E alua ion o H-BEA Zeoli e Dealumina ion and
Adso p ion S udy o Alkyla oma ics in Comme cial
Y-Type Zeoli es
Felipe Ma ´ınez Ba e o
Unde g adua e Thesis in Pa ial Ful illmen o he Requi emen s
o he Deg ee o Bachelo in:
Chemical Enginee ing
Thesis Ad iso :
Julio C´esa Va gas Saenz
UNIVERSIDAD NACIONAL DE COLOMBIA
FACULTY OF ENGINEERING
DEPARTMENT OF CHEMICAL ENGINEERING
BOGOT´
A, D.C. July 25 h, 2025
Solo us edes, mis pila es, mis he o´ınas, saben c´omo ha sido es e camino.
Los es amo es de mi ida, sin us edes simplemen e no es a ´ıa d´onde es oy.
G acias po impulsa me a llega has a aqu´ı, po le an a me en los
momen os di ´ıciles, po egala me son isas en los m´as bellos, y po
mo i a me siemp e a segui so˜nando con me as a´un m´as g andes, no solo en
lo acad´emico, sino en lo emocional especialmen e.
Pa a mis es elli as en el i mamen o que me cuidan siemp e,
es ´a Tesis a dedicada a us edes. Las amo...
Mam´a, Dani y Sa i a.
ACKNOWLEDGMENTS
I would like o hank my hesis ad iso , P o esso Julio C´esa Va gas Saenz.
This semes e , unde his men o ship, I lea ned so much—especially he deep
lo e o knowledge and he commi men o gi e back o ou coun y h ough
eaching and academia. I hope o one day ollow he same pa h. Thank
you o you pa ience du ing he econs uc ion o he eac o , and o he
coun less hou s you dedica ed o helping me unde s and and ca y ou each
o he expe imen s.
I would also like o especially hank P o esso Raj Gounde , who ga e
me he oppo uni y o begin his jou ney a Pu due Uni e si y in Wes
La aye e. Thank you o us ing me, o allowing me o wo k in you
labo a o ies, and o you always imely ad ice, which cons an ly mo i a ed
me o keep pu suing esea ch. I hope o con inue down ha pa h and ha
ou pa hs will c oss again soon.
To my amily: Rolis, Johana, and he gi ls. To Mam´a Lucy, hank you
o e e y ime you sen me a pla e o ”A oci o con Pollo”. Th oughou
he hesis, and du ing my en i e deg ee, I el you uncondi ional lo e and
suppo . Wo ds a e no enough o hank you.
To my uni e si y iends: So i, Ca los, Nakay, B ayan, and Cami. Thank
you o he good imes, o being he e when I needed you he mos , and o
making “la Nacho” ha magical place I always wan ed o e u n o. Thanks
o you, I’ll ca y wi h me he memo y o a uni e si y illed wi h laugh e ,
a ec ion, and un o ge able momen s. I wish you all he bes in he new
jou neys ahead.
And inally, o he Na ional Uni e si y o Colombia, my alma ma e , a
easu e I will ca y wi h me o he es o my li e. You augh me o lo e
wha I do, o g ow as a pe son, and o become he human being I am oday.
Thank you, deeply.
Con en s
ACKNOWLEDGMENTS ....................... 2
1. CHAPTER 1: E alua ion o H-BEA Zeoli e Dealumina ion 10
1.1 Abs ac .............................. 10
1.2 In oduc ion............................ 10
1.3 Ma e ials and Me hods . . . . . . . . . . . . . . . . . . . . . . 13
1.3.1 H-BEA Zeoli e Physicochemical P ope ies . . . . . . . . 13
1.3.2 H-BEA Dealumina ion Expe imen al Design . . . . . . . 14
1.3.3 Cha ac e iza ion o H-BEA Dealumina ed Samples . . . 16
1.4 Resul s and Discussion . . . . . . . . . . . . . . . . . . . . . . 20
1.5 Conclusions ............................ 34
2. CHAPTER 2: Adso p ion S udy o Alkyla oma ics in
Comme cial Y-Type Zeoli es ................... 36
2.1 Abs ac .............................. 36
2.2 In oduc ion............................ 37
2.3 Ma e ials and Me hods . . . . . . . . . . . . . . . . . . . . . . 38
2.3.1 Physicochemical P ope ies o Zeoli e HY Powde (Ze-
olys CBV100) ....................... 38
2.3.2 Equipmen Desc ip ion . . . . . . . . . . . . . . . . . . . 39
2.3.3 Calib a ion o Mass Flow Con olle s . . . . . . . . . . . 44
2.3.4 TPD Expe imen a ion Desc ip ion . . . . . . . . . . . . 51
2.3.5 Mass Spec ome e Calib a ion . . . . . . . . . . . . . . 53
2.4 Resul s and Discussion . . . . . . . . . . . . . . . . . . . . . . 54
2.4.1 Mass Spec ome e Calib a ion Resul s . . . . . . . . . . 54
2.4.2 Adso p ion/Deso p ion Resul s . . . . . . . . . . . . . . 57
2.5 Conclusions ............................ 67
5. REFERENCES ............................ 69
6. APPENDICES ............................ 72
A. S anda d Ope a ing P ocedu e’s (SOP’s) ........... 72
A.1 S anda d Ope a ing P ocedu e (SOP) - Di e en ial Reac o
Ope a ion ............................. 72
A.2 S anda d Ope a ing P ocedu e (SOP) - Adso p ion/Deso p ion 74
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Bachelo Thesis - Felipe Ma ´ınez Ba e o Uni e sidad Nacional de Colombia
B. Mass Spec ome e Calib a ion Resul s ............ 75
B.1 Smoo hed Resul s o Mass Spec ome e Calib a ion . . . . . 75
B.2 A ea unde smoo hed peaks o Mass Spec ome e Calib a ion 82
B.3 Resul s o P obe Injec ion Tes s in he Di e en ial Reac o :
Emp y and wi h a Bed o G ound Qua z and SiC . . . . . . . 89
C. Sa u a ion peaks and TPD Resul s ............... 93
4
Lis o Figu es
1 Dealumina ion Expe imen al Design o H-BEA (15) using
EDTAandHCl.......................... 15
2 Rigaku Sma Lab di ac ome e (XRD) a Chemical Enginee -
ing Pu due Labo a o ies . . . . . . . . . . . . . . . . . . . . . 16
3 Mic ome i ics 3-Flex ins umen (N2adso p ion) a Chemical
Enginee ing Pu due (Gounde G oup Labo a o ies) . . . . . . 17
4 Induc i ely Coupled Plasma Op ical Emission Spec oscopy
(ICP-OES) a Chemical Enginee ing Pu due (Gounde G oup
Labo a o ies) ........................... 18
5 Tempe a u e P og ammed Deso p ion (TPD) a Pu due
Chemical Enginee ing (Gounde G oup Labo a o ies) . . . . . 19
6a) T iangles - HCl, C osses - Na2H2EDTA 0.13M, Diamonds
-Na2H2EDTA 0.24M, Squa es - Na2H2EDTA pH = 8. b)
H4EDTA ............................. 20
7 H-BEA 15 XRD Pa e n (Top/Down)-([1] H-BEA 15 he lowes
one/Expe imen al Ob ained) . . . . . . . . . . . . . . . . . . . 21
8 HClXRDPa e n......................... 22
9Na2H2EDTA 0.13 and 0.24 M XRD Pa e n . . . . . . . . . . 22
10 C ys allini y Resul s a) Na2H2EDTA 0.13 and 0.24 M b) HCl 23
11 H4EDTA XRD Pa e n and Rela i e C ys allini y . . . . . . 24
12 [H+]/[Al] and [Si]/[Al] o a) HCl, b) Na2H2EDTA a pH =
8, c) Na2H2EDTA 0.13, d) Na2H2EDTA 0.24 M . . . . . . 25
13 HCl, Na2H2EDTA pH=8, Na2H2EDTA 0.13 and 0.24
FALn/FAL0cu es ....................... 27
14 S acked EFAL and FAL dealumina ion a) HCl, b)
Na2H2EDTA 0.13M, c) Na2H2EDTA 0.24M . . . . . . . . . 28
15 N2Adso p ion Iso he ms a) HCl, b) Na2H2EDTA a 0.13 M
c) Na2H2EDTA a 0.24M.................... 29
16 Su aceA eaHCl......................... 30
17 Su ace A ea Na2H2EDTA a) 0.13 M, b) 0.24M . . . . . . . . 31
18 Po eVolumenHCl ........................ 32
19 Po e Volumen Na2H2EDTA a) 0.13 M, b) 0.24M . . . . . . . 33
20 Gas Phase Di e en ial Reac o Diag am . . . . . . . . . . . . 39
21 Possible a angemen using wo ou -way al es . . . . . . . . 41
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Bachelo Thesis - Felipe Ma ´ınez Ba e o Uni e sidad Nacional de Colombia
22 Di e en ial Reac o and Mass Spec ome e Analysis. (a) Gas
Mixe , (b) Fu nace and Qua z U- ube Reac o , (c) Gas P e-
Hea ing Con olle s, (d) Mass Flow Con olle s, (e) Tempe a-
u e Display o he S eams En e ing he Val e A angemen ,
( ) Fu nace Tempe a u e Con olle , (g) QGA Mass Spec om-
e e . (h) Fou Ways Val es A angemen . . . . . . . . . . . . 43
23 a) Fu nace-Reac o Sys em and Packed Bed Reac o wi h Ze-
olys CBV 712 Dilu ed a 4.5% in SiC (see Figu e 33) . . . . . 43
24 (a) Gas Mixe , (e) Tempe a u e Display o he S eams En-
e ing he Val e A angemen , ( ) Fu nace Tempe a u e Con-
olle , (g) QGA Mass Spec ome e . . . . . . . . . . . . . . . 44
25 (c) Gas P e-Hea ing Con olle s, (d) Mass Flow Con olle s,
(h) Fou Ways Val es A angemen . . . . . . . . . . . . . . . 44
26 Pu e He Mass Flow Con olle Calib a ion . . . . . . . . . . . 45
27 Pu e He om Gas Mixe Mass Flow Con olle Calib a ion . . 46
28 Pu e CO2 om Gas Mixe Mass Flow Con olle Calib a ion . 46
29 Pu e CO2andHeDensi y .................... 48
30 CO2- He Mix u e Densi y using Peng-Robinson a 18°C . . . 48
31 CO2- He Mix u e Rela i e E o o lineal 5 h o de eg ession 49
32 CO2- He Mix u e Val e opening calib a ion o ob ain 50
mL/mina 40PSIG ....................... 51
33 U Reac o A angemen . . . . . . . . . . . . . . . . . . . . . 52
34 A ea unde peaks (Blank sample) o a) Toluene and b) Benzene 55
35 A ea unde peaks (SiC sample) o a) Toluene and b) Benzene 55
36 Benzene concen a ion and Tempe a u e Ramp Resul s a)
25°C, b) 75°C and c) 150°C ................... 57
37 Benzene TPD o Zeoli e H-Y dilu ed in SiC . . . . . . . . . . 58
38 Toluene concen a ion and Tempe a u e Ramp Resul s a)
25°C, b) 75°C and c) 150°C ................... 60
39 Benzene TPD o Zeoli e H-Y dilu ed in SiC . . . . . . . . . . 61
40 Benzene TPD Gaussian Con olu ion 25°Cn=5......... 63
41 Benzene TPD Gaussian Con olu ion 75°Cn=4......... 63
42 Benzene TPD Gaussian Con olu ion 150°C n=3 . . . . . . . . 64
43 Toluene TPD Gaussian Con olu ion 25°Cn=4......... 64
44 Toluene TPD Gaussian Con olu ion 75°Cn=5......... 65
45 Toluene TPD Gaussian Con olu ion 150°C n=3 . . . . . . . . 65
46 Toluene and Benzene TPD epo ed by [2] a 25°C as Adso p-
ionTempe a u e......................... 67
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Bachelo Thesis - Felipe Ma ´ınez Ba e o Uni e sidad Nacional de Colombia
47 Smoo hed Toluene peaks a 25°C (Blank sample) . . . . . . . 75
48 Smoo hed Toluene peaks a 75°C (Blank sample) . . . . . . . 76
49 Smoo hed Toluene peaks a 150°C (Blank sample) . . . . . . . 76
50 Smoo hed Benzene peaks a 25°C (Blank sample) . . . . . . . 77
51 Smoo hed Benzene peaks a 75°C (Blank sample) . . . . . . . 77
52 Smoo hed Benzene peaks a 150°C (Blank sample) . . . . . . . 78
53 Smoo hed Toluene peaks a 25°C (SiC sample) . . . . . . . . . 78
54 Smoo hed Toluene peaks a 75°C (SiC sample) . . . . . . . . . 79
55 Smoo hed Toluene peaks a 150°C (SiC sample) . . . . . . . . 79
56 Smoo hed Benzene peaks a 25°C (SiC sample) . . . . . . . . 80
57 Smoo hed Benzene peaks a 75°C (SiC sample) . . . . . . . . 80
58 Smoo hed Benzene peaks a 150°C (SiC sample) . . . . . . . . 81
59 A ea unde Toluene peaks a 25°C (Blank sample) . . . . . . . 82
60 A ea unde Toluene peaks a 75°C (Blank sample) . . . . . . . 83
61 A ea unde Toluene peaks a 150°C (Blank sample) . . . . . . 83
62 A ea unde Benzene peaks a 25°C (Blank sample) . . . . . . 84
63 A ea unde Benzene peaks a 75°C (Blank sample) . . . . . . 85
64 A ea unde Benzene peaks a 150°C (Blank sample) . . . . . . 85
65 A ea unde Toluene peaks a 25°C (SiC sample) . . . . . . . . 86
66 A ea unde Toluene peaks a 75°C (SiC sample) . . . . . . . . 86
67 A ea unde Toluene peaks a 150°C (SiC sample) . . . . . . . 87
68 A ea unde Benzene peaks a 25°C (SiC sample) . . . . . . . . 87
69 A ea unde Benzene peaks a 75°C (SiC sample) . . . . . . . . 88
70 A ea unde Benzene peaks a 150°C (SiC sample) . . . . . . . 88
71 A ea unde peaks as unc ion o Tempe a u e in (Blank sample)
a)Toluene b) Benzene ...................... 89
72 A ea unde peaks as unc ion o Tempe a u e in (SiC sample)
a)Toluene b) Benzene ...................... 90
73 A ea unde peaks as unc ion o Toluene 25°C pulse olume,
compa ison be ween Blanck and SiC . . . . . . . . . . . . . . 90
74 A ea unde peaks as unc ion o Toluene 75°C pulse olume,
compa ison be ween Blanck and SiC . . . . . . . . . . . . . . 91
75 A ea unde peaks as unc ion o Toluene 150°C pulse olume,
compa ison be ween Blanck and SiC . . . . . . . . . . . . . . 91
76 A ea unde peaks as unc ion o Benzene 25°C pulse olume,
compa ison be ween Blanck and SiC . . . . . . . . . . . . . . 92
77 A ea unde peaks as unc ion o Benzene 75°C pulse olume,
compa ison be ween Blanck and SiC . . . . . . . . . . . . . . 92
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Bachelo Thesis - Felipe Ma ´ınez Ba e o Uni e sidad Nacional de Colombia
78 A ea unde peaks as unc ion o Benzene 150°C pulse olume,
compa ison be ween Blanck and SiC . . . . . . . . . . . . . . 93
79 Benzene injec ion in 3µL pulses a 25°C ollowed by TPD anal-
ysis. ................................ 94
80 Benzene injec ion in 3µL pulses a 75°C ollowed by TPD anal-
ysis. ................................ 94
81 Benzene 25°C Adso p ion TPD . . . . . . . . . . . . . . . . . 95
82 Benzene 75°C Adso p ion TPD . . . . . . . . . . . . . . . . . 95
83 Benzene 150°C Adso p ion TPD . . . . . . . . . . . . . . . . 96
84 Toluene injec ion in 3µL pulses a 25°C ollowed by TPD analysis. 96
85 Toluene injec ion in 3µL pulses a 75°C ollowed by TPD analysis. 97
86 Toluene injec ion in 3µL pulses a 150°C ollowed by TPD anal-
ysis. ................................ 97
87 Toluene 25°C Adso p ion TPD . . . . . . . . . . . . . . . . . . 98
88 Toluene 75°C Adso p ion TPD . . . . . . . . . . . . . . . . . . 98
89 Toluene 150°C Adso p ion TPD . . . . . . . . . . . . . . . . . 99
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Bachelo Thesis - Felipe Ma ´ınez Ba e o Uni e sidad Nacional de Colombia
o 1 and 24 hou s a 100°C. Finally, aqueous solu ions o disodium EDTA
we e p epa ed a concen a ions o 0.13 and 0.24 M and applied o 1, 2, 4,
and 8 hou s a 100°C.
In gene al e ms, he expe imen al design ollows he scheme shown in
Figu e 1, s a ing wi h H-BEA (15) zeoli e supplied by Cla ian (HCZB-30).
App oxima ely 2.0000 ±0.0001 g ams o sample we e aken o dealumi-
na ion and 20 ml o he co esponding acid solu ion was added o a Te lon
essel. The acid ea men was hen ca ied ou a 100°C o he du a ions
men ioned p e iously o each acid. A e he dealumina ion s ep, he
samples we e cen i uged a 5000 pm and washed i e imes wi h DI wa e
o emo e he supe na an . Finally, he solids we e le in a s a ic o en a
373 K o e nigh .
Figu e 1: Dealumina ion Expe imen al Design o H-BEA (15) using EDTA
and HCl
Wi h he sample d ied and placed in he ials, mo phological analyzes
o he dealumina ed s uc u es we e ca ied ou using XRD, N2adso p ion,
ICP, and TPD echniques o de e mine su ace and olume ic p ope ies,
such as speci ic su ace a ea and o al, ex e nal, and mic opo e olume, as
well as he BJH po e size dis ibu ion. In addi ion, XRD pa e ns we e
15
Bachelo Thesis - Felipe Ma ´ınez Ba e o Uni e sidad Nacional de Colombia
analyzed o assess whe he any des uc ion o he c ys alline s uc u e had
occu ed a e ea men . Fu he mo e, he amoun o acid si es [FAL] and
he Si/Al a io o he s uc u e we e measu ed o enable a deepe analysis
o he s udied phenomenon. The ollowing sec ions desc ibe each o he
echniques in mo e de ail.
1.3.3 Cha ac e iza ion o H-BEA Dealumina ed Samples
•XRD
The c ys al s uc u es we e analyzed by ob aining powde X- ay di ac-
ion da a using a Rigaku Sma Lab di ac ome e equipped wi h a Cu
Kα adia ion sou ce (λ= 1.54 ˚
A, ope a ing condi ions: 40 kV and 44
mA). Di ac ion measu emen s we e pe o med o e a 2θ ange o 4° o
50°wi h a s ep o 0.01°and a scanning a e o 0.0167°pe second. The
equipmen can be seen in Figu e 2:
Figu e 2: Rigaku Sma Lab di ac ome e (XRD) a Chemical Enginee ing
Pu due Labo a o ies
•N2 Adso p ion
16
Bachelo Thesis - Felipe Ma ´ınez Ba e o Uni e sidad Nacional de Colombia
Ni ogen adso p ion iso he ms we e acqui ed a 77 K using a Mi-
c ome i ics 3-Flex ins umen . App oxima ely 0.05 g o sample was
i s degassed unde a dynamic acuum (p essu e below 0.67 kPa), hen
hea ed a 393 K o 2 hou s ollowed by u he hea ing a 623 K o
9 hou s wi h a con olled a e o 0.167 K pe second be o e conduc ing
he adso p ion expe imen s. 3-Flex equipmen can be seen in Figu e
3:
Figu e 3: Mic ome i ics 3-Flex ins umen (N2adso p ion) a Chemical
Enginee ing Pu due (Gounde G oup Labo a o ies)
•ICP-OES
Fo elemen al analysis, induc i ely coupled plasma op ical emission
spec oscopy (ICP-OES) was used, employing a The mo Scien i ic
iCAP 7000 Plus Se ies ins umen as i may be seen in Figu e 4. Fo
17
Bachelo Thesis - Felipe Ma ´ınez Ba e o Uni e sidad Nacional de Colombia
his pu pose, abou 0.02 g o he solid sample was dissol ed in 2.5 g o
hyd o luo ic acid (48 w %, Al a Aesa ). A e allowing he eac ion o
p oceed o o e 24 hou s, 1 g o ni ic acid (70 w %, Sigma-Ald ich)
was added, and he solu ion was u he dilu ed wi h 50 g o deionized
wa e .
Figu e 4: Induc i ely Coupled Plasma Op ical Emission Spec oscopy (ICP-
OES) a Chemical Enginee ing Pu due (Gounde G oup Labo a o ies)
•TPD
Ammonia empe a u e-p og ammed deso p ion (TPD) was ca ied ou
o de e mine he quan i y o p o onic (H+) si es p esen on BEA zeo-
li e samples. P io o he TPD analysis, he samples unde wen an ion-
exchange p ocedu e using ammonium ni a e o eplace sodium o o he
18
Bachelo Thesis - Felipe Ma ´ınez Ba e o Uni e sidad Nacional de Colombia
exchangeable ca ions wi h ammonium ions. Fo each un, be ween 0.02
and 0.06 g ams o sample we e packed in o a qua z U- ube eac o and
held in place wi h qua z wool on bo h ends. The TPD measu emen s
we e conduc ed using a Mic ome i ics Au oChem II 2920 Chemiso p-
ion Analyze seen in Figu e 5. A e ion exchange, he samples we e
subjec ed o a empe a u e amp unde helium low o he mally de-
compose he ammonium ions, leading o he deso p ion o ammonia
and allowing quan i ica ion o he B øns ed acid si es p esen in he
ma e ial.
Figu e 5: Tempe a u e P og ammed Deso p ion (TPD) a Pu due Chemical
Enginee ing (Gounde G oup Labo a o ies)
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Bachelo Thesis - Felipe Ma ´ınez Ba e o Uni e sidad Nacional de Colombia
1.4 Resul s and Discussion
The i s analysis ob ained, which p o ides he clea es o e iew o he
dealumina ion p ocess o each o he species, was he elemen al analysis
by ICP. Based on he me hodology desc ibed p e iously, i was possible o
calcula e he amoun o Si and Al in %w , and om his es ima e he [Si/Al]
a io o each o he a o emen ioned species as a unc ion o ime, as shown
in he ollowing Figu e 6:
Figu e 6: a) T iangles - HCl, C osses - Na2H2EDTA 0.13M, Diamonds -
Na2H2EDTA 0.24M, Squa es - Na2H2EDTA pH = 8. b) H4EDTA
Fu he mo e, i was ound ha he e is no signi ican change in he
Si w % o he dealumina ed samples, as also epo ed by [3] in hei
esul s. This obse a ion will become e en mo e ele an in a la e analysis.
Howe e , in he case o Al w %, a no iceable dec ease was obse ed, which
is e lec ed in a p og essi e inc ease in he [Si/Al] a io o each o he species.
In he case o HCl, i is e iden ha he dealumina ion p ocess is s onge
han ha obse ed wi h he h ee di e en EDTA o ms e alua ed. No ably,
he [Si/Al] a io does no con e ge o a s able alue, which may indica e
ha his pa icula ea men emo es bo h (FAL) and (EFAL) h oughou
he dealumina ion p ocess. In con as , o all EDTA-based ea men s,
he emo al o aluminum appea s o s abilize, sugges ing a p e e ence o
ex ac ing he mo e easily accessible s uc u es, EFAL, un il i eaches a
poin whe e u he emo al is no longe possible. This beha io implies
20
Bachelo Thesis - Felipe Ma ´ınez Ba e o Uni e sidad Nacional de Colombia
ha , unlike HCl, EDTA is no capable o ex ac ing s uc u al aluminum
om he zeoli e amewo k. La e , i will be con i med o no by analyzing
he TPD esul s.
Finally, in e ms o he ICP esul s, i is wo h no ing ha compa ed
o H4EDTA and Na2H2EDTA a pH = 8 ea men s, Na2H2EDTA
solu ions a concen a ions o 0.13 and 0.24 M a e mo e e ec i e a emo ing
aluminum, eaching [Si/Al] alues o up o 28. This sugges s ha ea men
wi h H4EDTA and Na2H2EDTA a pH = 8 does no possess enough acidi y
o emo e any o m o EFAL. Fo his eason, hey will no be discussed in
de ail in he u u e, unlike HCl and Na2H2EDTA a 0.13 and 0.24 M, which
will emain he ocus.
On he basis o he p e ious analysis, he nex echnique o u he
complemen he unde s anding o he dealumina ion p ocess was he s udy
o c ys allini y h ough XRD. Ini ially, special a en ion was gi en o he
pa e ns o HCl and Na2H2EDTA a 0.13 and 0.24 M, as hese a e he
condi ions ha , up o his poin , appea o ha e induced signi ican s uc u al
changes. Fi s , he XRD pa e n was compa ed wi h he li e a u e epo ed
in [1], as i may be seen in Figu e 7:
Figu e 7: H-BEA 15 XRD Pa e n (Top/Down)-([1] H-BEA 15 he lowes
one/Expe imen al Ob ained)
21
Bachelo Thesis - Felipe Ma ´ınez Ba e o Uni e sidad Nacional de Colombia
As can be obse ed, he e e ence zeoli e exhibi s he same cha ac e is ic
peaks epo ed by [1] o H-BEA (15) zeoli es, speci ically wi hin he anges
o 7-8°and 22-23°. Taking his in o accoun , he ollowing Figu e 8 and
Figu e 9 compa e his e e ence pa e n as he baseline in all diag ams wi h
he dealumina ed samples, ini ially o HCl and Na2H2EDTA a 0.13 and
0.24 M o each ea men ime:
Figu e 8: HCl XRD Pa e n
Figu e 9: Na2H2EDTA 0.13 and 0.24 M XRD Pa e n
A i s glance, no signi ican changes a e obse ed in he pa e ns,
meaning he e is no e idence o a o al deg ada ion o he s uc u e. Fo
his eason, he calcula ion o Rela i e C ys allini y wi h espec o he
22
Bachelo Thesis - Felipe Ma ´ınez Ba e o Uni e sidad Nacional de Colombia
e e ence pa e n is ca ied ou in o de o pe o m a mo e de ailed analysis
o he changes in he c ys alline s uc u e as a unc ion o he acid used
and he ea men ime. The ollowing p esen s he exp ession used o he
C ys allini y calcula ion and he co esponding esul s:
CRel =PISample
PIP a e n
(1)
The summa ion was pe o med o he cha ac e is ic peaks loca ed a 7
o 8 °and 22 o 23 °, esul ing in he ollowing:
Figu e 10: C ys allini y Resul s a) Na2H2EDTA 0.13 and 0.24 M b) HCl
In Figu e 10, a simila beha io can be obse ed in all ea men s,
showing an ini ial inc ease in c ys allini y ollowed by a decline. This can
be complemen ed by he obse a ions in [4], whe e an ini ial emo al o
EFAL loca ed in he mic opo es leads o po e opening. Howe e , as ime
p og esses, he in e ac ion wi h FAL becomes mo e equen . Up o his
poin , based on he esul s ob ained, his easoning appea s o be consis en
wi h he indings. Ne e heless, da a om TPD analysis p esen ed la e will
demons a e a no el e ec ha suppo s his p e e en ial emo al beha io
h oughou he dealumina ion p ocess.
Finally, XRD and c ys allini y esul s we e ob ained o H4EDTA,
con i ming—along wi h he ICP esul s in Figu e 6— ha no signi ican
dealumina ion occu ed. The same conclusion applies o Na2H2EDTA a
23
Bachelo Thesis - Felipe Ma ´ınez Ba e o Uni e sidad Nacional de Colombia
pH = 8.
Figu e 11: H4EDTA XRD Pa e n and Rela i e C ys allini y
Now, he complemen a y analysis o ICP o his expe imen a ion was
TPD, which allows de e mining he numbe o B ns ed acid si es associa ed
wi h an FAL, h ough ion exchange wi h NH4NO3 ollowed by ammonia des-
o p ion using a p og ammed empe a u e amp and an online ch oma og aph
in Au oChem. This means ha , om he o al aluminum con en es ima ed
by ICP, i is now possible o dis inguish be ween FAL and EFAL, allowing he
es ima ion o he [H+]
Al a io. Wi h his, he ollowing g aphs we e cons uc ed:
24
Bachelo Thesis - Felipe Ma ´ınez Ba e o Uni e sidad Nacional de Colombia
Table 3: Su ace A ea HCl
Sample Time (h) Su ace A ea (m2/g)
To al Mic opo e Ex e nal
Pa en -HBEA (15) HCZ30 0 618 468 151
H-BEA (15) HCl
0.25 643 449 194
0.5 592 417 175
1 549 379 169
2 566 400 156
Fo i s pa , he su ace ea ed wi h Na2H2EDTA does no seem o show
a signi ican change in he su ace a ea, bo h o mic opo es and ex e nal si es
o he c ys alline s uc u e, as can be seen in Figu e 17:
Figu e 17: Su ace A ea Na2H2EDTA a) 0.13 M, b) 0.24M
31
Bachelo Thesis - Felipe Ma ´ınez Ba e o Uni e sidad Nacional de Colombia
Table 4: Su ace A ea o H-BEA (15) unde Na2H2EDTA T ea men
Sample Time (h) Su ace A ea (m2/g)
To al Mic opo e Ex e nal
Pa en -HBEA (15) HCZ30 0 618 468 151
H-BEA(15) Na2H2EDTA 0.13M
1 614 444 169
2 620 444 175
8 605 435 170
H-BEA(15) Na2H2EDTA 0.13M
1 603 432 172
2 614 438 176
8 591 420 171
Jus as wi h he su ace a ea, an ini ial inc ease in po e olume can be
obse ed, associa ed wi h he e ec o aluminum emo al ha was blocking
he po es. Howe e , as in he p e ious case, when he s uc u e deg ades, he
olume o each ype o po e also dec eases, as shown in Figu e 18:
Figu e 18: Po e Volumen HCl
32
Bachelo Thesis - Felipe Ma ´ınez Ba e o Uni e sidad Nacional de Colombia
Table 5: Po e Volume o H-BEA (15) unde HCl T ea men
Sample Time (h) Po e Volume (m3/g)
To al Mic opo e Ex e nal
Pa en -HBEA (15) HCZ30 0 0.369 0.244 0.125
H-BEA (15) HCl
0.25 0.395 0.236 0.159
0.5 0.363 0.231 0.132
1 0.337 0.196 0.141
2 0.335 0.213 0.122
Fo he po e olume o he Na2H2EDTA- ea ed sample, he e was also
no signi ican change, which is desi able o he dealumina ion p ocess, as
shown in Figu e 19:
Figu e 19: Po e Volumen Na2H2EDTA a) 0.13 M, b) 0.24M
33
Bachelo Thesis - Felipe Ma ´ınez Ba e o Uni e sidad Nacional de Colombia
Table 6: Po e Volume o H-BEA (15) unde Na2H2EDTA T ea men s
Sample Time (h) Po e Volume (m3/g)
To al Mic opo e Ex e nal
Pa en -HBEA (15) HCZ30 0 0.369 0.244 0.125
H-BEA(15) Na2H2EDTA 0.13M
1 0.378 0.222 0.157
2 0.383 0.219 0.164
8 0.375 0.218 0.157
H-BEA(15) Na2H2EDTA 0.24M
1 0.371 0.225 0.146
2 0.375 0.217 0.158
8 0.367 0.209 0.158
1.5 Conclusions
Based on he esul s ob ained using he a ious p e iously desc ibed ech-
niques, i was ound ha he dealumina ing agen s wi h he mos signi ican
e ec s we e HCl and Na2H2EDTA a concen a ions o 0.13 and 0.24 M. In
con as , he basic and anhyd ous o ms o EDTA p oduced no obse able
s uc u al o physicochemical changes on he su ace. No ably, he mos
e ec i e dealumina ion was achie ed wi h Na2H2EDTA 0.24 M a e 8
hou s, eaching a FALn/FAL0 a io o 0.92, which co esponds o an 8%
loss o amewo k aluminum (FAL) compa ed o he e e ence ma e ial.
Addi ionally, he [H+/Al] a io inc eased om 0.62 o 0.93, indica ing a
dec ease in he ex a- amewo k aluminum (EFAL) popula ion om 38% o
7%, i.e., a 31% educ ion ela i e o he ini ial alue.
The second-bes pe o mance was obse ed wi h Na2H2EDTA 0.13 M,
showing a FALn/FAL0 a io o 0.87 a e 8 hou s, equi alen o a 13% loss
o FAL, and an inc ease in he [H+/Al] a io om 0.62 o 0.89, co esponding
o a 27% educ ion in EFAL con en .
In con as , he HCl ea men esul ed in an undesi ed e ec , wi h a
FALn/FAL0 a io d opping o 0.39 a e jus 2 hou s, indica ing excessi e
emo al o FAL. Mo eo e , he [H+/Al] a io inc eased only sligh ly, om
0.62 o 0.65, sugges ing ha no clea selec i i y was achie ed be ween EFAL
34
Bachelo Thesis - Felipe Ma ´ınez Ba e o Uni e sidad Nacional de Colombia
and FAL emo al. Figu e 14 clea ly illus a es his beha io .
Fu he mo e, combined ICP and TPD analysis e ealed pa ial einco -
po a ion o EFAL in o he amewo k as FAL in he samples ea ed wi h
Na2H2EDTA 0.13 and 0.24 M. This phenomenon is obse ed in Figu e
14 as an inc ease in he slope o amewo k aluminum con en and also
in Figu e 13 h ough he e olu ion o he FALn/FAL0 a io. Howe e ,
based on XRD esul s, his einco po a ion does no appea o p ese e he
c ys allini y o he o iginal s uc u e.
A ime-dependen end in he emo al a es o EFAL and FAL was
also iden i ied, as seen in Figu e 12. Ini ially, HCl ea men emo es
p ima ily EFAL, which is e lec ed in he 3-Flex analysis as an inc ease in
ex e nal po e olume (mic opo e opening). Howe e , a e a ce ain poin ,
he end shi s owa d p edominan emo al o FAL, esul ing in a g adual
dec ease in bo h su ace a ea and po e olume. In con as , Na2H2EDTA
ea men s a 0.13 and 0.24 M selec i ely emo e EFAL h oughou he en i e
ime ange s udied, wi h negligible changes in su ace and po osi y p ope ies.
In conclusion, ea men o H-BEA zeoli e (Si/Al = 15) wi h
Na2H2EDTA a 0.13 and 0.24 M allows o selec i e emo al o EFAL
species, achie ing [H+/Al] a ios o 0.89 and 0.93, espec i ely, wi h
con olled losses o FAL (13% and 8%). These modi ica ions we e ac-
complished wi hou signi ican changes in key p ope ies such as su ace
a ea, po e olume, o ela i e c ys allini y compa ed o he e e ence ma e ial.
Fo u u e esea ch, i would be aluable o unde s and, a a molecula
le el, he in e ac ions be ween Na2H2EDTA and he di e en o ms o EFAL
and FAL, o in es iga e how EFAL einco po a ion may be in luenced by
di usion limi a ions, and o explo e how he educed acidi y o EDTA—due
o sodium coun e ions—a ec s dealumina ion e iciency. Fu he s udies on
zeoli es wi h na owe po e sys ems a e also encou aged.
35
Bachelo Thesis - Felipe Ma ´ınez Ba e o Uni e sidad Nacional de Colombia
2 CHAPTER 2: Adso p ion S udy o Alky-
la oma ics in Comme cial Y-Type Zeoli es
2.1 Abs ac
The adso p ion and deso p ion beha io o alkyl a oma ic compounds on
H-Y CBV 100 zeoli e was in es iga ed using empe a u e-p og ammed
deso p ion (TPD) expe imen s wi h oluene and benzene as p obe molecules.
The s udy aimed o e alua e he in luence o adso p ion empe a u e and
bed con igu a ion on deso p ion p o iles, ocusing on di usion limi a ions
wi hin he po ous zeoli e ne wo k. A dilu ed bed using SiC was employed o
minimize anspo a i ac s, allowing a clea e dis inc ion o adso p ion si e
dis ibu ions and ene ge ic p o iles.
Resul s showed dis inc di e ences be ween he deso p ion beha io s o
benzene and oluene. Benzene exhibi ed sha pe , well-de ined peaks wi hou
shoulde s, indica ing less hinde ed deso p ion, while oluene showed b oade
peaks wi h pseudo-peaks (shoulde s), pa icula ly a lowe adso p ion
empe a u es (25°C and 75°C), e lec ing s onge di usional cons ain s. In-
c easing he adso p ion empe a u e led o a shi o deso p ion peaks owa d
lowe empe a u es and a no able educ ion in peak in ensi y, a ibu ed o
educed molecula loading and weake coope a i e in e ac ions. In he case
o benzene, addi ional high- empe a u e peaks we e obse ed a ele a ed
adso p ion empe a u es, likely due o enhanced access o mic opo es by
mo e mobile, high-ene gy molecules.
A quali a i e analysis o he numbe and dis ibu ion o adso p ion
si es was pe o med by i ing he TPD da a using a Gaussian con olu ion
app oach wi h he lsqcu e i op imiza ion unc ion in MATLAB. While
his me hod p o ided insigh in o he dominan deso p ion si es, i emains
a phenomenological app oxima ion. Compa a i e analysis wi h a p e ious
s udy using undilu ed beds [2] con i med he posi i e impac o SiC dilu ion
in minimizing di usional esis ance and enhancing he in e p e abili y o
deso p ion beha io in zeoli e sys ems.
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Bachelo Thesis - Felipe Ma ´ınez Ba e o Uni e sidad Nacional de Colombia
2.2 In oduc ion
The s udy o adso p ion and deso p ion phenomena in po ous ma e ials
has been widely in es iga ed due o i s impo ance in sepa a ion p ocesses,
s o age sys ems, and he e ogeneous ca alysis. In pa icula , Y- ype zeoli es,
owing o hei well-de ined c ys alline s uc u e and he p esence o B øns ed
acid si es, ha e been ex ensi ely used in s udies ocusing on he in e ac ion o
o ganic and ino ganic molecules wi h mic opo ous su aces. Howe e , due o
he complexi y o hei po e ne wo k, mass anspo wi hin hese s uc u es
is o en limi ed by in ac ys alline o in e pa icle di usion phenomena,
which can signi ican ly a ec he expe imen ally obse ed adso p ion and
deso p ion p o iles.
Se e al s udies ha e highligh ed how di usi e anspo can dis o
he da a ob ained h ough echniques such as empe a u e-p og ammed
deso p ion (TPD). Fo ins ance, he in oduc ion o meso- and mac opo os-
i y in hie a chical zeoli es has been shown o enhance molecula mobili y
and educe he dis o ion o TPD p o iles [12]. Likewise, di usion inside
mic opo ous amewo ks can lead o b oadened peaks o mul iple deso p ion
signals in TPD cu es, which a e o en associa ed wi h a dis ibu ion o
adso p ion ene gies and in e nal anspo ba ie s [13, 14]. Addi ional wo k
has emphasized how bed compac ion, po osi y, and c ys al size a ec he
deso p ion kine ics o a oma ic compounds, in oducing he mal hys e esis
and di usional delay e ec s [15].
In line wi h his esea ch, a p e ious s udy ocused on he deso p ion
beha io o oluene and benzene in H-Y CBV 100 zeoli e using TPD
analysis [2]. The esul ing deso p ion p o iles exhibi ed b oad peaks,
high- empe a u e shi s, and he p esence o shoulde -like ea u es, all o
which sugges in e nal di usion limi a ions and a he e ogeneous dis ibu ion
o ac i e si es. The use o a compac bed in ha s udy e ealed he in luence
o anspo phenomena supe imposed on he ene ge ic beha io o he
adso ba e–adso ben sys em.
O he in es iga ions ha e explo ed s a egies o educe anspo e ec s
by modi ying bed a chi ec u e. Dilu ion o he zeoli e phase wi h ine
ma e ials such as SiC has been shown o imp o e he mal uni o mi y and
acili a e deso p ion by educing he esis ance o bulk low and in e nal
di usion [16]. Mo eo e , he de elopmen o mesos uc u ed zeoli es wi h
37
Bachelo Thesis - Felipe Ma ´ınez Ba e o Uni e sidad Nacional de Colombia
enhanced po e accessibili y and sho e di usion pa hs has u he enabled
he gene a ion o sha pe and mo e in e p e able TPD peaks [17].
Wi hin his amewo k, he p esen chap e p esen s a compa a i e
analysis o he TPD esul s o benzene and oluene adso bed on H-Y
CBV 100 zeoli e using a bed dilu ed wi h SiC, as opposed o con en ional
con igu a ions such as ha employed in [2]. The objec i e is o assess how
adso p ion empe a u e and bed s uc u e in luence he eme gence o di u-
si e phenomena, and how hese, in u n, a ec he quali a i e in e p e a ion
o adso p ion ene ge ics and he dis ibu ion o ac i e si es wi hin he zeoli e.
2.3 Ma e ials and Me hods
2.3.1 Physicochemical P ope ies o Zeoli e HY Powde (Zeolys
CBV100)
Zeolys CBV100 is a comme cially a ailable HY- ype zeoli e (NaY) syn he-
sized as a ine whi e powde , odo less and insoluble, in ended o adso p ion
and ca aly ic applica ions [18]. I possesses a aujasi e (FAU) amewo k,
cha ac e ized by a h ee-dimensional ne wo k o supe cages ( 13˚
A) in e con-
nec ed ia 12-membe ed ing windows ( 7.4˚
A), which enables access o ela-
i ely la ge molecules [19, 20].
The ma e ial ypically exhibi s a Si/Al mola a io a ound 5–5.1, p o iding
s ong B øns ed acidi y associa ed wi h amewo k aluminum si es, making
HY zeoli es highly ac i e in acid-ca alyzed eac ions [21, 22]. The su ace
a ea is high ( 900m²/g) wi h signi ican mic opo e and o al po e olume,
al hough ex e nal su ace a ea emains low [21, 23].
CBV100 is u ilized ex ensi ely in ca aly ic c acking p ocesses due o i s
s ong acidi y and he mal s abili y. I is also e ec i e in polyme deg ada ion
s udies, whe e i s s ong acid si es accele a e he onse o c acking eac ions
[22]. Addi ionally, i s s uc u e allows o applica ions in ionic sepa a ions
and molecula sie ing [24].
Upon dealumina ion (e.g., ia s eaming o acid ea men s), CBV100 can
be con e ed o HY o H-USY o ms, enhancing hyd o he mal s abili y and
gene a ing mesopo osi y ha imp o es ca aly ic li e ime and access o ac i e
si es [20, 17]. In NOx educ ion, coppe -loaded CBV100 has demons a ed
s able ca aly ic pe o mance abo e 300°C in lue-gas condi ions [25].
38
Bachelo Thesis - Felipe Ma ´ınez Ba e o Uni e sidad Nacional de Colombia
2.3.2 Equipmen Desc ip ion
Based on he Mas e ’s hesis by Cindy Ly Ta e a [2], he equipmen used o
he adso p ion es s o alkyl a oma ics on comme cial zeoli es was eassem-
bled, as i had been ou o ope a ion since 2022. The se up o his sys em is
shown in Figu e 20.
Figu e 20: Gas Phase Di e en ial Reac o Diag am
The sys em can be be e unde s ood by i s p o iding an o e iew o
he equipmen . A i s co e, he se up cen e s a ound a Di e en ial Reac o ,
consis ing o a qua z U- ube enclosed wi hin a u nace. The u nace supplies
he necessa y ene gy o main ain a cons an empe a u e o o ollow
a p og ammed empe a u e amp, egula ed p ecisely by a empe a u e
con olle .
To achie e be e con ol o e he eac ion o adso p ion a e, a sligh
dilu ion o he eed was essen ial. Fo his pu pose, wo gas inle s we e
connec ed: one o a mixed gas s eam such like Helium (He), A gon (A ),
Hid ogen (H2), Oxygen (O2), Me hane (CH4), Ca bon Dioxide (CO2) o
Ni ogen (N2) and he o he o a pu e gas low. The mixed gas line is ed by
39
Bachelo Thesis - Felipe Ma ´ınez Ba e o Uni e sidad Nacional de Colombia
a gas mixe composed o se e al Mass Flow Con olle s (MFCs), while he
second line supplies pu e helium o a gon di ec ly. The speci ic use o each
gas s eam du ing he expe imen al p ocedu e will be discussed la e .
Each o he gas inle lines is equipped wi h a empe a u e con olle , a
hea ing ape, and a he mocouple. This con igu a ion allows o p ecise em-
pe a u e con ol du ing he gas p ehea ing s age, ensu ing ha he desi ed
empe a u e is eached inside he eac o unde s eady-s a e condi ions.
Bo h lines will independen ly en e an a angemen o wo ou -way al es
(di e e al es), which will allow o di e en con igu a ions depending on
he speci ic case, as shown below in Figu e 21:
40
Bachelo Thesis - Felipe Ma ´ınez Ba e o Uni e sidad Nacional de Colombia
The ollowing ma hema ical de elopmen was conside ed o he calib a-
ion o he CO2-He mix u e wi h a de ined ou le composi ion and a o al
low o 50 mL/min:
Mass Balance and Composi ion De ini ion in Volume ic F ac-
ion
˙mmix = ˙mHe + ˙mCO2(4)
yCO2=QCO2
QHe +QCO2
(5)
Since he CO2–He sys em is conside ed app oxima ely ideal unde a mo-
sphe ic p essu e condi ions acco ding o [26], he ollowing app oxima ion
can be made. Howe e , i he sys em beha es non-ideally, an excess model
should be used o p edic VEand calcula e he espec i e Z alue o each
species:
ρmixQmix =ρHeQHe +ρCO2QCO2(6)
Whe e Qiis he olume ic low a e o componen iin (mL/min), and
ρiis he densi y in (kg/mL). Assuming ideal gas beha io , he densi y is ap-
p oxima ely linea wi h espec o empe a u e and p essu e. Howe e , o
alida e his assump ion, he densi y o bo h componen s and he mix u e
was modeled using Peng-Robinson in Aspen Plus. I was ound ha He i s a
linea end mo e closely han CO2, which is consis en wi h he in e molec-
ula in e ac ions o each gas. The mixing empe a u e emained a ambien
condi ions, i.e., 18◦C in Bogo ´a, and a p essu e o 40 PSIG.
47
Bachelo Thesis - Felipe Ma ´ınez Ba e o Uni e sidad Nacional de Colombia
Figu e 29: Pu e CO2and He Densi y
The mix u e densi y was hen es ima ed as a unc ion o CO2composi ion
a he ambien empe a u e o Bogo ´a, esul ing in he ollowing plo :
Figu e 30: CO2- He Mix u e Densi y using Peng-Robinson a 18°C
I was ound ha a i h-o de polynomial eg ession esul ed in e o s
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Bachelo Thesis - Felipe Ma ´ınez Ba e o Uni e sidad Nacional de Colombia
below 0.2%, while linea eg ession p oduced e o s be ween 0.9% and 2.4%:
Figu e 31: CO2- He Mix u e Rela i e E o o lineal 5 h o de eg ession
Wi h he densi ies o he pu e componen s and he mix u e calcula ed
using he Peng-Robinson equa ion, and knowing ha he desi ed o al low is
50 mL/min wi h a de ined olume ic composi ion, he sys em o Equa ions
5and 6allows de e mining he necessa y low a es o He and CO2 o be
in oduced in o he gas mixe . This esul s in a di ec calib a ion cu e o
he pe cen age openings o bo h mass low con olle s:
yCO2=QCO2
QHe +QCO2
QCO2=yCO2(QCO2+QHe)
QHe =QCO21
yCO2
−1(7)
Subs i u ing in o Equa ion 6, we ob ain:
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Bachelo Thesis - Felipe Ma ´ınez Ba e o Uni e sidad Nacional de Colombia
QHe =ρmixQmix
1
yCO2
−1ρHe +ρCO2
1
yCO2
−1(8)
Using he alue o QHe om Equa ion 7, QCO2can be de e mined. Wi h
hese alues and he calib a ion cu es, he co esponding opening pe cen -
ages o each low con olle we e ob ained. The ollowing esul s we e ob-
se ed:
Table 7: Compa ison be ween heo e ical and expe imen al low a es o
di e en CO2/He mix u es
yCO2( ol/ ol) QCO2QHe %A ea CO2%A ea He Flow Ra e Flow Ra e Rela i e
(mL/min) (mL/min) Theo e ical Expe imen al E o (%)
(cm3/min) (cm3/min)
0.05 2.5 47.1 12.4 82.7 50.00 50.34 0.67
0.10 4.9 44.5 24.7 78.0 50.00 49.93 0.13
0.15 7.4 41.9 37.0 73.5 50.00 50.13 0.25
0.20 9.8 39.4 49.2 69.1 50.00 50.19 0.37
This con i ms ha he linea adjus men o densi ies using he Peng-
Robinson model consis en ly ep esen s he CO2–He mix u e beha io . The
inal calib a ion cu e o ob ain a 50 mL/min gas mix u e a 40 PSIG is
shown below:
50
Bachelo Thesis - Felipe Ma ´ınez Ba e o Uni e sidad Nacional de Colombia
Figu e 32: CO2- He Mix u e Val e opening calib a ion o ob ain 50 mL/min
a 40 PSIG
2.3.4 TPD Expe imen a ion Desc ip ion
Fo his sec ion, ammonium- o m zeoli e HY- ype (Zeolys CBV 100) will be
used. This ma e ial will i s unde go calcina ion in he U-shaped eac o ,
ollowed by ei he a TPD expe imen o a s udy o di usional phenomena
h ough he injec ion o oluene and benzene p obes in o he zeoli e. In bo h
cases, he eac o is con igu ed as ollows:
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Bachelo Thesis - Felipe Ma ´ınez Ba e o Uni e sidad Nacional de Colombia
Figu e 33: U Reac o A angemen
The eac o has a diame e o 1.5 cm and an app oxima e leng h o 30
cm. Inside, a zeoli e laye wi h a hickness o 0.10 cm will be placed in i s
pu e o m, o 0.17 cm when dilu ed wi h silicon ca bide a 4.5 w %. This
zeoli e laye is suppo ed by qua z wool, which p o ides mechanical s abili y
and ensu es ha he bed emains in place. In addi ion, a 0.10 cm laye o
g ound qua z is included o imp o e empe a u e dis ibu ion wi hin he
eac o and o p e en he o ma ion o ho spo s, pa icula ly du ing he
calcina ion s ep. Las ly, a second laye o g ound qua z is added o p omo e
uni o m gas low h ough he bed and o a oid s agna ion zones. This packed
bed dis ibu ion, will ha e signi ican implica ions in T anspo Phenomena
along he TPD compa ed o he only Zeoli e packed bed eac o .
A ixed bed was loaded wi h 60 ±5 mg o sie ed zeoli e mixed
wi h 1273 ±5 mg o SiC, wi hin he Mesh 140–200 ange, co esponding o
pa icle sizes o app oxima ely 74 o 105 µm. The bed leng h was 1.7±0.2 cm.
Adso p ion o he p obe molecule was ca ied ou a h ee empe a u es:
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Bachelo Thesis - Felipe Ma ´ınez Ba e o Uni e sidad Nacional de Colombia
25°C, 75°C, and 150°C, based on he p e ious TPD esul s epo ed by [2].
Liquid pulses o 3, 4, o 6 µL o oluene and benzene we e injec ed, apidly
e apo a ing in o a 50 mL/min helium s eam (ine ca ie gas). Each pulse
con ained a known amoun o he p obe molecule, which was anspo ed in
apo phase o he bed.
Sa u a ion o he solid was conside ed o be achie ed when he signals
o successi e pulses showed no signi ican di e ences in heigh o a ea,
indica ing ha he solid could no longe adso b addi ional amoun s o he
injec ed species. This me hod enabled con olled s epwise sa u a ion and
was p e e ed o e di ec sa u a ion o imp o e esolu ion and con ol o he
adso bed amoun , as men ioned in [2].
Once he bed was sa u a ed, he mal deso p ion o he adso bed species
was pe o med s a ing in 298 K. The bed was hea ed up om he e o 623 K
a a linea a e o 10 K/min while main aining a cons an low o helium. The
deso p ion p o ile was eco ded as a unc ion o empe a u e, allowing analysis
o he in e ac ion s eng h be ween he p obe molecule and he zeoli e su ace.
2.3.5 Mass Spec ome e Calib a ion
Fo he calib a ion o he Mass Spec ome e , he in luence o he packed bed
on he a ea unde he peak cu e a di e en empe a u es was e alua ed.
To his end, 3 pulse injec ions o 3, 4, and 6 µL each we e pe o med a h ee
empe a u es: 25, 75, and 150°C. The expe imen s we e conduc ed using
bo h an emp y qua z eac o (Blanck) and eac o s packed wi h g ound
qua z and silicon ca bide (SiC). The co esponding peak a eas ob ained
om each expe imen a e p esen ed in Appendice B. These a eas we e
de e mined a e smoo hing he esponse cu es using he Sa i zky–Golay
me hod, applying a s onge eg ession window in egions wi hou peaks and
a ligh e one a ound he peak a eas.
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Bachelo Thesis - Felipe Ma ´ınez Ba e o Uni e sidad Nacional de Colombia
2.4 Resul s and Discussion
2.4.1 Mass Spec ome e Calib a ion Resul s
F om he da a ob ained and p esen ed in Appendix B, he ollowing was
ound:
Table 8: A eas unde he cu e o Toluene pulses a di e en empe a u es
and packing ma e ials (% Alkyl A oma ic ·second)
T (°C)
Pulse (µL) 3 4 6 Sample
25 338 466 795 Blank
25 456 659 943 SiC
75 231 329 497 Blank
75 369 474 723 SiC
150 327 433 713 Blank
150 395 510 766 SiC
Table 9: A eas unde he cu e o Benzene pulses a di e en empe a u es
and packing ma e ials (% Alkyl A oma ic ·second)
T (°C)
Pulse (µL) 3 4 6 Sample
25 681 849 1225 Blank
25 1033 1265 1920 SiC
75 637 861 1208 Blank
75 768 920 1370 SiC
150 815 1002 1293 Blank
150 792 902 1254 SiC
When plo ing he peak a ea as a unc ion o he pulse size o he p obe
a he h ee empe a u es, o bo h he blank es s and hose wi h SiC
(see Appendice B.3), a dec easing end in peak a ea wi h inc easing
empe a u e is obse ed up o a ce ain poin . Beyond ha poin , he
peak a ea measu ed by he mass spec ome e inc eases again in he case o
oluene. Howe e , o benzene, he inc ease in peak a ea is only obse ed
a e 75°C, as shown in Figu e 34 and Figu e 38:
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Bachelo Thesis - Felipe Ma ´ınez Ba e o Uni e sidad Nacional de Colombia
Figu e 34: A ea unde peaks (Blank sample) o a) Toluene and b) Benzene
Figu e 35: A ea unde peaks (SiC sample) o a) Toluene and b) Benzene
In he case o Toluene, i is impo an o conside wo key concep s:
axial dispe sion and anspo es ic ion. The o me is di ec ly ela ed o
he gas densi y, while he la e depends on he medium h ough which he
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Bachelo Thesis - Felipe Ma ´ınez Ba e o Uni e sidad Nacional de Colombia
gas lows. In his expe imen , when he qua z di e en ial eac o is emp y,
he obse ed peak a ea is lowe compa ed o he case whe e he eac o is
illed wi h a bed o g ound qua z mixed wi h SiC, ac oss all empe a u e
anges. This is a ibu ed o he educ ion o axial dispe sion caused by
low es ic ion, which allows highe concen a ions o Toluene o accumula e
wi hin he gas phase.
Addi ionally, a empe a u e-dependen end is obse ed: a 25°C, he
peak a ea is highes , bo h in he blank and wi h SiC ; i hen dec eases a
75°C and inc eases again a 150°C. To unde s and his beha io , wo speci ic
physical aspec s o he sys em mus be conside ed. Fi s , since he injec ion
is done by pulsing, Toluene en e s as disc e e d ople s, which e apo a e mo e
o less apidly depending on he empe a u e. Second, empe a u e also plays
a di ec ole in he axial dispe sion o he alkyla oma ic compound. These
wo opposing ac o s p oduce he obse ed end: a lowe empe a u es,
he e ec o lowe gas densi y (which inc eases concen a ion) domina es;
as empe a u e inc eases o 75°C, he highe densi y educes concen a ion
and hus peak a ea. Howe e , once he boiling poin o oluene (110.6°C) is
su passed, he e ec o immedia e e apo a ion becomes dominan . The e o e,
a 150°C, al hough he gas densi y is highe , he apid apo iza ion o he
d ople s esul s in signi ican ly highe concen a ion and consequen ly, a
la ge peak a ea. This a i ma ion may be seen in Appendice B.3.
Fo he case o Benzene, he same ela ionship is obse ed: he peak a ea
is g ea e wi h he SiC-packed bed compa ed o he emp y eac o . On he
o he hand, in he emp y eac o , he e appea s o be no signi ican di e ence
be ween 25°C and 75°C due o densi y e ec s, likely because he boiling poin
o Benzene (80°C) is close o bo h empe a u es. Howe e , once he sys em
eaches 150°C, Benzene unde goes apid apo iza ion, causing a sudden in-
c ease in concen a ion, which in u n leads o a la ge peak a ea. In he case
o he packed bed, he s uc u e appea s o dispe se he p obe mo e e ec-
i ely a 25°C, o e coming he e ec o densi y and esul ing in an inc eased
peak a ea. Howe e , a 75°C, he in luence o densi y begins o play a mo e
signi ican ole.
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Bachelo Thesis - Felipe Ma ´ınez Ba e o Uni e sidad Nacional de Colombia
Figu e 40: Benzene TPD Gaussian Con olu ion 25°C n=5
Figu e 41: Benzene TPD Gaussian Con olu ion 75°C n=4
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Figu e 42: Benzene TPD Gaussian Con olu ion 150°C n=3
And o Toluene:
Figu e 43: Toluene TPD Gaussian Con olu ion 25°C n=4
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Bachelo Thesis - Felipe Ma ´ınez Ba e o Uni e sidad Nacional de Colombia
Figu e 44: Toluene TPD Gaussian Con olu ion 75°C n=5
Figu e 45: Toluene TPD Gaussian Con olu ion 150°C n=3
F om he e, he ollowing Tables we e abula ed:
Fu he mo e, as a inal commen in his sec ion, he e is a signi ican
di e ence compa ed o he da a ob ained in he hesis by [2], in which a
g ea e numbe o di usional limi a ions can be obse ed o he H-Y Zeoli e
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T (°C) n A µ σ
25
1 0.29 46.45 9.15
2 1.91 131.13 31.20
3 4.22 234.73 19.15
4 3.98 202.47 26.78
5 0.45 330.40 14.12
75
1 2.13 138.59 30.70
2 3.89 193.68 21.26
3 2.68 218.56 15.72
4 0.40 306.20 14.57
150
1 0.46 99.03 27.05
2 2.28 181.58 27.26
3 2.77 213.47 19.72
4 0.13 310.47 12.73
Table 10: Fi ed pa ame e s om Gaussian con olu ion o Benzene TPD
cu es a di e en adso p ion empe a u es.
T (°C) n A µ σ
25
1 0.70 101.25 20.40
2 4.33 223.87 49.65
3 6.32 301.49 34.60
4 0.19 405.08 10.47
75
1 0.26 102.17 17.15
2 3.81 275.44 28.79
3 2.69 209.40 45.06
4 0.08 373.07 10.99
5 0.08 425.14 6.75
150
1 0.0001 99.0421 0.0343
2 1.1727 253.8591 19.8697
3 2.1445 211.2541 29.8077
Table 11: Fi ed pa ame e s om Gaussian con olu ion o Toluene TPD
cu es a di e en adso p ion empe a u es.
CBV 100, as shown below in Figu e 46:
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Figu e 46: Toluene and Benzene TPD epo ed by [2] a 25°C as Adso p ion
Tempe a u e
The abo e compa ison wi h he esul s ob ained in he p esen hesis is
consis en , conside ing ha in Cindy Ly’s expe imen s, he zeoli e bed was
no dilu ed wi h SiC. This hinde s he anspo o alkyl a oma ics h ough
he bed, esul ing in b oade TPD p o iles ha each signi ican ly highe
empe a u es han hose obse ed in he p esen wo k. In con as , in his
hesis, he ca i ies o med due o he g ain size o he SiC p omo e enhanced
mobili y, acili a ing anspo compa ed o he undilu ed bed expe imen s.
2.5 Conclusions
Based on he esul s ob ained in his sec ion, clea di e ences we e obse ed
in he TPD deso p ion p o iles be ween benzene and oluene, which a e
mainly a ibu ed o molecula size and di usional limi a ions wi hin he
po ous s uc u e o he H-Y zeoli e CBV 100. Benzene exhibi ed mo e de ined
cu es, wi h well-sepa a ed peaks and no shoulde s, indica ing a deso p ion
p ocess less limi ed by di usional phenomena. In con as , oluene showed
peaks wi h pseudo-peaks (shoulde s), especially a adso p ion empe a u es
o 25°C and 75°C, sugges ing g ea e di icul y in he adso p ion–deso p ion
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p ocesses due o in e nal di usion ba ie s and a g ea e di e si y o adso p-
ion si es.
When analyzing he e ec s o adso p ion empe a u e, i was ound
ha he deso p ion peaks end o shi owa d lowe empe a u es as he
adso p ion empe a u e inc eases. This beha io can be explained by a lowe
popula ion o adso bed molecules, which educes coope a i e in e ac ions
and a o s ea lie deso p ion. Mo eo e , he in ensi y o he peaks was ound
o dec ease signi ican ly as he adso p ion empe a u e inc eased, indica ing
ha he sys em ends o emain in he adso bed s a e o a sho e ime
due o he highe kine ic ene gy o he alkyl a oma ic molecules. In he
case o benzene, new highe -ene gy peaks appea ed when he adso p ion
empe a u es we e highe , which may be unde s ood as he esul o weake
in e ac ions wi h neighbo ing adso bed molecules and inc eased kine ic
ene gy ha allows access o mic opo es ha we e p e iously inaccessible.
The applica ion o he Gaussian con olu ion model allowed only o a
quali a i e (no phenomenological) cha ac e iza ion and iden i ica ion o
he p edominan adso p ion si es. Howe e , i emains necessa y o apply
a phenomenological model capable o adequa ely p edic ing he obse ed
adso p ion–deso p ion beha io s.
Finally, when compa ing he esul s o his hesis wi h hose ob ained
in Cindy Ly’s hesis, i was ound ha he absence o SiC dilu ion in
he expe imen al se up led o g ea e es ic ions in molecula mobili y
wi hin he sys em, esul ing in b oade TPD p o iles and signi ican ly highe
maximum deso p ion empe a u es. In con as , he use o a SiC-dilu ed bed
in his wo k enhanced he di usion o a oma ic compounds h ough he bed,
educing anspo limi a ions and cla i ying mo e p ecisely he es ic i e
e ec s o adso p ion–deso p ion in he H-Y zeoli e CBV 100, pa icula ly
wi h espec o he in luence o bed con igu a ion (dilu ion).
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Y. Ku oda, Y. K. Takahashi, R. A. Sasaki, M. Taka a, Y. Wakiha a, and
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beha io o be a zeoli e,” Jou nal o Ca alysis, ol. 148, no. 2, pp. 569–
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[10] J. Wei kamp, “Zeoli es and ca alysis,” Solid S a e Ionics, ol. 131, no.
1–2, pp. 175–188, 2000.
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hzsm-5 zeoli es by dealumina ion and ealumina ion wi h s eaming and
ci ic acid ea men s,” The Jou nal o Physical Chemis y B, ol. 110,
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a chical zeoli es: Enhanced molecula di usion and ca alysis o alkyla o-
ma ics,” Ca alysis Today, ol. 82, pp. 145–154, 2003.
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ing he s uc u e and dynamics o zeoli e ca alys s by solid-s a e nm ,”
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114, no. 14, pp. 7268–7316, 2016.
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alkanes and a oma ics,” Jou nal o Ca alysis, ol. 323, pp. 34–46, 2015.
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[20] M. Nich e wi z, M. Bo cha d , and T. Thielmann, “Sol en - ee hie a -
chiza ion o zeoli es by ca bochlo ina ion,” Jou nal o Ma e ials Chem-
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p oduc s/cb -100.
[22] C. Blazek, A. Klam , and R. Gl¨ase , “Ca aly ic c acking o polyme s o e
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o zeolys nay cb 100,” SSRN Elec onic Jou nal, 2023, a ailable a :
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[24] S. Tu ne , M. J. Hudson, and J. Klinowski, “Cha ac e iza ion o zeoli e
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He a 295 K.
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APPENDICES
A S anda d Ope a ing P ocedu e’s (SOP’s)
This sec ion includes he S anda d Ope a ing P ocedu es (SOPs) o he op-
e a ion o he Mass Spec ome e and he execu ion o he adso p ion and
deso p ion uns in he qua z di e en ial eac o , de eloped in his hesis.
A.1 S anda d Ope a ing P ocedu e (SOP) - Di e en-
ial Reac o Ope a ion
1. Check ha all plugs a e connec ed o hei espec i e con olle s (Box,
He/A , and Val e 1) and o hei powe sou ces.
2. Tu n on he hea ing apes wi h he con olle s and se he se poin o
p ehea he gas.
3. Tu n on he u nace and p og am he co esponding empe a u e amps
acco ding o he ollowing p o ocol:
a. P ess he up and down a ows simul aneously. Use Mode o go o
Global and check ha RATE is in P yp. P ess DSPY.
b. P og am he amp: P ess Mode, hen use he up a ow o go o
P og, selec File 1 wi h Mode, hen s ep 1 wi h Mode,Mode (en-
e se poin ), Mode (inpu desi ed se poin alue), Mode (se he
hea ing a e in °C/min), Mode o go o File 1, s ep 2, and se
SOAH o main ain empe a u e o xhou s, yminu es, zseconds.
c. Once he hea ing amp is p og ammed, u n on he u nace using
Hold/Run (hold and selec he ile you wan o ac i a e).
d. Ensu e he u nace con olle swi ch is poin ing upwa ds.
No e: I is impo an o hea slowly, wi h a maximum a e o 1 °C/min,
as o e shoo ing he se poin is possible due o he u nace’s elec ic
powe .
4. Once he u nace is on, open he al es o he gases o be used o 40
psi.
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Bachelo Thesis - Felipe Ma ´ınez Ba e o Uni e sidad Nacional de Colombia
Figu e 54: Smoo hed Toluene peaks a 75°C (SiC sample)
Figu e 55: Smoo hed Toluene peaks a 150°C (SiC sample)
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Bachelo Thesis - Felipe Ma ´ınez Ba e o Uni e sidad Nacional de Colombia
Figu e 56: Smoo hed Benzene peaks a 25°C (SiC sample)
Figu e 57: Smoo hed Benzene peaks a 75°C (SiC sample)
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Figu e 58: Smoo hed Benzene peaks a 150°C (SiC sample)
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Bachelo Thesis - Felipe Ma ´ınez Ba e o Uni e sidad Nacional de Colombia
B.2 A ea unde smoo hed peaks o Mass Spec ome-
e Calib a ion
Figu e 59: A ea unde Toluene peaks a 25°C (Blank sample)
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Bachelo Thesis - Felipe Ma ´ınez Ba e o Uni e sidad Nacional de Colombia
Figu e 60: A ea unde Toluene peaks a 75°C (Blank sample)
Figu e 61: A ea unde Toluene peaks a 150°C (Blank sample)
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Figu e 62: A ea unde Benzene peaks a 25°C (Blank sample)
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Bachelo Thesis - Felipe Ma ´ınez Ba e o Uni e sidad Nacional de Colombia
Figu e 63: A ea unde Benzene peaks a 75°C (Blank sample)
Figu e 64: A ea unde Benzene peaks a 150°C (Blank sample)
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Figu e 65: A ea unde Toluene peaks a 25°C (SiC sample)
Figu e 66: A ea unde Toluene peaks a 75°C (SiC sample)
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Bachelo Thesis - Felipe Ma ´ınez Ba e o Uni e sidad Nacional de Colombia
Figu e 67: A ea unde Toluene peaks a 150°C (SiC sample)
Figu e 68: A ea unde Benzene peaks a 25°C (SiC sample)
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Bachelo Thesis - Felipe Ma ´ınez Ba e o Uni e sidad Nacional de Colombia
Figu e 69: A ea unde Benzene peaks a 75°C (SiC sample)
Figu e 70: A ea unde Benzene peaks a 150°C (SiC sample)
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Bachelo Thesis - Felipe Ma ´ınez Ba e o Uni e sidad Nacional de Colombia
Figu e 81: Benzene 25°C Adso p ion TPD
Figu e 82: Benzene 75°C Adso p ion TPD
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Bachelo Thesis - Felipe Ma ´ınez Ba e o Uni e sidad Nacional de Colombia
Figu e 83: Benzene 150°C Adso p ion TPD
Figu e 84: Toluene injec ion in 3µL pulses a 25°C ollowed by TPD analysis.
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Bachelo Thesis - Felipe Ma ´ınez Ba e o Uni e sidad Nacional de Colombia
Figu e 85: Toluene injec ion in 3µL pulses a 75°C ollowed by TPD analysis.
Figu e 86: Toluene injec ion in 3µL pulses a 150°C ollowed by TPD anal-
ysis.
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Bachelo Thesis - Felipe Ma ´ınez Ba e o Uni e sidad Nacional de Colombia
Figu e 87: Toluene 25°C Adso p ion TPD
Figu e 88: Toluene 75°C Adso p ion TPD
98
Bachelo Thesis - Felipe Ma ´ınez Ba e o Uni e sidad Nacional de Colombia
Figu e 89: Toluene 150°C Adso p ion TPD
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