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Adsorption

is a separation using the surface properties of a solid (rarely of a liquid) Adsorption uses different thermodynamical and mass transfer principles as distillation. Adsorptive: Adsorbate: Adsorbens: Load: Adsorber: Chemisorption: Physisorption: component which has to be adsorbed component which underwent adsorption and is now on the surface solid (liquid) to be suited to adsorb the gas on the surface concentration of the adsorbate in the adsorbens [mol/kg or kg/m2] the apparatus used driving forces come from a chemical reaction (used as a rescue filter) driving forces come from van-der-Waals forces

in 99,99% the heat of adsorption is exothermic (minus sign) because the bulk of the adsorbens is not used, there is no excess volume

Trenntechnik I Prof. Arlt Adsorption

solvent/Volatile Organic Compounds recovery from offgas (dry cleaning) gas scrubbing/gas separation (oxygen-nitrogen) separation of odor from air or water decolouring of liquids (wine) drying of liquids (from water)

kitchen hood little bags in electronic devices (for water)

examples for adsorption

Trenntechnik I Prof. Arlt Adsorption

gas phase adsorption exoothermic desorption endothermic Adsorptive

boundary layer pore

Adsorbate

active center Adsorbens

The surface is not completely covered by the adsorbent. The adsorbate molecules are so far away from each other that they in general- do not see each other. So there is no link between the thermodynamics of each molecule. On a heterogenous surface, not all locations are equally suited for adsorption. molecular sight
Trenntechnik I Prof. Arlt Adsorption

T1> T2> T3> T4

P1> P2> P3> P4

x1< x2< x3<x4

because of the 99,99% unique sign of the heat of adsorption, all isotherms/isobars/isosters follow the same route (Gibbs-Helmholtz equation) The adsorption isotherm is the pure component data in adsorption! Thermodynamics: adsorption isotherms
Trenntechnik I Prof. Arlt Adsorption

T=const

capillary condensation multi-layer adsorption


Henry l ine

concentration, e.g.Pi/PiLV

load

mono-layer adsorption

mono- and multi-layer adsorption

Trenntechnik I Prof. Arlt Adsorption

bulk or mobile phase

phase boundary

adsorbate

adsorbens or stationary phase

stronger adsorbing component

weaker adsorbing component selectivity


Trenntechnik I Prof. Arlt Adsorption

Xi

Gibbs phase boundary (Findenegg [1996])

real behaviour

distance from the adsorbance surface phase boundary


Trenntechnik I Prof. Arlt Adsorption

empirical approach (Freundlich isotherm)

X i = m Pi

X i = m Yi

an approach from kinetics: Langmuir isotherm mono-molecular layer energetically homogenous surface no interaction between adsorbed molecules no mobility of adsorbed molecules on the surface only one molecule per adsorption site

Thermodynamics

Trenntechnik I Prof. Arlt Adsorption

Irving Langmuir was born in Brooklyn, New York, on January 31, 1881 He graduated as a metallurgical engineer from the School of Mines at Columbia University in 1903. Postgraduate work in Physical Chemistry under Nernst in Gttingen earned him the degrees of M.A. and Ph.D. in 1906. Returning to America, Dr. Langmuir became Instructor in Chemistry at Stevens Institute of Technology, Hoboken, New Jersey, where he taught until July 1909. He then entered the Research Laboratory of the General Electric Company at Schenectady where he eventually became Associate Director. After a short illness, he died on August 16, 1957. Nobel Prize in Chemistry (1932)

Langmuir

Trenntechnik I Prof. Arlt Adsorption

the kinetics between adsorption and desorption are in equilibrium

dX dX = dt Adsorption dt Desorption

1st order kinetics for adsorption proportional to pressure; N is the number of all sites being able to adsorb; (1-Z) is the fraction of empty sites same approach for desorption

dX = k A P N (1 Z ) dt

dX = kD N Z dt
kA P kA P kD NZ=N =N k kA P + kD 1+ A P kD

adsorption equals desorption

Langmuirs adsorption isotherm 1

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kA P kA P kD in terms of load = XS X = XS k kA P + kD The model has 2 adjustable parameters: 1+ A P kD red and blue

A model for multi-layer adsorption: Brunauer, Emmett and Teller (BET)

Langmuirs adsorption isotherm 2

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compound

normal boiling point C 46,2 64,6 61,2 76,7 34,5 80,1 -103,9

enthalpy of vaporization kJ/kg 351 1118 244 194 370 389 394

adsorption temperature C 25 25 25 25 25 25 25

integr. enthalpy of adsorption kJ/kg 703 1790 522 461 940 866 1040

CS2 CH3 OH CHCl3 CCl4 (C2 H5 )2 O C6 H6 C2 H4

The integral heat of adsorption is more or less 2 times the heat of vaporization! heats of vaporization and integral heat of adsorption on active carbon
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mass transfer zone MTZ loaded absorber BA unloaded absorber FA

mass transfer

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phase boundary

The total adsorption area is determined by the adsorption of nitrogen at low temperatures.

The macropores are determined by pressing mercury in the sample. The micropores are determined by capillary condensation of nitrogen at low temperatures.

Because of the size mesopores are preferred for capillary condensation.

pores

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adsorbens

surfac e area m/g 1000 1500

micro pore cm/g 0,6-0,8

macro pore cm/g 0,5- 0,8

powder density g/l

true density g/cm

apparent density g/cm ca. 0,6

specifi c heat J/kgK 840

active carbon for gas- u. vapour adsorption active carbon for water purification active carbon for decouloring silica gel

300-450 ca. 2,0

500 - 800 700 -1400 600 - 850 250 - 350 300 350 500 1000

0,3-0,6

0,3-0,4

300-550 ca. 2,0

ca. 0,6

840

0,45-1,2

0,5- 1,9

250-500 ca. 2,0

840

0,35-0,45

<0,1

700-800 ca. 2,2

ca. 1,1

920

silica gel aluminium oxide Molecular sieve

0,3- 0,45 0,4

0,05- 0,1 ca. 0,1

400-800 ca. 2,2 700-800 ca. 3

ca. 1,1 ca. 1,2

920 880

0,25-0,30

0,35- 0,4

600-900 ca. 2,6

ca. 1,1-1,5

920
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thermo-physical data for adsorbens

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equilibrium slope A(1)/F

Y [kg adsorptiv/kg fluid]

slope A(2)/F

F (Y(1) Y0 ) = A (1) (X (1) X 0 )


F (Y( 2 ) Y(1) ) = A ( 2 ) (X ( 2 ) X 0 )

X [kg adsorbate/kg adsorbens]


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mass balance for a cross-current adsorption process

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1-> 2: temperature swing 1-> 3: pressure swing 1-> 4: pressure + temperature swing

X load of adsorbens

Y(1),in

Y (Tcond)

Y(2),in

adsorptive in regeneration medum temperature increase pressure decrease concentration decrease desorption
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2 fixed bed adsorber (upright or horizontal)

fluidized bed adsorber

moving bed adsorber

2 rotary adsorber (upright or horizontal)

flue dust adsorber radial flow uncommon types of adsorber for VOC flue gas
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fixed bed adsorber by Lurgi/steam regenerated

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100

PSA-Festbett TSA fixed bed

concentration feed [g/cm3] Konzentration Eintritt [g/m]

10

TSA-Dampf-Festbett TSA-vapour fixed bed

mobile adsorber Wechsel-Adsorber

TSA-Ox-Festbett TSA/ox fixed bed TSA-Rotor

0,1

Grenzwert TA Luft (Klasse I) 0,01 10 100 1000 10000 100000 1000000

Volumenstrom [m/h] volumetric flow [m3/h]

range of application

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