Title
Application of nonlinear frequency response method for investigation of equlibrium and kinetics of gas-solid adsorption
Creator
Brzić, Danica V., 1973-
Copyright date
2016
Object Links
Select license
Autorstvo-Nekomercijalno-Bez prerade 3.0 Srbija (CC BY-NC-ND 3.0)
License description
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Language
English
Cobiss-ID
Committee report
Theses Type
Doktorska disertacija
description
Datum odbrane: 24.06.2016.
Other responsibilities
mentor
Petkovska, Menka, 1957-
član komisije
Nikačević, Nikola
član komisije
Garić-Grulović, Radmila, 1957-
Academic Expertise
Tehničko-tehnološke nauke
University
Univerzitet u Beogradu
Faculty
Tehnološko-metalurški fakultet
Alternative title
Primena nelinearne frekventne metode na ispitivanje ravnoteže i kinetike adsorpcionih sistema gas-čvrsto.
Publisher
[D. V. Brzić]
Format
VIII, 128 listova
description
Chemistry and Chemical Technology - Chemical Engineering / Hemija i hemijska tehnologija - Hemijsko inženjerstvo
Abstract (en)
The understanding of complex kinetic mechanisms of gas-solid adsorption is a challenging
issue. The Frequency Response (FR) method, which has commonly been used for studying the
kinetics of adsorption, analyzes the frequency response of the system in a linear range, and
therefore partly fails to identify and characterize the kinetics of nonlinear adsorption
phenomena. In the frame of this thesis, the applicability of a new Nonlinear Frequency
Response (NFR) method for characterization of kinetics and equilibria of gas adsorption, was
investigated.
The NFR method is based on the analysis of the frequency responses for a rather large
amplitude input excitation, named Nonlinear Frequency Responses, and determination of the
higher-order frequency response functions (FRFs), by applying the Volterra series and
generalized Fourier transform. The applicability of the NFR method for characterization of
kinetics and equilibria of pure gas adsorption was investigated both theoretically and
experimentally, for the case of a batch adsorber. The critical issue regarding the applicability of
the NFR method was determination of the second-order FRF on the adsorbent particle scale.
The theoretical investigation comprises two parts. The first part of investigation is based on the
numerical simulations of the dynamic responses of a batch adsorption system, by using
mathematical models on the adsorber scale and adsorbent particle scale. As a result, the
procedure for designing the NFR experiments has been established. In the second part, the
theoretical FRFs up to the second-order for nonisothermal macropore diffusion (NMD) model,
as one of the common mechanisms of gas-solid adsorption, have been derived and analyzed.
As a result, the methodology for estimation of the parameters of NMD model, based on the
characteristics of the FRFs, was established. In order to validate the NFR method
experimentally, a new experimental set-up was designed and constructed. The working
principle of the apparatus is modulation of the volume of the closed cell in a sinusiodal way,
with variable amplitude and frequency, and measuring the pressure, adsorbent temperature and
gas temperature responses. The test system was CO2/ zeolite 5A particles. The results showed
that the NFR method can be applied for identification of the kinetic mechanism and estimation
of equilibrium and kinetic data. It was also shown, that it is advantageous compared to the
linear FR method in terms of reliability of identification of the kinetic model based on the
second-order FRF, as well as in the possibility to estimate both kinetic and equilibrium data.
Since this work represents the first evidence of experimental application of the NFR method for
investigation of gas adsorption, it opens significant new perspectives in this field.
Abstract (sr)
Razumevanje složenih kinetičkih mehanizama adsorpcije gas-čvrsto predstavlja izazov u
savremenom istraživanju. Klasična Frekventna metoda, koja se uobičajeno koristi za ispitivanje
kinetike adsorpcije, analizira frekventni odziv sistema u linearnoj oblasti i zato ne može u
potpunosti da okarakteriše kinetiku nelinearnih procesa adsorpcije. U okviru ove disertacije
ispitivana je primenljivost metode Nelinearnog Frekventnog Odziva (NFO) za karakterizaciju
kinetike i ravnoteže adsorpcije gas-čvrsto.
Metoda NFO se zasniva na analiziranju frekventnog odziva sistema na ulaznu pobudu relativno
velike amplitude i određivanju frekventnih prenosnih funkcija (FPF) višeg reda, uz korišćenje
Volterra redova i generalizovane Furijeove transformacije. Primenljivost metode NFO za
karakterizaciju kinetike i ravnoteže adsorpcije čistih gasova je ispitivana teorijski i
eksperimentalno u zatvorenom (šaržnom) sistemu. Ključno pitanje u pogledu primenljivosti
metode NFO je mogućnost određivanja frekventne prenosne funkcije drugog reda na nivou
čestice adsorbensa. Teorijsko istraživanje se sastoji od dva dela. Prvi deo se zasniva na
numeričkim simulacijama dinamičkih odziva šaržnog adsorbera, uz korišćenje matematičkih
modela na nivou adsorbera i na nivou čestice adsorbensa. Na osnovu dobijenih rezultata
ustanovljena je procedura za planiranje nelinearnih frekventnih eksperimenata. U drugom delu,
izvedene su i analizirane FPF prvog i drugog reda za model neizotermne diffuzije kroz
makropore, koji je jedan od čestih mehanizama adsorpcije gasova. Na osnovu rezultata
ustanovljena je procedura za određivanje parametara pomenutog modela na osnovu
karakteristika FPF. Da bi se metoda eksperimentalno potvrdila, projektovan je i izgrađen novi
eksperimentalni sistem. Princip rada ovog sistema je promena zapremine sistema po sinusnom
zakonu, sa promenljivom amplitudom i frekvencijom, i merenje odziva pritiska gasa,
temperature adsorbensa i temperature gasa. Kao test sistem za eksperimente korišćen je
adsorpcioni sistem CO2/ zeolit 5A. Rezultati su pokazali da je moguće primeniti metodu NFO
za utvrđivanje kinetičkog mehanizma adsorpcije gasova kao i za određivanje kinetičkih i
ravnotežnih parametara. Takođe je pokazano da metoda NFO ima značajne prednosti u odnosu
na klasičnu (linearnu) frekventnu metodu, i to u pogledu pouzdanosti utvrđivanja kinetičkog
mehanizma na osnovu oblika FPF drugog reda kao i u pogledu mogućnosti određivanja i
kinetičkih i ravnotežnih podataka iz istih eksperimentalnih podataka.
U ovom radu je prvi put eksperimentalno potvrđena mogućnost ispitivanja adsorpcije gasčvrsto
korišćenjem metode NFO, čime se otvaraju značajne nove perspektive u toj oblasti.
Authors Key words
Nonlinear frequency response, Gas adsorption, Second-order FRF, Model
identification, Parameter estimation, Nonisothermal macropore diffusion
Authors Key words
Nelinearni frekventni odziv, Adsorpcija gas-čvrsto, Frekventna funkcija drugog
reda, Identifikacija modela, Određivanje parametara, Neizotermna difuzija kroz makropore
Classification
66.021.3.081.3:531.3:66.071.6
Type
Tekst
Abstract (en)
The understanding of complex kinetic mechanisms of gas-solid adsorption is a challenging
issue. The Frequency Response (FR) method, which has commonly been used for studying the
kinetics of adsorption, analyzes the frequency response of the system in a linear range, and
therefore partly fails to identify and characterize the kinetics of nonlinear adsorption
phenomena. In the frame of this thesis, the applicability of a new Nonlinear Frequency
Response (NFR) method for characterization of kinetics and equilibria of gas adsorption, was
investigated.
The NFR method is based on the analysis of the frequency responses for a rather large
amplitude input excitation, named Nonlinear Frequency Responses, and determination of the
higher-order frequency response functions (FRFs), by applying the Volterra series and
generalized Fourier transform. The applicability of the NFR method for characterization of
kinetics and equilibria of pure gas adsorption was investigated both theoretically and
experimentally, for the case of a batch adsorber. The critical issue regarding the applicability of
the NFR method was determination of the second-order FRF on the adsorbent particle scale.
The theoretical investigation comprises two parts. The first part of investigation is based on the
numerical simulations of the dynamic responses of a batch adsorption system, by using
mathematical models on the adsorber scale and adsorbent particle scale. As a result, the
procedure for designing the NFR experiments has been established. In the second part, the
theoretical FRFs up to the second-order for nonisothermal macropore diffusion (NMD) model,
as one of the common mechanisms of gas-solid adsorption, have been derived and analyzed.
As a result, the methodology for estimation of the parameters of NMD model, based on the
characteristics of the FRFs, was established. In order to validate the NFR method
experimentally, a new experimental set-up was designed and constructed. The working
principle of the apparatus is modulation of the volume of the closed cell in a sinusiodal way,
with variable amplitude and frequency, and measuring the pressure, adsorbent temperature and
gas temperature responses. The test system was CO2/ zeolite 5A particles. The results showed
that the NFR method can be applied for identification of the kinetic mechanism and estimation
of equilibrium and kinetic data. It was also shown, that it is advantageous compared to the
linear FR method in terms of reliability of identification of the kinetic model based on the
second-order FRF, as well as in the possibility to estimate both kinetic and equilibrium data.
Since this work represents the first evidence of experimental application of the NFR method for
investigation of gas adsorption, it opens significant new perspectives in this field.
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