DecanterPS (L/L)

V-Vapour, L-Liquid

T.BP

ComponentTB [K]Tm[K]

HOAc391.15289.75

MeOH338.15175.55

MeOAc330.05175.15

H20373.15273.15

EthOAc350.25189.55

DMSO462.00291.65

Azeotrope Search

Binary PairAzeotrope T(K), x (mole %)

MeOAC/H2O329.8K, 92.8% MeAc

MeOAc/MeOH326.4K, 68.6% MeAc

HOAc/H2O371.8K, 15.7% HOAc

Collection & Analysis of PCP

ComponentTB [K]

HOAc391.15

MeOH338.15

MeOAc330.05

H20373.15

EthOAc350.25

DMSO462.00

ComponentMolecular Weight (MW) [kg/kmol]TB [K]TM [K]log (Ws) i.e. log (mg/l)log (Kow)Radius of gyration, Rg [Å]Molar Volume, VM [m3/kmol]Van der Waals Volume, VdV [m3/kmol]Solubility Parameter δSP [MPa0.5]

H2O18.00373.15273.155.45-1.380.620.060.0147.80

MeOH32.04337.95175.555.030.011.560.040.0229.59

HOAc60.05391.05289.755.25-0.172.610.180.0419.01

MeOAc74.08329.95175.154.880.333.020.080.0519.35

Estimated from Marrero‐Gani‐Approach

Estimated from ASPEN

PropertyH2O /MeOHH2O /HOAcH2O /MeOAcMeOH /HOAcMeOH /MeOAcHOAc /MeOAc

TB [K]1.1040.9541.1310.8641.0241.185

TM [K]1.5560.9431.5600.6061.0021.654

log (Ws) i.e. log (mg/l)1.0831.0381.1170.9581.0311.076

log (Kow)-138.0008.118-4.182-0.0590.030-0.515

Radius of gyration, Rg [Å]0.3940.2360.2040.5990.5170.864

Molar Volume, VM [m3/kmol]1.2560.3110.6880.2480.5482.211

Van der Waals Volume, VdV [m3/kmol]0.5700.2910.2740.5100.4800.941

Solubility Parameter δSP [MPa0.5]1.6152.5142.4701.5571.5290.982

Enthalpy of Formation

CompoundΔHf [kJ/mol]ν

H2O-285.831

MeOH-239.11-1

HOAc-484.09-1

MeOAc-442.791

ΔHf [kJ/mol]-5.42

-4

Equilibrium Caculation

X0.000218781

nA0.0002961

nB0.0041454

Keq45

Keqcalc45.0289141127

nA-X0.000077319

ConvA0.7388753794

nB-X0.003926619

ConvB0.0527768128

Table9

Unit-OpPhenomenaOperating Window

ReactorReaction (R)Tlow=175.15K (Lowest Melter)

Thigh=378,15 (Maximum T for reactor operation)

Vapour Mixing (MV)Tlow=330,05K (Lowest boiler)

Thigh=391,05 (Highest Boiler)

All concentrations are below the dew point line

DistillationMldTlow=175.55K (Lowest Melter)


Vapour Mixing (MV)Tlow=326,41K (Lowest boiling azeotrope)

Phase Contact (PC) V-LV-L present

Phase Transition (PT)Tlow=326,41K (Lowest boiling azeotrope)


Phase Separation (PS)V-L present


LLSMIdTlow=175.55K (Lowest Melter)


Phase Contact (PC) L-LL-L present

Phase Separation (PS)L-L present

DecanterPhase Separation (PS)L-L present

Table 10

Limitation/Bottleneck

Necessary TaskRRRRSSS

Desireable TaskSHSMRRMS

Separation is not sufficient

limiting equilibrium

azeotrope

high energy demand

limited mass transfer

limited heat transfer

driving forces too low

Reaction is not sufficient

contact problems of educts; limited mass transfer

product reacts further/is intermediate

activation problems

degradation by T

degradation by pH

difficulties to control conditions, reaction too exotherm/endotherm


R-reaction, S-Separation, HS-Heat Supply, M-mixing

Particular intensified option is reported to overcome this limitation

The activation of an option through a knowledge search

Table 11&12-modified

Separation TypeImportant PCPReaction is not sufficientMeOAc/HOAc+ MeOH+H2OH2O/HOAc+ MeOH+MeOAcMeOAc+H2O/HOAc+MeOHReaction of co-product-H2O

V-LTb***

S-LTM**

L-Llog (Kow), δSP**

L-separationVM, Rg, δSP, VdV**

L-pervaporationVM, Rg, δSP, VdV**

V-permeationVM, Rg, δSP, VdV**

G-LTb, δSP***

R-


V-LTb***

S-LTM**





G-LTb, δSP***

R-

Table13

ClassMixingPhase TransitionPhase SeparationPhase ContactDividerEnergy TransferReaction

Sub-class1-Phase2-PhaseV-LV-LV:VL:LV-LV:VL:L-Thermal-

PhenomenaMIDMFl,tubMFl,recMV2phMPT (V-L)PT (P:V-L)PS (V-L)PS (V:V)PS (L:L)PC (V-L)PC (V:V)PC (L:L)DHCR

Selection use for belows2s10s11s1/s3s4/s5/s8s5/s6/s7s12s6/s7/s12s13/s14s9s5/s6/s12s13/s14s8/s9s1/s6/s11/s15s1/s6/s11/s16s1

Mixing1-PhaseMIDI

MFl,tubI

MFl,recI

MVI/s1s1

2-Phase2phMI/s5/s8s5s8

Phase TransitionV-LPT(V-L)I/s5/s7s7s5

PT(P:V-L)I

Phase SeparationV-LPS(V-L)s6s12I/s6/s12

V:VPS(V:V)I/s14s14

L:LPS(L:L)I/s8s8

Phase ContactV-LPC(V-L)s6s12I/s6/s12

V:VPC(V:V)s13I/s13

L:LPC(L:L)s9I/s9

Divider-Dccccccccccccccc

Energy TransferThermalHs6s12I/s1/s6/s12s1

Cs6s12I/s1/s6/s12s1

Reaction-RI

NotesFor Mixing the inlet could be either liquid of vapour


Sub-class1-Phase2-PhaseV-LV-LV-L-Thermal-

PhenomenaMIDMFl,tubMFl,recMV2phMPT(V-L)PT(P:V-L)PS(V-L)PC(V-L)DHCR

Selection use for below123457.17.2861011129

Mixing1-PhaseMID+xxxx

MFl,tub+xxxx

MFl,rec+xxxx

MV+x

2-Phase2phM+xxx

Phase TransitionV-LPT(V-L)+x

PT(P:V-L)+x

Phase SeparationV-LPS(V-L)+

Phase ContactV-LPC(V-L)xx+

Divider-DAAAAAAAAA+AAA

Energy TransferThermalHx+x

Cx+x

Reaction-Rx+

Table14

No.PhenomenaOperating Window (OPW)

PB.1MID (Concentrations below dew point line)Tlow=175.55K (Lowest Melter)

Thigh=391,15K (Highest Boiler)

PB.2MFl,tub (Concentrations below dew point line)Tlow=175.55K (Lowest Melter)


PB.3MFl,rec (Concentrations below dew point line)Tlow=175.55K (Lowest Melter)


PB.4MV (Concentrations above boiling point line)Tlow=326,4K (Lowest boiling azeotrope)

PB.52phM (Concentrations in V‐L regions between dew and boiling point lines.)Tlow=326,4K (Lowest boiling azeotrope)


PB.6PT(V-L) (Concentrations in V‐L regions between dew and boiling point lines)Tlow=326,4K (Lowest boiling azeotrope)


PB.7PT(P:V-L)Tlow=175.55 (Melting point of Methanol)

Thigh=GET VALUE (Membrane Stability)

PB.8PS(V-L)V-L present

PB.9PS(V:V)V-V present

PB.10PS(L:L)L-L present

PB.11PC(V-L)V-L present

PB.12PC(V:V)V-V present

PB.13PC(L:L)L-L present

PB.14D-

PB.15H-

PB.16C-

PB.17RTlow=175.55 (Lowest Melter)

Thigh= 393K (Catalyst degradation T)http://goo.gl/w9UiS

















PB.10D-

PB.11H-

PB.12C-


Thigh= 393K (Catalyst degradation T)

Table14_modified



















PB.12D-

PB.13H-

PB.14C-



NSPB_Calc

ABA!B!A!*B!ABA!B!A!*B!

1113991680013991680012121479001600147900160013

102362880027257600661123991680027983360078

93362880621772802201033628800621772800286

84403202496768049594362880248709120715

755040120604800792854032012048384001287

6672072051840092476504072036288001716

57120504060480079267720504036288001716

482440320967680495581204032048384001287

39636288021772802204016

Deenesh K. Babi: Deenesh K. Babi:The sum is taken here because np,max has been reached49243628808709120715

2102362880072576006631063628800217728002868099

Deenesh K. Babi: Deenesh K. Babi:The sum is taken here because np,max has been reached

11113991680039916800122112399168007983360078

01214790016004790016001112147900160047900160013

0131622702080062270208001

np,max9

np,tot13np,max10

NSPB4017

Deenesh K. Babi: Deenesh K. Babi:+1 where it represents the divider

Deenesh K. Babi: Deenesh K. Babi:The sum is taken here because np,max has been reachednp,tot14

NSPB8100


ABA!B!A!*B!

212123

121223

0316617

np,max3

np,tot4

NSPB8


ABA!B!A!*B!

13162270208001622702080014

122479001600295800320091

113399168006239500800364

104362880024870912001001A

95362880120435456002002

8640320720290304003003

7750405040254016003432

6872040320290304003003

59120362880435456002002

410243628800870912001001

31163991680023950080036416277

np,max11

np,tot15

NSPB16278



SPB's_rev1

SPBInterconnection Phenomena InOut

SPB.1M1..n(L)1(L)

SPB.2M=R1..n(L)1(L)

SPB.3M=H1..n(L)1(L)

SPB.4M=C1..n(L)1(L)

SPB.5M=R=H1..n(L)1(L)

SPB.6M=R=C1..n(L)1(L)

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

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

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

SPB.10M=R=2phM=PC=PT(VV)=PS(VV)1..n(L,VL)2(V;L)

SPB.11M=H=2phM=PC=PT(VL)1..n(L,VL)1(VL)

SPB.12M=H=2phM=PC=PT(VL)=PS(VL)1..n(L,VL)2(V;L)

SPB.13M=H=2phM=PC=PT(PVL)=PS(VL)1..n(L,VL)2(V;L)

SPB.14M=H=2phM=PC=PT(VV)=PS(VV)1..n(L,VL)2(V;L)

SPB.15M=C=2phM=PC=PT(VL)1..n(VL)1(VL)

SPB.16M=C=2phM=PC=PT(VL)=PS(VL)1..n(VL)2(V;L)

SPB.17M=C=2phM=PC=PT(PVL)=PS(VL)1..n(VL)2(V;L)

SPB.18M=R=H=2phM=PC=PT(VL)1..n(L,VL)1(V/L)

SPB.19M=R=H=2phM=PC=PT(VL)=PS(VL)1..n(L,VL)2(V;L)

SPB.20M=R=H=2phM=PC=PT(PVL)=PS(VL)1..n(L,VL)2(V;L)

SPB.21M=R=H=2phM=PC=PT(VV)=PS(VV)1..n(L,VL)2(V;L)

SPB.22M=R=C=2phM=PC=PT(VL)1..n(L,VL)1(V/L)

SPB.23M=R=C=2phM=PC=PT(VL)=PS(VL)1..n(L,VL)2(V;L)

SPB.24M=R=C=2phM=PC=PT(PVL)=PS(VL)1..n(L,VL)2(V;L)

SPB.25M1..n(L)1(L)

SPB.26M=R1..n(L)1(L)

SPB.27M=H1..n(L)1(L)

SPB.28M=C1..n(L)1(L)





















SPB.49M1..n(L)1(L)
























SPB's_rev2


SPB.1M1..n(L)1(L)

SPB.2M=R1..n(L)1(L)

SPB.3M=H1..n(L)1(L)

SPB.4M=C1..n(L)1(L)
















SPB.20M1..n(L)1(L)



















SPB.39M1..n(L)1(L)



















SPB.58D1(L;VL,V)1..n(L;V; VL)


SPB.1M1..n(L)1(L)

SPB2M=R1..n(L)1(L)






SPB.1M=R=H=C1..n(L)1(L)







SPB.8M=R=2phM=PC=PT(VL)=PS(VL)1..n(L,VL)2(V;L)Process OptionStage1Stage 2Stage 3

1M=RM=RM=R=C=2phM=PC=PT(VL)=PS(VL)

Process OptionStage1Stage 2Stage 3

1MMM=H=2phM=PC=PT(L=>V)

2MMM=C=2phM=PC=PT(V=>L)

3M=R=2phM=PC=PT(PVL)=PS(VL)M=R=2phM=PC=PT(PVL)=PS(VL)M=R=2phM=PC=PT(PVL)=PS(VL)

Figures5&6

ACM NameNew NameDuty [W]Duty [kW]

Condenser1.QcT1.cond2517324.19432517.3241942669




Reboiler1.QhT1.reb2769550.68542769.5506854236

Reboiler2.QhT2.reb5736528.56435736.5285642791

Reboiler3.QhT3.reb5748382.83325748.3828331897

Reboiler4.QhT4.reb1276645.64081276.6456408204

DMC_Cooler.QcDMC.cool289403.3666289.4033665544

PDO_Cooler.QcPDO.cool440295.8373440.2958373021

PC_Cooler.QcPC.cool201485.93201.4859287002

Heater_Feed2.Q_exFeed.heat365456.47365.4564711572

Heater_PS.Q_exPressure Swing.heat431976.77431.9767679506

T1.condT2.condT3.condT4.cond2517324.19426693125686907.72969832189194730.99644899551229990.1571143158T1.rebT2.rebT3.rebT4.reb2769550.68542361915736528.56427907945748382.83318965231276645.6408204371DMC.coolPDO.coolPC.cool289403.36655436386440295.83730209945201485.9287001518Feed.heatPressure Swing.heat365456.47115721332431976.76795063878T1.condT2.condT3.condT4.condDMC.coolPDO.coolPC.cool2517324.19426693125686907.72969832189194730.99644899551229990.1571143158289403.36655436386440295.83730209945201485.9287001518T1.rebT2.rebT3.rebT4.rebFeed.heatPressure Swing.heat2769550.68542361915736528.56427907945748382.83318965231276645.6408204371365456.47115721332431976.76795063878

Analysis of SPB's

SPB'sSPBCoCrossflowCounter current

SPB.1, SPB.20, SPB.39, SPB.58MNo reactionNo reactionNo reaction

SPB.3, SPB.23, SPB.42M=CNo reactionNo reactionNo reaction

SPB.2, SPB.21, SPB.40M=R0.729/inf1 phase1 phase

SPB.5, SPB.24, SPB.43M=R=H0.725/inf1 phase1 phase

SPB.6, SPB.25, SPB.42M=R=C0.733/inf1 phase1 phase

SPB.7, SPB.26, SPB.45M=Mv=R=2pM=PC=PT(VL)0.729/infno separate phasesno separate phases

SPB.8, SPB.27, SPB.46M=Mv=R=2pM=PC=PT(VL)=PS(VL)

Reaction Analysis

Heat Capacity Data, obtained from ICAS

Expression=A+B*T+C*T^2+D*T^3+E*T^4J/kmolK

HOAc139640-320.80.8985

MeOH105800-362.230.9379

MeOAc61260270.9

Water276370-2090.18.125-0.0141169.37E-06

Tref=303.15KT0=303.15T0=313.15T0=323.15

Xe(T)XEB(T)XEB(T)XEB(T)

TXeXEBXEBXEB

303.150.73699386160

304.150.73658152240.063896894

305.150.73617147480.1284984414

306.150.73576370070.1937937385

307.150.7353581820.2597705869

308.650.73475409410.3599838129

309.150.734553840.3937134824

310.150.73415498170.461648383

311.150.73375830870.5302024899

312.150.73336380390.5993566993

313.150.73297145050.669090459

3140.7326396290.72880342340

314.060.73261626430.73303330810.0593519558

314.150.73258123160.73938175380.0652517854

315.150.73219313070.81020709520.1311613016

316.150.73180713130.88154151450.197712032

317.150.73142321710.95335856060.2648860501

318.150.7310413721.0256303030.332664001

319.150.730661581.09832733850.4010250865

320.150.73028382541.17141880440.4699470536

321.150.72990809241.24487239540.5394061877

322.150.72953436561.31865438790.6093773096

323.150.72916262961.39272966770.67983377750

323.850.72890359070.72942709770.046634863

324.150.72879286910.75074749360.0667120247

325.150.72842506920.82208891560.1340199229

330.150.72661496010.4786570939

332.150.72590412880.6197814048

333.150.72555148780.6909220764

333.630.72538287130.725192799

334.150.72520067790.7624035615

335.150.72485168570.8341905546

Kremser Example

Example taken from Page 170, SEPARATION PROCESS PRINCIPLES 2ND ED

[email protected], 400 psiaA=L0/KiV0Si=1/AphiA

C16.650.0310150376

C21.640.1257621951

C30.5840.3531678082

nC40.1951.05769230770.9454545455

nC50.07132.89270687240.3456969697

Oil0.00010.0004848485

CompOil composition [lbmol/h]CompFeed gas Composition [lbmol/h]

C40.05C1160

C50.78C2370

Oil164.17C3240

L0165nC425

nC55

V0800

M=R=2phM=PC(VL)=PT(VL)=PS(VL)

InitialAnalysis of M=Mv=R=2pM=PC=PT(VL)=PS(VL)ConversionCalcuation of xi initial

xHOAcxMeOHxMeOAcxH2OT[K]xHOAcxMeOHxMeOAcxH2OyHOAcyMeOHyMeOAcyH2OKHOAcKMeOHKMeOAcKH2OWalWBlWClCheckWAVWBVWCVCheckV [kmol/hr]L [kmol/hr]XMeOHXHOAcFeed1kmol/hr

0.09090909090.909090909100339.48863.49E-040.75735480.02339480.21890164.17E-050.82251870.09558310.08185651.19E-011.08604144324.08565578680.37394199042.32E-027.63E-012.14E-011.00E+008.73E-028.38E-017.48E-021.00E+000.93439560.06560440.84710194120.9993201765Molar Ratio1.56HOAc:MeOH

0.13043478260.869565217400339.9187.33E-040.67016120.03216060.29694519.19E-050.74809380.14275750.10905671.25E-011.11628933464.43889417490.36726216393.18E-026.80E-012.88E-011.00E+001.25E-017.80E-019.55E-021.00E+000.88709390.11290610.76734971590.998740252NHOAc0.609375kml/hr

0.16666666670.833333333300340.47071.23E-030.58553570.03741370.37581861.66E-040.67880110.18510490.13592841.34E-011.15928217534.94751655140.36168619653.72E-026.00E-013.63E-011.00E+001.56E-017.29E-011.15E-011.00E+000.87311970.12688030.7169059840.9981946015xHOAc0.609375

0.20.800340.86931.82E-030.51272390.0411640.44428992.62E-040.61538640.22639180.15796011.44E-011.20022959735.49975221070.3555338534.12E-025.31E-014.28E-011.00E+001.85E-016.86E-011.29E-011.00E+000.85488150.14511850.66507014390.9975592475xMeOH0.390625

0.23076923080.769230769200341.25352.48E-030.44606810.0429040.50854353.84E-040.55664120.26515480.17781961.55E-011.24788389936.18018832740.3496644834.34E-024.68E-014.89E-011.00E+002.10E-016.49E-011.41E-011.00E+000.8420630.1579370.6181539850.9968970281

0.25925925930.740740740700341.62293.20E-030.38517510.0429990.56862625.38E-040.50207910.30167350.19570981.68E-011.30350871597.01582594940.34418006064.42E-024.09E-015.47E-011.00E+002.32E-016.17E-011.51E-011.00E+000.83222720.16777280.57382822370.9962035029

0.28571428570.714285714300341.8613.98E-030.3324790.04268410.62085827.22E-040.45140020.33780060.2100771.82E-011.35768033477.91396796470.33836550764.46E-023.58E-015.97E-011.00E+002.53E-015.90E-011.57E-011.00E+000.81906210.18093790.52842719080.9954099074

0.31034482760.689655172400342.20654.78E-030.28218180.04068280.67235179.54E-040.40379170.37054040.2247141.99E-011.43096294669.10803582840.33422091444.35E-023.09E-016.48E-011.00E+002.71E-015.65E-011.65E-011.00E+000.81244080.18755920.48674649910.9946115711

0.31972789120.680272108800342.31885.13E-030.26398650.03988420.69100331.06E-030.38560.38349740.22984282.07E-011.46068075459.61527121020.33262185584.31E-022.91E-016.66E-011.00E+002.78E-015.55E-011.67E-011.00E+000.80907110.19092890.46980140650.9942569355

0.38650306750.613496932500343.08278.59E-031.47E-010.03330460.81096592.34E-030.25403860.4803950.26322292.73E-011.726558730114.42428373260.32457949224.02E-021.73E-017.87E-011.00E+003.26E-014.95E-011.79E-011.00E+000.78170.21830.33553943790.9904066232

0.43502824860.564971751400343.67710.01461130.07931470.02959030.87648354.84E-030.15560450.55494860.28461133.31E-011.961862050818.75440938420.32471951844.23E-021.04E-018.53E-011.00E+003.59E-014.56E-011.86E-011.00E+000.75802910.24197090.22144950430.9834469194

0.47089947090.529100529100344.16160.02844150.04096040.03029920.90029880.01024020.0847890.60815360.2968173.60E-012.070023730220.0716058510.32968721055.55E-026.73E-028.77E-011.00E+003.82E-014.28E-011.90E-011.00E+000.73645380.26354620.13310994370.9680673172

0.48979591840.510204081600344.37310.04850320.02686610.03550510.88912550.01692030.05372850.63115650.29819473.49E-011.9998622817.77650253060.33537976367.75E-025.75E-028.65E-011.00E+003.93E-014.16E-011.91E-011.00E+000.71939420.28060580.09528534660.9473604333

0.49238578680.507614213200344.62140.05250230.02503780.03607370.88638610.01836850.05014540.63054060.30094543.50E-012.002787784917.47923279290.33951953898.14E-025.61E-028.62E-011.00E+003.94E-014.13E-011.94E-011.00E+000.72066010.27933990.09104296850.9433301427

0.50.500344.91250.06719850.02118410.04035940.87125790.02275130.04111376.34E-010.30227883.39E-011.940781057515.70529046520.34694526169.71E-025.56E-028.47E-011.00E+003.96E-014.07E-011.96E-011.00E+000.71476620.28523380.08179732540.9291417125

0.50738916260.492610837400345.24930.08519150.01840860.04624270.8501570.02760860.03427320.63479690.30332123.24E-011.861803722213.72750509810.35678257071.16E-015.71E-028.27E-011.00E+003.98E-014.02E-011.99E-011.00E+000.70805120.29194880.07666855680.9124540652

0.52153110050.478468899500345.63060.12805920.01560040.06481340.79152690.03664820.02583480.63761160.29990532.86E-011.65603446079.83765085620.37889464021.62E-016.74E-027.71E-011.00E+004.03E-013.96E-012.01E-011.00E+000.6827320.3172680.07984123720.8741206707

0.52606635070.473933649300346.0520.14288090.01471130.07022350.77218420.04012110.02384650.63353460.30249782.81E-011.62096483669.02168932050.39174305821.76E-017.00E-027.54E-011.00E+004.03E-013.93E-012.05E-011.00E+000.67953770.32046230.08167511920.8611358781

0.57081545060.429184549400348.02960.27492430.0109520.13614360.577980.0656180.0146050.62352190.2962552.39E-011.33354638424.57988403420.51256963912.91E-011.04E-016.04E-011.00E+004.08E-013.78E-012.14E-011.00E+000.57448250.42551750.15452993790.7290166317

0.6093750.39062500350.30610.36221568.06E-030.16206930.46765110.09028030.01065220.60652250.29254492.49E-011.3209688083.74236514870.62556230493.44E-011.12E-015.44E-011.00E+004.11E-013.64E-012.26E-011.00E+000.49322440.50677560.22370995430.6256976823

0.61538461540.384615384600350.9010.37654387.54E-030.1619880.45392320.0959660.01007510.59996790.29399082.55E-011.33533642853.70377990960.64766638943.50E-011.10E-015.40E-011.00E+004.10E-013.60E-012.30E-011.00E+000.48825760.51174240.22832005660.6107319703

0.62962962960.370370370400351.52680.402026.87E-030.16818670.42292630.10420069.20E-030.5972550.28934492.59E-011.33969182743.55114286680.6841496973.63E-011.11E-015.25E-011.00E+004.12E-013.56E-012.31E-011.00E+000.45274990.54725010.25975431190.5756516468

0.66666666670.333333333300354.12550.47165365.01E-030.16807690.35526060.13452097.07E-030.57374560.28466222.85E-011.41175425393.41358985080.8012771473.90E-011.06E-015.04E-011.00E+004.15E-013.40E-012.45E-011.00E+000.39302260.60697740.31439415210.4912707554

0.750.2500360.04160.60783362.48E-030.1488780.24081040.21576214.10E-030.51586930.26426813.55E-011.65480600823.46504721991.09741149054.31E-018.62E-024.83E-011.00E+004.23E-013.00E-012.77E-011.00E+000.2676080.7323920.44053769970.3294504933

0.80.200364.3680.68786561.49E-030.12592540.18471760.28531412.82E-030.46399030.2478714.15E-011.89388036983.68464424171.34189162274.49E-017.02E-024.81E-011.00E+004.28E-012.67E-013.05E-011.00E+000.21385850.78614150.49799627710.247779325

0.83333333330.166666666700367.27090.73703961.04E-030.11043940.15148520.33833282.16E-030.42757560.23193164.59E-012.08530522013.87158568411.53105121824.59E-016.03E-024.81E-011.00E+004.34E-012.43E-013.23E-011.00E+000.17341610.82658390.54997193870.198523094

0.85714285710.142857142900370.45940.78228046.94E-040.09155210.12547290.40091441.61E-030.37811640.21935945.12E-012.31783244884.13006801591.74826117834.66E-014.92E-024.84E-011.00E+004.38E-012.13E-013.49E-011.00E+000.1760490.8239510.5300252750.1656684868

0.88888888890.111111111100373.99350.83059514.16E-040.07310920.095880.47945651.09E-030.32478070.19467435.77E-012.61855273294.44240533342.03039528584.75E-013.86E-024.87E-011.00E+004.46E-011.81E-013.74E-011.00E+000.14894810.85105190.56143689910.1244196182

0.90.100375.26150.84676783.39E-040.06681850.08607430.50982949.29E-040.30498640.18425526.02E-012.73721939534.56440057772.1406529014.77E-013.51E-024.87E-011.00E+004.49E-011.69E-013.82E-011.00E+000.13755410.86244590.57755155230.1106438426

0.90909090910.090909090900376.57910.86234752.73E-040.06011450.07726480.54235167.82E-040.28247390.17439236.29E-012.86419508984.69893120632.25707307864.80E-013.14E-024.89E-011.00E+004.52E-011.55E-013.93E-011.00E+000.13694820.86305180.57188004490.0996228988

Feed, from the RD paper by Pöpken, the ration or HOAC:MeOH should be 1.56

Rectifying Section

Need to convert to groupsAbsorption: Water is removed from the V phase

GroupsC2H2OCH4OH2Oalpha

ABC

C2H2OCH4OH2O

C2H4O2101

CH4O010ReactionAC+B=AB+C

C3H6O2110

H2O001

Formular Matrix

C2H4O2CH4OC3H6O2H2O

A1010

B0110

C1001

,max

,

1

,

(1)!

1

(1)!!

p

n

ptot

k

ptot

n

nkk

=

éù

-

+

êú

--

êú

ëû

å

,max,1,(1)!1(1)!!pnptotkptotnnkk

Table 3

ϕ/ϑLoStOpPc

Reaction Present*













Yield ≥90%*




PCa6.5

MeOH13

DMC-

PDi-






DecanterPS (L/L)

V-Vapour, L-Liquid

T.BP


HOAc391.15289.75

MeOH338.15175.55

MeOAc330.05175.15

H20373.15273.15

EthOAc350.25189.55

DMSO462.00291.65

Azeotrope Search






ComponentTB [K]

HOAc391.15

MeOH338.15

MeOAc330.05

H20373.15

EthOAc350.25

DMSO462.00


H2O18.00373.15273.155.45-1.380.620.060.0147.80

MeOH32.04337.95175.555.030.011.560.040.0229.59

HOAc60.05391.05289.755.25-0.172.610.180.0419.01

MeOAc74.08329.95175.154.880.333.020.080.0519.35




TB [K]1.1040.9541.1310.8641.0241.185

TM [K]1.5560.9431.5600.6061.0021.654

log (Ws) i.e. log (mg/l)1.0831.0381.1170.9581.0311.076

log (Kow)-138.0008.118-4.182-0.0590.030-0.515







H2O-285.831

MeOH-239.11-1

HOAc-484.09-1

MeOAc-442.791

ΔHf [kJ/mol]-5.42

-4


X0.000218781

nA0.0002961

nB0.0041454

Keq45

Keqcalc45.0289141127

nA-X0.000077319

ConvA0.7388753794

nB-X0.003926619

ConvB0.0527768128

Table9




















Table 10






azeotrope

high energy demand







activation problems

degradation by T

degradation by pH








V-LTb***

S-LTM**





G-LTb, δSP***

R-


V-LTb***

S-LTM**





G-LTb, δSP***

R-

Table13





Mixing1-PhaseMIDI

MFl,tubI

MFl,recI

MVI/s1s1



PT(P:V-L)I


V:VPS(V:V)I/s14s14

L:LPS(L:L)I/s8s8


V:VPC(V:V)s13I/s13

L:LPC(L:L)s9I/s9



Cs6s12I/s1/s6/s12s1

Reaction-RI







MFl,tub+xxxx

MFl,rec+xxxx

MV+x

2-Phase2phM+xxx


PT(P:V-L)+x





Cx+x

Reaction-Rx+

Table14





















PB.14D-

PB.15H-

PB.16C-



















PB.10D-

PB.11H-

PB.12C-



Table14_modified



















PB.12D-

PB.13H-

PB.14C-



NSPB_Calc


1113991680013991680012121479001600147900160013

102362880027257600661123991680027983360078

93362880621772802201033628800621772800286

84403202496768049594362880248709120715

755040120604800792854032012048384001287

6672072051840092476504072036288001716

57120504060480079267720504036288001716

482440320967680495581204032048384001287

39636288021772802204016


2102362880072576006631063628800217728002868099


11113991680039916800122112399168007983360078

01214790016004790016001112147900160047900160013

0131622702080062270208001

np,max9

np,tot13np,max10

NSPB4017



NSPB8100


ABA!B!A!*B!

212123

121223

0316617

np,max3

np,tot4

NSPB8


ABA!B!A!*B!

13162270208001622702080014

122479001600295800320091

113399168006239500800364

104362880024870912001001

95362880120435456002002

8640320720290304003003

7750405040254016003432

6872040320290304003003

59120362880435456002002

410243628800870912001001

31163991680023950080036416277

np,max11

np,tot15

NSPB16278



SPB's_rev1


SPB.1M1..n(L)1(L)

SPB.2M=R1..n(L)1(L)

SPB.3M=H1..n(L)1(L)

SPB.4M=C1..n(L)1(L)





















SPB.25M1..n(L)1(L)
























SPB.49M1..n(L)1(L)
























SPB's_rev2


SPB.1M1..n(L)1(L)

SPB.2M=R1..n(L)1(L)

SPB.3M=H1..n(L)1(L)

SPB.4M=C1..n(L)1(L)
















SPB.20M1..n(L)1(L)



















SPB.39M1..n(L)1(L)





















SPB.1M=R=H=C1..n(L)1(L)





M=R=H=C1..n(L)1(L)

Figures5&6

ACM NameNew NameDuty [W]Duty [kW]





Reboiler1.QhT1.reb2769550.68542769.5506854236

Reboiler2.QhT2.reb5736528.56435736.5285642791

Reboiler3.QhT3.reb5748382.83325748.3828331897

Reboiler4.QhT4.reb1276645.64081276.6456408204

DMC_Cooler.QcDMC.cool289403.3666289.4033665544

PDO_Cooler.QcPDO.cool440295.8373440.2958373021

PC_Cooler.QcPC.cool201485.93201.4859287002

Heater_Feed2.Q_exFeed.heat365456.47365.4564711572

Heater_PS.Q_exPressure Swing.heat431976.77431.9767679506

T1.condT2.condT3.condT4.cond2517324.19426693125686907.72969832189194730.99644899551229990.1571143158T1.rebT2.rebT3.rebT4.reb2769550.68542361915736528.56427907945748382.83318965231276645.6408204371DMC.coolPDO.coolPC.cool289403.36655436386440295.83730209945201485.9287001518Feed.heatPressure Swing.heat365456.47115721332431976.76795063878T1.condT2.condT3.condT4.condDMC.coolPDO.coolPC.cool2517324.19426693125686907.72969832189194730.99644899551229990.1571143158289403.36655436386440295.83730209945201485.9287001518T1.rebT2.rebT3.rebT4.rebFeed.heatPressure Swing.heat2769550.68542361915736528.56427907945748382.83318965231276645.6408204371365456.47115721332431976.76795063878

Analysis of SPB's

SPB'sSPBCoCrossflowCounter current

SPB.1, SPB.20, SPB.39, SPB.58MNo reactionNo reactionNo reaction

SPB.3, SPB.23, SPB.42M=CNo reactionNo reactionNo reaction

SPB.2, SPB.21, SPB.40M=R0.729/inf1 phase1 phase

SPB.5, SPB.24, SPB.43M=R=H0.725/inf1 phase1 phase

SPB.6, SPB.25, SPB.42M=R=C0.733/inf1 phase1 phase

SPB.7, SPB.26, SPB.45M=Mv=R=2pM=PC=PT(VL)0.729/infno separate phasesno separate phases

SPB.8, SPB.27, SPB.46M=Mv=R=2pM=PC=PT(VL)=PS(VL)

Reaction Analysis

Heat Capacity Data, obtained from ICAS

Expression=A+B*T+C*T^2+D*T^3+E*T^4J/kmolK

HOAc139640-320.80.8985

MeOH105800-362.230.9379

MeOAc61260270.9

Water276370-2090.18.125-0.0141169.37E-06

Tref=303.15KT0=303.15T0=313.15T0=323.15

Xe(T)XEB(T)XEB(T)XEB(T)

TXeXEBXEBXEB

303.150.73699386160

304.150.73658152240.063896894

305.150.73617147480.1284984414

306.150.73576370070.1937937385

307.150.7353581820.2597705869

308.650.73475409410.3599838129

309.150.734553840.3937134824

310.150.73415498170.461648383

311.150.73375830870.5302024899

312.150.73336380390.5993566993

313.150.73297145050.669090459

3140.7326396290.72880342340

314.060.73261626430.73303330810.0593519558

314.150.73258123160.73938175380.0652517854

315.150.73219313070.81020709520.1311613016

316.150.73180713130.88154151450.197712032

317.150.73142321710.95335856060.2648860501

318.150.7310413721.0256303030.332664001

319.150.730661581.09832733850.4010250865

320.150.73028382541.17141880440.4699470536

321.150.72990809241.24487239540.5394061877

322.150.72953436561.31865438790.6093773096

323.150.72916262961.39272966770.67983377750

323.850.72890359070.72942709770.046634863

324.150.72879286910.75074749360.0667120247

325.150.72842506920.82208891560.1340199229

330.150.72661496010.4786570939

332.150.72590412880.6197814048

333.150.72555148780.6909220764

333.630.72538287130.725192799

334.150.72520067790.7624035615

335.150.72485168570.8341905546

Kremser Example

Example taken from Page 170, SEPARATION PROCESS PRINCIPLES 2ND ED

[email protected], 400 psiaA=L0/KiV0Si=1/AphiA

C16.650.0310150376

C21.640.1257621951

C30.5840.3531678082

nC40.1951.05769230770.9454545455

nC50.07132.89270687240.3456969697

Oil0.00010.0004848485

CompOil composition [lbmol/h]CompFeed gas Composition [lbmol/h]

C40.05C1160

C50.78C2370

Oil164.17C3240

L0165nC425

nC55

V0800

M=R=2phM=PC(VL)=PT(VL)=PS(VL)

InitialAnalysis of M=Mv=R=2pM=PC=PT(VL)=PS(VL)ConversionCalcuation of xi initial

xHOAcxMeOHxMeOAcxH2OT[K]xHOAcxMeOHxMeOAcxH2OyHOAcyMeOHyMeOAcyH2OKHOAcKMeOHKMeOAcKH2OWalWBlWClCheckWAVWBVWCVCheckV [kmol/hr]L [kmol/hr]XMeOHXHOAcFeed1kmol/hr

0.09090909090.909090909100339.48863.49E-040.75735480.02339480.21890164.17E-050.82251870.09558310.08185651.19E-011.08604144324.08565578680.37394199042.32E-027.63E-012.14E-011.00E+008.73E-028.38E-017.48E-021.00E+000.93439560.06560440.84710194120.9993201765Molar Ratio1.56HOAc:MeOH

0.13043478260.869565217400339.9187.33E-040.67016120.03216060.29694519.19E-050.74809380.14275750.10905671.25E-011.11628933464.43889417490.36726216393.18E-026.80E-012.88E-011.00E+001.25E-017.80E-019.55E-021.00E+000.88709390.11290610.76734971590.998740252NHOAc0.609375kml/hr

0.16666666670.833333333300340.47071.23E-030.58553570.03741370.37581861.66E-040.67880110.18510490.13592841.34E-011.15928217534.94751655140.36168619653.72E-026.00E-013.63E-011.00E+001.56E-017.29E-011.15E-011.00E+000.87311970.12688030.7169059840.9981946015xHOAc0.609375

0.20.800340.86931.82E-030.51272390.0411640.44428992.62E-040.61538640.22639180.15796011.44E-011.20022959735.49975221070.3555338534.12E-025.31E-014.28E-011.00E+001.85E-016.86E-011.29E-011.00E+000.85488150.14511850.66507014390.9975592475xMeOH0.390625

0.23076923080.769230769200341.25352.48E-030.44606810.0429040.50854353.84E-040.55664120.26515480.17781961.55E-011.24788389936.18018832740.3496644834.34E-024.68E-014.89E-011.00E+002.10E-016.49E-011.41E-011.00E+000.8420630.1579370.6181539850.9968970281

0.25925925930.740740740700341.62293.20E-030.38517510.0429990.56862625.38E-040.50207910.30167350.19570981.68E-011.30350871597.01582594940.34418006064.42E-024.09E-015.47E-011.00E+002.32E-016.17E-011.51E-011.00E+000.83222720.16777280.57382822370.9962035029

0.28571428570.714285714300341.8613.98E-030.3324790.04268410.62085827.22E-040.45140020.33780060.2100771.82E-011.35768033477.91396796470.33836550764.46E-023.58E-015.97E-011.00E+002.53E-015.90E-011.57E-011.00E+000.81906210.18093790.52842719080.9954099074

0.31034482760.689655172400342.20654.78E-030.28218180.04068280.67235179.54E-040.40379170.37054040.2247141.99E-011.43096294669.10803582840.33422091444.35E-023.09E-016.48E-011.00E+002.71E-015.65E-011.65E-011.00E+000.81244080.18755920.48674649910.9946115711

0.31972789120.680272108800342.31885.13E-030.26398650.03988420.69100331.06E-030.38560.38349740.22984282.07E-011.46068075459.61527121020.33262185584.31E-022.91E-016.66E-011.00E+002.78E-015.55E-011.67E-011.00E+000.80907110.19092890.46980140650.9942569355

0.38650306750.613496932500343.08278.59E-031.47E-010.03330460.81096592.34E-030.25403860.4803950.26322292.73E-011.726558730114.42428373260.32457949224.02E-021.73E-017.87E-011.00E+003.26E-014.95E-011.79E-011.00E+000.78170.21830.33553943790.9904066232

0.43502824860.564971751400343.67710.01461130.07931470.02959030.87648354.84E-030.15560450.55494860.28461133.31E-011.961862050818.75440938420.32471951844.23E-021.04E-018.53E-011.00E+003.59E-014.56E-011.86E-011.00E+000.75802910.24197090.22144950430.9834469194

0.47089947090.529100529100344.16160.02844150.04096040.03029920.90029880.01024020.0847890.60815360.2968173.60E-012.070023730220.0716058510.32968721055.55E-026.73E-028.77E-011.00E+003.82E-014.28E-011.90E-011.00E+000.73645380.26354620.13310994370.9680673172

0.48979591840.510204081600344.37310.04850320.02686610.03550510.88912550.01692030.05372850.63115650.29819473.49E-011.9998622817.77650253060.33537976367.75E-025.75E-028.65E-011.00E+003.93E-014.16E-011.91E-011.00E+000.71939420.28060580.09528534660.9473604333

0.49238578680.507614213200344.62140.05250230.02503780.03607370.88638610.01836850.05014540.63054060.30094543.50E-012.002787784917.47923279290.33951953898.14E-025.61E-028.62E-011.00E+003.94E-014.13E-011.94E-011.00E+000.72066010.27933990.09104296850.9433301427

0.50.500344.91250.06719850.02118410.04035940.87125790.02275130.04111376.34E-010.30227883.39E-011.940781057515.70529046520.34694526169.71E-025.56E-028.47E-011.00E+003.96E-014.07E-011.96E-011.00E+000.71476620.28523380.08179732540.9291417125

0.50738916260.492610837400345.24930.08519150.01840860.04624270.8501570.02760860.03427320.63479690.30332123.24E-011.861803722213.72750509810.35678257071.16E-015.71E-028.27E-011.00E+003.98E-014.02E-011.99E-011.00E+000.70805120.29194880.07666855680.9124540652

0.52153110050.478468899500345.63060.12805920.01560040.06481340.79152690.03664820.02583480.63761160.29990532.86E-011.65603446079.83765085620.37889464021.62E-016.74E-027.71E-011.00E+004.03E-013.96E-012.01E-011.00E+000.6827320.3172680.07984123720.8741206707

0.52606635070.473933649300346.0520.14288090.01471130.07022350.77218420.04012110.02384650.63353460.30249782.81E-011.62096483669.02168932050.39174305821.76E-017.00E-027.54E-011.00E+004.03E-013.93E-012.05E-011.00E+000.67953770.32046230.08167511920.8611358781

0.57081545060.429184549400348.02960.27492430.0109520.13614360.577980.0656180.0146050.62352190.2962552.39E-011.33354638424.57988403420.51256963912.91E-011.04E-016.04E-011.00E+004.08E-013.78E-012.14E-011.00E+000.57448250.42551750.15452993790.7290166317

0.6093750.39062500350.30610.36221568.06E-030.16206930.46765110.09028030.01065220.60652250.29254492.49E-011.3209688083.74236514870.62556230493.44E-011.12E-015.44E-011.00E+004.11E-013.64E-012.26E-011.00E+000.49322440.50677560.22370995430.6256976823

0.61538461540.384615384600350.9010.37654387.54E-030.1619880.45392320.0959660.01007510.59996790.29399082.55E-011.33533642853.70377990960.64766638943.50E-011.10E-015.40E-011.00E+004.10E-013.60E-012.30E-011.00E+000.48825760.51174240.22832005660.6107319703

0.62962962960.370370370400351.52680.402026.87E-030.16818670.42292630.10420069.20E-030.5972550.28934492.59E-011.33969182743.55114286680.6841496973.63E-011.11E-015.25E-011.00E+004.12E-013.56E-012.31E-011.00E+000.45274990.54725010.25975431190.5756516468

0.66666666670.333333333300354.12550.47165365.01E-030.16807690.35526060.13452097.07E-030.57374560.28466222.85E-011.41175425393.41358985080.8012771473.90E-011.06E-015.04E-011.00E+004.15E-013.40E-012.45E-011.00E+000.39302260.60697740.31439415210.4912707554

0.750.2500360.04160.60783362.48E-030.1488780.24081040.21576214.10E-030.51586930.26426813.55E-011.65480600823.46504721991.09741149054.31E-018.62E-024.83E-011.00E+004.23E-013.00E-012.77E-011.00E+000.2676080.7323920.44053769970.3294504933

0.80.200364.3680.68786561.49E-030.12592540.18471760.28531412.82E-030.46399030.2478714.15E-011.89388036983.68464424171.34189162274.49E-017.02E-024.81E-011.00E+004.28E-012.67E-013.05E-011.00E+000.21385850.78614150.49799627710.247779325

0.83333333330.166666666700367.27090.73703961.04E-030.11043940.15148520.33833282.16E-030.42757560.23193164.59E-012.08530522013.87158568411.53105121824.59E-016.03E-024.81E-011.00E+004.34E-012.43E-013.23E-011.00E+000.17341610.82658390.54997193870.198523094

0.85714285710.142857142900370.45940.78228046.94E-040.09155210.12547290.40091441.61E-030.37811640.21935945.12E-012.31783244884.13006801591.74826117834.66E-014.92E-024.84E-011.00E+004.38E-012.13E-013.49E-011.00E+000.1760490.8239510.5300252750.1656684868

0.88888888890.111111111100373.99350.83059514.16E-040.07310920.095880.47945651.09E-030.32478070.19467435.77E-012.61855273294.44240533342.03039528584.75E-013.86E-024.87E-011.00E+004.46E-011.81E-013.74E-011.00E+000.14894810.85105190.56143689910.1244196182

0.90.100375.26150.84676783.39E-040.06681850.08607430.50982949.29E-040.30498640.18425526.02E-012.73721939534.56440057772.1406529014.77E-013.51E-024.87E-011.00E+004.49E-011.69E-013.82E-011.00E+000.13755410.86244590.57755155230.1106438426

0.90909090910.090909090900376.57910.86234752.73E-040.06011450.07726480.54235167.82E-040.28247390.17439236.29E-012.86419508984.69893120632.25707307864.80E-013.14E-024.89E-011.00E+004.52E-011.55E-013.93E-011.00E+000.13694820.86305180.57188004490.0996228988

Feed, from the RD paper by Pöpken, the ration or HOAC:MeOH should be 1.56

Rectifying Section

Need to convert to groupsAbsorption: Water is removed from the V phase

GroupsC2H2OCH4OH2Oalpha

ABC

C2H2OCH4OH2O

C2H4O2101

CH4O010ReactionAC+B=AB+C

C3H6O2110

H2O001

Formular Matrix

C2H4O2CH4OC3H6O2H2O

A1010

B0110

C1001

,max

,

1

,

(1)!

1

(1)!!

p

n

ptot

k

ptot

n

nkk

=

éù

-

+

êú

--

êú

ëû

å

,max,1,(1)!1(1)!!pnptotkptotnnkk

Table 3

ϕ/ϑLoStOpPc

Reaction Present*













Yield ≥90%*




PCa6.5

MeOH13

DMC-

PDi-






DecanterPS (L/L)

V-Vapour, L-Liquid

T.BP


HOAc391.15289.75

MeOH338.15175.55

MeOAc330.05175.15

H20373.15273.15

EthOAc350.25189.55

DMSO462.00291.65

Azeotrope Search






ComponentTB [K]

HOAc391.15

MeOH338.15

MeOAc330.05

H20373.15

EthOAc350.25

DMSO462.00


H2O18.00373.15273.155.45-1.380.620.060.0147.80

MeOH32.04337.95175.555.030.011.560.040.0229.59

HOAc60.05391.05289.755.25-0.172.610.180.0419.01

MeOAc74.08329.95175.154.880.333.020.080.0519.35




TB [K]1.1040.9541.1310.8641.0241.185

TM [K]1.5560.9431.5600.6061.0021.654

log (Ws) i.e. log (mg/l)1.0831.0381.1170.9581.0311.076

log (Kow)-138.0008.118-4.182-0.0590.030-0.515







H2O-285.831

MeOH-239.11-1

HOAc-484.09-1

MeOAc-442.791

ΔHf [kJ/mol]-5.42

-4


X0.000218781

nA0.0002961

nB0.0041454

Keq45

Keqcalc45.0289141127

nA-X0.000077319

ConvA0.7388753794

nB-X0.003926619

ConvB0.0527768128

Table9




















Table 10






azeotrope

high energy demand







activation problems

degradation by T

degradation by pH








V-LTb***

S-LTM**





G-LTb, δSP***

R-


V-LTb***

S-LTM**





G-LTb, δSP***

R-

Table13





Mixing1-PhaseMIDI

MFl,tubI

MFl,recI

MVI/s1s1



PT(P:V-L)I


V:VPS(V:V)I/s14s14

L:LPS(L:L)I/s8s8


V:VPC(V:V)s13I/s13

L:LPC(L:L)s9I/s9



Cs6s12I/s1/s6/s12s1

Reaction-RI







MFl,tub+xxxx

MFl,rec+xxxx

MV+x

2-Phase2phM+xxx


PT(P:V-L)+x





Cx+x

Reaction-Rx+

Table14





















PB.14D-

PB.15H-

PB.16C-



















PB.10D-

PB.11H-

PB.12C-



Table14_modified



















PB.12D-

PB.13H-

PB.14C-



NSPB_Calc


1113991680013991680012121479001600147900160013

102362880027257600661123991680027983360078

93362880621772802201033628800621772800286

84403202496768049594362880248709120715

755040120604800792854032012048384001287

6672072051840092476504072036288001716

57120504060480079267720504036288001716

482440320967680495581204032048384001287

39636288021772802204016


2102362880072576006631063628800217728002868099


11113991680039916800122112399168007983360078

01214790016004790016001112147900160047900160013

0131622702080062270208001

np,max9

np,tot13np,max10

NSPB4017



NSPB8100


ABA!B!A!*B!

212123

121223

0316617

np,max3

np,tot4

NSPB8


ABA!B!A!*B!

13162270208001622702080014

122479001600295800320091

113399168006239500800364

104362880024870912001001

95362880120435456002002

8640320720290304003003

7750405040254016003432

6872040320290304003003

59120362880435456002002

410243628800870912001001

31163991680023950080036416277

np,max11

np,tot15

NSPB16278



SPB's_rev1


SPB.1M1..n(L)1(L)

SPB.2M=R1..n(L)1(L)

SPB.3M=H1..n(L)1(L)

SPB.4M=C1..n(L)1(L)

















SPB.21

Documents

SustainableProcess Synthesis- Intensification › ... › iets-expert-workshop-rgani.pdf · 2018-04-11 · SPEED SustainableProcess Synthesis-Intensification Rafiqul Gani. Department