uni-oldenburg.pdf

8/22/2019 uni-oldenburg.pdf

1/28

Techn ische Chemie

Computer Aided Synthesis, Designand Optimization of Chemical Processes

Development of thermodynamic models:

UNIFAC, Mod. UNIFAC (Do), PSRK, LIFAC, ...

Development of Software Tools:

Selection of selective solvents,

construction of residual curves,

fitting of recom. model parameters,

environment protection,laboratory safety,

CAMD, ...

Pilot plants:

e.g. for reactive distillation

methanol

acetic acidmethyl acetate

water

reaction

extractive distillation

methanol stripper

}

}

}

uebrshte.cdr, 13.09.99

x P = y Pi i i iS f = fi

L iV

x = yi

iL

i

iV

(e.g. VLE)

Research

activities

DECHEMA

Thermodynamik

Dortmund Data Bank:

VLE, h , ...

P , , c

E

is v Ph ,...

Measurements of phase equilibria,excess properties, pure component

properties, kinetic data, ... in a widetemperature and pressure range

Development of sophisticatedexperimental facilities:

TP

www.uni-oldenburg.de/tchemie


2/28

Aspects to be Considered During theSynthesis of Separation Processes

Technische Chemie

Separation

Process

?

?

?

?

?

Nth=?

?x1

x1

y1

T

12=

1 1sP

2 2sP

1

Suitable Solvent for Extractiveor Azeotropic Distillation ?

?ABCD

AB

CD

A

B

C

D

S =n

[2(n-1)]!

n! (n-1)!Tn-1

Distillation? Crystallization?

Separation Problems ?

Sequence ?

Column Height ?

sepproc1.cdr; 04.05.99


3/28

Ruhrchemie / Rhone-Poulenc ProcessRCH_RP_process.cdr, 06.11.2000

CO + H2

51 bar

55 bar

gas solubilitiesVLE

reaction kinetics

gas solubilities

partition coefficientsLLE

VLEco-solvent ?

reactor design:

stripper design:

phases:

aqueous

organic

gas / vapor

propylene + CO + H2

crude (n/i)-butyraldehyde

(n / i) butyraldehyde

125 C

propylene

Technisch e Chemie

HRh(CO)[P(C H SO Na) ]6 4 3 3 3


4/28

Techn ische Chem ie

Prediction of a Chemicals Fatein the Various Environment Compartments

ri

i

i

KOW_dist.cdr

air

soil

water

sediment

aerosol

K = 0.0082 Ksoil-water OW

K = v H / RTair-water

Wi,W

K = = 0.1508 OW

= v P / RTW

i,W

is

i

,W

i,O

K = 0.045 Kfish-wate r OW

K = 0.0164 Ksediment-water OW

(1/c )is,W P / RT

is

=BCF

ciO

ciW


5/28

Tech nisc he Ch emie

Measurements in our research groupri

i

i

ri

i

i

solid-liquid equilibria(visual technique)-90C < T < 50C

P = Patm

vapor-liquid equilibria(static and

dynamic apparates)T up to 190C

P up to 120 bar

(batch and flow reactors)T up to 100CP up to 10 bar

kinetics

adsorption equilibria(flow apparatus)

0 < T < 50CP = P

atm

(spinning band column)T up to 150CP up to 3 bar

azeotropic data

(GLC or Dilutor-technique)

0C < T < 150CP = P

atm

activity coefficientsat infinite dilution

pure component properties(various apparates)

T up to 150C

P up to 600 bar

(flow calorimeter)

25 C < T < 150CP up to 150 bar

excess enthalpies

cP

PiS

i8

More details on: www.ltp-oldenburg.de


6/28

Status of the Dortmund Data Bank* (April 2002)

41000 References, 1800 Journals, 15000 Compounds

DDB

22900 (VLE)

2917 (ELE)

19398 (HPV)

VLE**

(total: 45215 data sets)

* detailed information is available via internet (www.ddbst.de)** includin un ublished VLE data of com anies from the former German Democratic Re ublic

40769 data points for puresolvents

885 data points forsolvent mixtures

10769 data sets for non-electrolytes

3528 data sets

for electrolytes

12943 data sets

45716 data points

13861 data sets3067 data sets

16423 data sets

1483 data sets

15865 data sets

130219 data sets

LLE

azeotr. data

GLEADS

vE

cPE

hE

DDBstat3e.cdr, 17.05.2002

(E)SLE

Pure Component Properties


7/28

Status of DDB-Pure (April 2002)

Pure_April_2002.xls

Property Compounds References Sets Points

Vapor Pressures 5000 5473 19661 140275

Critical Data 884 835 3071 3073

Densities 6869 5183 35344 258573Virial Coefficients 267 414 1244 6737

Molar Heat Capacities 1874 1390 7647 120688

Heats of Vaporization 2151 966 4385 9549

Heats of Fusion 1652 989 2767 2806Melting Points 4485 2576 11303 12042

Transition Heats / Temperatures 645 546 1168 1183

Entropies 1436 876 2566 7556

Heats of Combustion / Formation 3700 1420 4933 4940

Viscosities 2091 2172 15190 91907

Thermal Conductivity 762 876 8365 76285

Surface Tensions 1992 569 4363 18987

... ... ... ... ...

Sum 13321 16833 130218 840619


8/28

per_year.doc, 03.11.2000

Typical Number of Mixture Data Sets* Published Every Year

Vapor-liquid equilibria

a) normal boiling substances: 800 data sets

b) low boiling substances: 1000 data sets

c) electrolyte systems: 200 data sets

Activity coefficients of infinite dilution: 1250 data points

Azeotropic data: 1000 data points

Liquid-liquid equilibria: 400 data sets

Solid-liquid equilibria: 400 data sets

Gas solubilities: 700 data sets

Excess enthalpies: 600 data sets

Excess volumes: 1200 data sets

Sum: 5300 data sets + 1250 + 1000 az. data

*data set = isothermal, isobaric, ..., (appr. 15 data points)


9/28

Techn ische Chemie

Availability of the Dortmund Data Bank

availability.cdr, 03.11.2000

inhouse-

version

D

D B

ortmund

ata ank

Internet

www.dechema.de

integrated inuser interface

andavailable via internet

ASPEN PlusDETHERM Data Base

(www.fiz-karlsruhe.de)responsible:FIZ CHEMIE

www.ddbst.com(free data directory)

Textbooks:DECHEMA Data Series

and VCH-Wiley

inhouse-version

software package

(free demo version)DDBSP


10/28

Different Applications of DDB

DDB(MIX, PURE

Data Base for Fitting(gE, EOS)-Model Parameters

(Recommended Values)

Validation ofParameters

Prior to Process

Simulation

Development ofThermodynamic Models(UNIFAC, mod. UNIFAC, PSRK, ...)

Publication of Data Compilations

(DECHEMA Series, Azeotropic Data)

Selection of Selective

Solvents by DDB-Access

planned:Publication of

Recommended

Values as f(T,P),

Data Compilations

Further Development of

Prediction Methods forPure Component

Properties

Computer Aided

Molecular

Design(ARTIST, ...)


11/28

benzene in ethanol

ethanol in benzene

1000 / T [K]

h[

J/m

ol]

E

ideal vapor phase

real vapor phase

data base: VLE

data base: VLE, h ,E

Tec hnisch e Chemie

Simultaneous Correlation (Wilson)Ethanol (1) + Benzene (2)

ri

i

i ri

i

i

180 mmHg300 mmHg450 mmHg760 mmHg

90C45C25C

1.0

3.0 250.

1.0

3.6

1.0

1.0

0.8

2.6 200.

0.8

3.4

0 .8

0.8

0.6

2.2 150.

0.6

3 .2

0.6

0.6

0.4

1.8 100.

0.4

3.0

0.4

0.4

0.2

1.4 50.

2000.

1000.

1500.

500.

0.0.2

2 .6 2.8

0.2

0.2

0.0

1.0 0.

0.0

2.4

0.0

y1

x1

x1

y1,az

lni

Temperatur

e[C]

1131wilson_e.cdr, 08.11.2000


12/28

Tech nische Ch emie

DDB: An Ideal Tool for the CriticalExamination of Model Parameters:

Acetone (1) + Cyclohexane (2) (Wilson)

ri

i

i

azeotropicdata

cyclohexane in acetoneacetone in cyclohexane

0o

C

25oC

50 Co 25 Co35 Co

14 0 Co

SLE

P

/mm

Hg

Temperature/C

Temperature/C

x , y1 1

x1

x1y1,az

VLE

1000T /K-1

lni

i8

8

h

/J

mol

E

-1

hE

wilson.cdr, 18.05.99


13/28

data_base.doc, 03.11.2000

Models Developed With the Help

of the Dortmund Data Bank

Model Data Base Used for Fitting the Parameters

UNIFAC: VLE (LLE, )

Modified UNIFAC (Dortmund): VLE, hE, SLE, ,LLE, azeotropic data (cP

E)

KOW-UNIFAC: KOW, , water solubilities

LIQUAC / LIFAC: VLE, osmotic coefficients, ,

SLE, LLE of electrolyte systems

PSRK: VLE of low boiling systems, gas solubilities

extended PSRK: VLE for asymmetric mixtures + LIFAC model


14/28

original UNIFACri

i

i

P / mmHg

/ C

h /Jmol

E

-1

number of carbon-atoms

acetone + heptane

acetone + heptane

F = VLE (+ LLE + ) 8

no

quantitativeinfomationabout (T)

ln i iE

h

= !

no data forcompounds

of verydifferent size

extrapolationto infinite

dilutioncan bedangerous

0C

40C

50C

x , y1 1

heptanein

n-alkanes

8

heptanein

acetone

acetone

inheptane

8

8

x1

90C35C10C

0.0 0.5 1.0

0.0 0.5 1.0

20. 40. 60. 80. 100. 0.0 25. 50.

700.

400.

300.

200.

100.0.

500.

600.

1.2

1.0

0.8

0.6

0.4

0.2

2000.

1000.

0.

10.

8.

6.

4.

2.

unifac1.cdr, 14.06.99

Modified UNIFAC (Dortmund)ri

i

i

0C

35C

55CP / mmHg

x , y1 1

T / C

0. 40. 80.

16.

12.

8.

140C 90C25C

x1

0. 0.5 1.0

2000.

1000.

0.

h /

Jmol

E

-1

acetone + cyclohexanenumber of carbons

0. 25. 50.

1.0

0.2

hexanein

alkanes

8cyclohexanein

aniline

8

acetone + aniline

lnE

h

F = VLE + LLE + + h + c E PE

+ SLE+ AZD

8

quantitative

infomation about(T) usingenthalpies of mixing

improved results forasymmetric mixtures

using a modifiedcombinatorial part

mixtureinformation of

the dilute region

are used forfitting

!

0. 0.5 1.0

1000.

500.

0.

ln i iE

T

h

R1

= !

ln i iE

T

h

R1

= !


15/28

-100 0 100 200

h (c )E EP

VLE(azeotropic data)

LLESLE

i is

,P

ln i iE

T

h

R1

=

ln,

,x

h

RT

T

Ti i

m i

m i =

1 i i

' ' '

Temperature / C

Technische Chemie

Temperature Ranges ofThermodynamic Mixture Data

ri

i

i

nm= -(a + b T + c T )nm nm nm2

Texp

nm= -anmTexp

Modified UNIFAC (Dortmund):

UNIFAC:

F = VLE + LLE +

+ SLE + h + c E

PE

+ AZD

8

F = VLE (+ LLE + ) 8


16/28


17/28

Technische Chemie

Experimental and Predicted (Modified UNIFAC (Dortmund))Data for the System Ethanol (1) + Benzene (2)

ri

i

i

1131modu_e.cdr, 03.11.2000

x1x1

y1,az

x1

y1

h

/Jm

ol-1

E

140C90C

45C25C

760 mm Hg400 mm Hg

300 mm Hg180 mm Hg

Temperature [C]

Temperature

[C]

Temperature[C]

benzeneinethanol8

ethanolin benzene8

i8

8

VLE

azeotropicpoints

SLE

hE Modified UNIFAC (Dortmund)

ideal


18/28

Techn ische Chemie

Deviations between experimental and calculatedVLE-Data for 2200 consistent Data Sets

ri

i

i

T [K]

0.55

0.87

1.68

P [kPa]

0.42

0.68

1.06

y [%]

0.58

0.88

1.41

UNIQUAC Modified UNIFAC (Dortmund) UNIFAC


19/28

Techn ische Chemie

Objectives of the UNIFAC consortium(UNIFAC and Modified UNIFAC (Dortmund))

ri

i

i

filling gaps (DDB, additional measure-ments or confidential data)

extension withthe view tonew groups{

examination and (if necessary) revision (DDB)

improvement of predictions for hydrocarbon / water solubilities:improvement of predictions for isomeric compounds

consideration of proximity effects

additionally:

l

l

l

l eventually filling gaps using molecular-modelling results (e.g. COSMO-RS)( )all missing parameters ( 1400) ?; only parameters of special interest ?

D

D

D

D

D

D

D

D

D

published parameters

new or revisedparameters


20/28

S f h PSRK P M i


21/28

no parameters fitted

original UNIFAC parameters

Ind. Eng. Chem. Res. 30, 2352 (1991)

70, 251 (1991)and 121, 185 (1996)

PSRK parameters

Fluid Phase Equilibria



141, 113 (1997)

167, 173 (2000)

PSRK parameters

NH3

CO2

CH4

O2Ar

N2

H2S

H2

CO

SO2NO

N2O

SF6

He

Ne

Kr

XeHF

HCl

HBr

HI

COS

F2

Cl2

Br2

HCN

NO2

CF4O3

ClNO

1

23

45

67

89

1011

1213

1415

1617

1819

2021

2223

2425

2627

2829

3031

32

3334

35

3637

38

3940

4142

43

4445

4647

4849

5051

5556

57

5859

6061

62

63

65

6667

6869

70

7172

7374

757677

7879

8081

8283

84

85

PSRK parameters

latest progress

PSRK parameters

Status of the PSRK Parameter Matrix

(November 2000)

Fi ld f li ti


22/28

Technisch e Chem ie

Fields of applicationfor thermodynamic models

ri

i

i

knowledge of

the real mixturebehavior ( , , PVT)

required for i i

synthesis of separation processes(selection of selective solvents,optimum separation sequence,...)

design ofseparation columns (N )th

chemical reactions(selection of co-solvents for biphasic reactions,kinetic expressions, ...)

analytical purposes (GLC, ..)

diffusional mass transfer

safety aspects

(flash points, ...)

calculation of thermodynamic

properties (h, s, ..., h , h (P), ...) v R

calculation ofphase equilibria

(VLE, LLE, SLE, GLE, ...)

calculation ofexcess properties(h , c , v , ...)E P

E E

standard properties

( h , g ) Bo

Bo

chemical equilibrium(K , K )

labor safety(safety clothes, exposition, ...)

environmental protection

(K fate of a chemical,

bioaccumulation, ...)

OW

ddb t d


23/28

Calculation ProgramsParameter Fitting

PCPPresentation Programs

Techn ische Chem ie

D D B S P ortmund ata ank oftware ackage (DDBSP)r

i

i

i

DDB - Mixture Data

VLE h ACT GLE LLE AZD SLE ...E

DDB - Pure Component Data

P c crit. T his

P m fus

Recommended ValuesRecommended Values

PredictionPrediction

Wilson NRTL UNIQUAC SRK PR ...

UNIFAC Mod. UNIFAC (Do) ASOG PSRK . ..

...

Phase EquilibriaSimulation ProgramsFlash Points

UNIFACMod. UNIFAC (Do)PSRKLIQUAC

experimentalcorrelated

predicted

DiagramsTables

DDBSP_win.cdr; 06.11.2000

www.ddbst.de

A eotropic data for the q aternar s stem


24/28

Azeotropic data for the quaternary system

benzene(1)-cyclohexane(2)-acetone(3)-ethanol(4)

predicted (mod. UNIFAC (Do)) experimental*

system

type of

azeotrope

/ C y1,az y2,az type of

azeotrope

/ C y1,az y2,az

1-2 homPmax 77.5 0.543 homPmax 77.6 0.543

1-3 none none

1-4 homPmax 68.0 0.537 homPmax 67.9 0.5522-3 homPmax 54.3 0.221 homPmax 53.2 0.248

2-4 homPmax 65.3 0.545 homPmax 64.8 0.553

3-4 none none

1-2-3 none none

1-2-4 homPmax 65.1 0.126 0.441 homPmax 64.9 0.113 0.462

1-3-4 none none

2-3-4 none none


25/28

32

14

4

4

(1) 56.4 C

(2) 61.1 C(3) 64.9 C

(4) 155.0 C

(1)-(2) 64.4 C

(1)-(3) 59.6 C

(2)-(3) 53.7 C(1)-(2)-(3) 57.8 C

Residual Curves and Distillation Border Plain of the System

Acetone(1) - Chloroform(2) - Methanol(3) - Cyclohexanone(4)

Mod. UNIFAC (Do)

P = 1 atm

stable point

saddle point

instable pointResidue_quat_1e.ppt


26/28

Tech nische Chemie

Azeotropic and Extractive Distillationri

i

i

cyclohexane benzene

entrainer

cyclohexane+benzene

benzene +entrainer

Formation of a lowboiling binary or ternary(hetero-) azeotrope

1 212=

1

1

sP

2 2sP

1

S =12

1,entrainer8

2,entrainer8

8

Azeotropic Distillation

Extractive Distillation

cyclohexane in aniline

benzene in aniline

1000 / T[K]

ln i8 Mod. UNIFAC (Do)

exp. data

>>1 (


27/28

Input:ComponentsPressure (Temperature)Distillation Process

Examination of thebinary VLE behavior

Search of binary data

(azeotropic data, )for component 1 and 2

Search of ternary

data withcomponent 1 and 2

Output:

List of suitable solventsincluding experimentalinformation

Selection criterionfulfilled ?

Determination of

and T (P )

for given P(T)

12 az az

Technische Chemie

Selection of SelectiveSolvents by DDB Access

ri

i

i

DDB-MIX

azeotropic data(43000 values)

(34400 values)

Recommendation ofalternative distillationprocesses in case of:1. Zeotropy2. Heteroazeotropy3. Strong pressure

dependence of y4. Zeotropy at low

(high) pressure

az


28/28

com ponents to be s eparated : (1) ACETIC ACID (2) W ATER

lis t of sol vents i ntroduci ng o ne furth er binar y az eot rope (wi th press ure maximum)

--- -------- ------- -------- ------------ -------- ------- -------- -------- ------------ --- ---- -sel ective s olvent (3) typ es o f azeotr opes introdu ced : Tb(az,bin.)Tb( az,ter.) Tm(3)

(1)-( 3) (2)-(3) (1)- (2)- (3) [ K]--- -------- ------- -------- ------------ -------- ------- -------- -------- ------------ --- ---- -

CYC LOPENTAN ONE no ne hetPmax Misgap n.a. 3 67.75 -- - 2 22. 503-P ENTANONE no ne hetPmax Misgap n.a. 3 55.98 -- - 2 34. 15

ETH YL PROPI ONATE no ne hetPmax Misgap n.a. 3 53.15 -- - 1 99. 25

BUT YL ACETA TE no ne hetPmax Misgap none Mis gap 3 63.81 -- - 1 99. 70

PRO PYL ACET ATE no ne hetPmax Misgap none Mis gap 3 55.52 -- - 1 78. 00

DIP ROPYL ET HER no ne hetPmax Misgap n.a. 3 48.55 -- - 1 47. 05

DIE THYL ETH ER no ne hetPmax Misgap n.a. 3 07.34 -- - 1 56. 85DIB UTYL ETH ER no ne hetPmax Misgap n.a. 3 66.65 -- - 1 75. 30

2-P ENTANONE no ne hetPmax Misgap n.a. 3 56.15 -- - 1 96. 25

DII SOPROPYL ETHER no ne hetPmax Misgap none 3 36.15 -- - 1 86. 35

ETH YL BUTYL ETHER no ne hetPmax Misgap n.a. 3 49.15 -- - 1 49. 15

1,2 -DICHLOR OETHANE no ne hetPmax Misgap none Mis gap 3 44.80 -- - 2 37. 65

DIC HLOROMET HANE no ne hetPmax Misgap none 3 11.25 -- - 1 78. 01

ISO PENTYL A CETATE no ne hetPmax Misgap n.a. 3 66.95 -- - 1 95. 15

DII SOBUTYL KETONE no ne hetPmax Misgap n.a. 3 70.15 -- - 2 27. 17

2,3 -BUTANED IONE no ne hetPmax Misgap n.a. 3 51.60 -- - 2 70. 75

MET HYL PROP IONATE none hetPmax Misgap n.a. 3 44.75 --- 1 85. 70

BUT YL PROPI ONATE no ne hetPmax Misgap n.a. 3 67.95 -- - 1 83. 65

... .. . ... ... ... . .. ...

--- -------- ------- -------- ------------ -------- ------- -------- -------- ------------ --- ---- -

P = 1 01 .32 kPa Tb (1 ) = 39 1.01 [K ] Tb(2) = 373.1 5 [ K]

DDB acce ss

Technisc he Ch emie

Typical Result for the Search of Suitable Solventsby DDB Access

ri

i

i

solvent (3)

-----------------

CYCLOPENTANONE3-PENTANONE

ETHYL PROPION ATE

BUTYL ACETATE

PROPYL ACETAT E

DIPROPYL ETHE RDIETHYL ETHER

DIBUTYL ETHER

...

(1) ACETIC ACID (2) WATER

azeotropic disti llation: one further

(heterogeneous pressure maximum ) azeotrope

DDB access; P = 101.32 kPa

azeotrope introduced:

(2) - (3) Tb [K]

--------------------

hetPmaxMisgap 367.75hetPmaxMisgap 355.98

hetPmaxMisgap 353.15



hetPmaxMisgap 348.55hetPmaxMisgap 307.34

hetPmaxMisgap 366.65... ...

seloutde.cdr; 04.05.99

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