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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
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)
Adsorbate
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
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
concentration, e.g.Pi/PiLV
load
mono-layer adsorption
phase boundary
adsorbate
Xi
real behaviour
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
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
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
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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
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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
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
Trenntechnik I Prof. Arlt Adsorption
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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.
pores
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adsorbens
active carbon for gas- u. vapour adsorption active carbon for water purification active carbon for decouloring silica gel
500 - 800 700 -1400 600 - 850 250 - 350 300 350 500 1000
0,3-0,6
0,3-0,4
ca. 0,6
840
0,45-1,2
0,5- 1,9
840
0,35-0,45
<0,1
ca. 1,1
920
920 880
0,25-0,30
0,35- 0,4
ca. 1,1-1,5
920
Trenntechnik I Prof. Arlt Adsorption
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slope A(2)/F
F (Y( 2 ) Y(1) ) = A ( 2 ) (X ( 2 ) X 0 )
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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
Trenntechnik I Prof. Arlt Adsorption
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flue dust adsorber radial flow uncommon types of adsorber for VOC flue gas
Trenntechnik I Prof. Arlt Adsorption
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19
100
10
0,1
range of application
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