Table Of ContentSPRINGER BRIEFS IN
APPLIED SCIENCES AND TECHNOLOGY
Angelo Freni · Belal Dawoud
Lucio Bonaccorsi · Stefanie Chmielewski
Andrea Frazzica · Luigi Calabrese
Giovanni Restuccia
Characterization
of Zeolite-Based
Coatings for
Adsorption
Heat Pumps
123
SpringerBriefs in Applied Sciences
and Technology
More information about this series at http://www.springer.com/series/8884
Angelo Freni Belal Dawoud
(cid:129)
Lucio Bonaccorsi Stefanie Chmielewski
(cid:129)
Andrea Frazzica Luigi Calabrese
(cid:129)
Giovanni Restuccia
Characterization
of Zeolite-Based Coatings
for Adsorption Heat Pumps
123
Angelo Freni Andrea Frazzica
ConsiglioNazionaledelleRicerche,Istituto ConsiglioNazionaledelleRicerche,Istituto
diTecnologieAvanzate perl’Energia diTecnologieAvanzate perl’Energia
“Nicola Giordano” “Nicola Giordano”
Messina Messina
Italy Italy
Belal Dawoud LuigiCalabrese
EastBavarian Technical University Department of ElectronicEngineering,
(OTH-Regensburg) IndustrialChemistryand Engineering
Regensburg Universityof Messina,Contrada di Dio
Germany Messina
Italy
LucioBonaccorsi
Department of ElectronicEngineering, GiovanniRestuccia
IndustrialChemistryand Engineering ConsiglioNazionaledelleRicerche,Istituto
Universityof Messina,Contrada di Dio diTecnologieAvanzate perl’Energia
Messina “Nicola Giordano”
Italy Messina
Italy
Stefanie Chmielewski
Viessmann Werke Allendorf GmbH
Allendorf (Eder)
Germany
ISSN 2191-530X ISSN 2191-5318 (electronic)
SpringerBriefs inApplied Sciencesand Technology
ISBN 978-3-319-09326-0 ISBN 978-3-319-09327-7 (eBook)
DOI 10.1007/978-3-319-09327-7
LibraryofCongressControlNumber:2015934678
SpringerChamHeidelbergNewYorkDordrechtLondon
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Contents
1 Basics of Adsorption Heat Pump Processes . . . . . . . . . . . . . . . . . . 1
1.1 Thermodynamics of Thermally Driven Heat Pumps . . . . . . . . . . 2
1.2 Working Pairs. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
1.2.1 Silica Gels . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
1.2.2 Composite Materials . . . . . . . . . . . . . . . . . . . . . . . . . . 8
1.2.3 Activated Carbons. . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
1.2.4 Zeolites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
1.2.5 New Trends . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
1.3 The Ideal Intermittent Adsorption Heat Pump Cycle. . . . . . . . . . 15
1.4 Energetic Evaluation of the Real Intermittent Adsorption
Heat Pump Cycle. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21
1.5 Basic Features and Design Requirements of Intermittent
Adsorption Heat Pumps . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25
1.6 Short Overview on Advanced Cycles. . . . . . . . . . . . . . . . . . . . 28
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30
2 Adsorption Heat Exchangers . . . . . . . . . . . . . . . . . . . . . . . . . . . . 35
2.1 Ideal Adsorber Design Requirements . . . . . . . . . . . . . . . . . . . . 35
2.2 Overview on Adsorber Developments for Adsorption
Heat Pumps . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 36
2.3 Introduction to the Concept of Coated Adsorbers. . . . . . . . . . . . 42
2.4 Methodologies for the Experimental Characterization
of Zeolites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 44
2.5 Experimental Methodologies to Verify the Performance
of Adsorbers. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 47
2.5.1 Small Scale Large Pressure Jump (LPJ) . . . . . . . . . . . . . 47
2.5.2 Small Scale Large Temperature Jump (LTJ) . . . . . . . . . . 48
2.5.3 Full Scale Experimental Setup for Cycling
Characterization. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 50
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 51
v
vi Contents
3 Hydrothermal Stability of Adsorbent Coatings . . . . . . . . . . . . . . . 55
3.1 Hydrothermal Aging of Zeolites . . . . . . . . . . . . . . . . . . . . . . . 55
3.2 Real-Time or Long-Term Heat Pump Aging Cycling
Procedure. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 59
3.2.1 Description of the Set-up . . . . . . . . . . . . . . . . . . . . . . . 59
3.2.2 Experimental Testing. . . . . . . . . . . . . . . . . . . . . . . . . . 61
3.3 Accelerated Aging Cycling Procedure. . . . . . . . . . . . . . . . . . . . 65
3.3.1 Description of the Set-up . . . . . . . . . . . . . . . . . . . . . . . 65
3.3.2 Estimation of the Operating Conditions
for AQSOA- FAMZ02 Zeolite . . . . . . . . . . . . . . . . . . . 67
3.3.3 Experimental Testing. . . . . . . . . . . . . . . . . . . . . . . . . . 69
3.4 Very-Quick Aging Cycling Procedure . . . . . . . . . . . . . . . . . . . 71
3.4.1 Description of the Set-up . . . . . . . . . . . . . . . . . . . . . . . 71
3.4.2 Experimental Testing. . . . . . . . . . . . . . . . . . . . . . . . . . 72
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 78
4 Mechanical Stability of Adsorbent Coatings. . . . . . . . . . . . . . . . . . 81
4.1 Static Mechanical Tests . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 81
4.1.1 Flexural Test. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 81
4.1.2 Shear Test . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 83
4.1.3 Micro-hardness Test. . . . . . . . . . . . . . . . . . . . . . . . . . . 83
4.1.4 Scratch Test . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 85
4.1.5 Pull-off Test. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 85
4.1.6 Peel Test . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 86
4.2 Dynamic Tests . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 87
4.2.1 Impact Test. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 87
4.2.2 Vibrational Test. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 88
4.3 Methods Comparison. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 91
4.4 Experimental Case History: Adhesion Quality Control
on a Coated Adsorber. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 92
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 95
Introduction
The present book illustrates novel methods for the complete characterization of
advancedcoatedadsorberstobeusedinthermallyefficientadsorptionheatpumps.
It provides a deep analysis of the different procedures necessary for the evaluation
oftheachievableperformanceoftheadsorberaswellasforitsstabilityagainstboth
hydrothermal and mechanical stresses.
InChap.1wetreatthethermodynamicfundamentalsofthebasicadsorptionheat
pumpprocess.Themostcommonworkingpairs,aswellasthenewresearchtrends,
are explained with emphasis on the zeolite–water pair, which is the specific
adsorbent/adsorbatesystemaddressedinthisbook.Weprovidedbasicinformation
about the structural characteristics of the zeolites (NaA, 13X, Y, SAPO34), which
are commonly employed in adsorption heat pumps. Afterwards, the ideal and real
intermittent adsorption heat pump cycles are precisely described and the corre-
spondent energetic evaluations are developed. These formulations permit to
investigatetheinfluenceofdesignparametersontheperformanceofanadsorption
heatpumpmodule,focusingontheadsorberdesign.Thisstudyleads,inessence,to
identify the adsorption heat exchanger basic design requirements, which will be
treated in the following chapter. This chapter ends with a short overview of other
more sophisticated adsorption heat pump processes.
InChap.2,weinitiallyreporttheevolutionofadsorberconceptsovertheyears,
starting from the earlier configurations employing loose adsorbent grains, to the
modern concept of coated adsorber, which is the focus of this book. Then we
explain the most common coating procedures that, essentially, consist of the
deposition, by means of a binder or by direct crystallization, of the adsorbent
material over a metallic heat exchanger, aiming at the improvement of the heat
transfer efficiency. After having introduced the coated adsorber concept, we deal
withthefundamentaltaskoftheexperimentalcharacterizationofcoatedadsorbers.
Initially, standard methodologies for the experimental characterization of pure
zeolites are given as fundamental background to better understand the more
sophisticatedtechniquesdevelopedtoassesstheperformanceandstabilityofcoated
adsorbers. Subsequently, we provide the description of the recent experimental
methodologies for adsorber dynamic efficiency evaluation. Two main approaches
vii
viii Introduction
are distinguished considering the scale of the tested adsorber: small scale, which
allows to test small but representative piece of adsorber concepts, and full scale,
where the entire adsorber can be tested under almost-realistic boundary conditions
Chapters 3 and 4 are focused on the crucial subject of the verification of
mechanicalandhydrothermalcyclingstabilityofadsorbentcoatings.InChap.3we
initially discuss the effects of hydrothermal aging of pure zeolites due to repeated
cyclic adsorption and desorption of water, which can result in reduced adsorption
capacity and adsorption rate. Afterwards, we propose three original methodologies
for hydrothermal aging treatment suitable for adsorbent coatings and pelletized
adsorbers: (a) real-time or long-term heat pump cycling under realistic vacuum
adsorptionheatpumpingconditions,(b)acceleratedagingcyclingunderwet/dryair
flux, and (c) very quick aging cycling under severe hot air blow/cold liquid water
treatment. Such techniques have been applied on samples of pelletized adsorbent
and adsorbent coatings prepared according to different methods having different
maturitylevels:fromlaboratoryscaletopre-commercialpilotscale.Foreachaging
method, advantages and limits are explained and some results of aging tests are
provided and compared.
In Chap. 4, we address the mechanical characterization of the same adsorbent
coating samples characterized in the previous chapter. In this chapter, the experi-
mentalprotocolsunderstaticanddynamictestingsetupweredeveloped,inorderto
ensure a broad, comprehensive, and reliable identification of the mechanical per-
formance of the coatings used in the heat exchangers. In particular, the results of
tests carried out on coatings at laboratory-scale level have shown a quite brittle
behavior that influences its mechanical stability especially under dynamic loading.
Instead, the pilot-scale coating, characterized by high hardness, showed good
adhesion with the metallic substrate and very good performance in static and
dynamic testing conditions. This chapter ends with an experimental case history
dealing with the adhesion quality control on a coated adsorber.
Combined results of the testing protocol presented in Chaps. 3 and 4 indicate
that some coating techniques still at laboratory level of development need further
improvement to reach sufficiently high lifetime to meet durability requirements of
commercial applications. Good hydrothermal and mechanical stabilities were
exhibitedbythepilot-scale coated adsorber heat exchangers.Inalarge-scale serial
productionprocess, it isa fundamentalrequirementtoguarantee orevento further
improvebothmechanicalandhydrothermalstabilitiesofthecoatedheatexchangers
at moderate costs. Full commercial state of adsorber heat exchangers should be
approved according to a quality assurance test protocol based on the experimental
methods introduced in this book, which could be a subject of the future work.
Wehopethatthisbookwillgiveahandtoresearchers anddevelopingteamsof
adsorption heat pumps for heating and cooling applications, helping to guide and
intensifybothresearchanddevelopmentactivities,mostspecificallyfordeveloping
and approving novel adsorbents and novel adsorbent beds.
Introduction ix
Finally, the authors are highly grateful to the German Federal Ministry of
Economy and Technology (BMWi) for partial funding of the research and devel-
opment activities between July 2007 and March 2010 (Förderkennzeichen:
0327435A)aswellasbetweenJune2010andNovember2012(Förderkennzeichen:
0327435B).
