Study of Almond Shell Characteristics

12 Pages·2017·7.38 MB·English

materials
Article
Study of Almond Shell Characteristics
XueminLi,YinanLiu,JianxiuHaoandWeihongWang*
KeyLaboratoryofBio-basedMaterialScience&Technology(EducationMinistry),NortheastForestry
University,Harbin150040,China;[email protected](X.L.);[email protected](Y.L.);
[email protected](J.H.)
* Correspondence:[email protected]
(cid:1)(cid:2)(cid:3)(cid:1)(cid:4)(cid:5)(cid:6)(cid:7)(cid:8)(cid:1)
(cid:1)(cid:2)(cid:3)(cid:4)(cid:5)(cid:6)(cid:7)
Received:17August2018;Accepted:12September2018;Published:19September2018
Abstract: Alargeamountofalmondshellsaredisposedofeveryyear. Theanatomicalandchemical
characteristics of almond shells are investigated in this paper in order to contribute to better
utilizationoftheseshells. Themicromorphology,surfaceelements,thermalstability,crystallization,
chemicalcomposition,andrelativepropertiesofalmondshellsareanalyzed. Underobservationby
microscopeandelectronmicroscope,thediameterofalmondshellsis300–500µmforlargeholes,
and 40–60 µm for small holes present in the shell. X-ray photoelectron spectroscopy shows the
elements of almond shells include C (72.27%), O (22.88%), N (3.87%), and Si (0.87%). The main
chemical constituents of cellulose, hemicellulose and lignin in almond shells account for 38.48%,
28.82%and29.54%,respectively. Thealkalineextractcontentofalmondshellsis14.03%,andbenzene
alcohol extraction is 8.00%. The benzene alcohol extractives of almond shells mainly contain
17 types of organic compound, including benzene ring, ethylene, carbon three bond, and other
mufti-functional groups. Thermal stability analysis shows almond shells mainly lose weight at
260◦Cand335◦C.Thesecharacteristicsindicatethatalmondshellshavethecapacitytobeusedin
compositesandabsorptionmaterials.
Keywords: almondshells;anatomicalstructure;chemicalcomposition;thermalstability
1. Introduction
Biomassnutshellisalargeyieldcropresiduewhichisgenerallydiscardedorincinerated. Thisnot
onlypollutestheenvironment,butalsowastesalargeamountofresources. Inordertoavoidthis,
many scholars have undertaken research into its potential uses, including the use of biomass nut
shellstoproduceactivatedcarbon. Ahmadetal. usedpeanutshelladsorptionoftrichloroethylenefor
cleaningwater[1],whileLanetal.preparedactivatedcarbonfromHawaiinutshells[2].Martínewetal.
preparedactivatedcarbonfromwalnutshells,andstudieditsproperties[3],andYangetal.formulated
highspecificsurfaceareaactivatedcarbonfromcoconutshellsbymicrowaveheating[4].Okutucuetal.
producedfungicidaloilandactivatedcarbonfrompistachioshells[5].Inadditiontothemanufacturing
ofactivatedcarbon,biomassnutshellshaveanumberofotheruses.Wongchareeetal.usedmacadamia
nutshellresidueasmagneticnanosorbents[6],andPinoetal. studiedthebiosorptionofcadmium
usingcoconutshells[7]. Notably,biomassnutshellhasalsobeenusedincomposites. Alsaadietal.
studiedtheeffectofthecontentofparticlesonthemechanicalpropertiesofpolymercomposites[8],
andBaeetal. havepreparedcompositebymacadamianutshellforcapturingCO [9]. Bledzkietal.
2
studiedtheeffectsoffiberphysicsandchemistryonthepropertiesofcompositespreparedfrombarley
shellandcoconutshellreinforcedpolypropylene[10],andAyrilmisetal. manufacturedchestnutshell
reinforcedpolypropylenecomposite[11]. Inaddition,Kasiramanetal. usedcashewnutshellsasfuel
forcamphoroilblending[12],andBartoccietal. provedthatbiomassshellsimprovesoilhealthand
fertilitywhenusedasoilamendment[13]. Wangetal. demonstratedthatbiocarboncouldpossibly
replacefossilfuel,andhelpreducegreenhousegasemissions[14].
Materials2018,11,1782;doi:10.3390/ma11091782 www.mdpi.com/journal/materials
Materials2018,11,1782 2of12
Almondsareatypeofbiomassnutshellandarewidelygrowninmanyregionsoftheworld
includingIndia,Pakistan,Iran,andChina. Asof2014,globaloutputofalmondswasthreemillion
tonsannually(data). Almondshellsaccountforaround35–75%ofthetotalfruitweight,soabout
10.5–22.5milliontonsofshellswereleft[15]. Thishugequantityofshellshasgreateconomicand
practical potential, and investigation into the best way to utilize the shell is attracting increasing
attention. Rodríguez-Reinoso et al. and Toles et al. prepared activated carbon with almond
shells, studying its physical, chemical and adsorptive properties, as well as estimated cost of
production[16,17].Senturketal. haveusedalmondshellsasadsorbentstoremovedyerhodamine
fromaqueoussolutions[18]. Mohanetal. preparedmagneticandactivatedcarbonbyalmondshellsto
remove2,4,6-trinitrophenolfromwater[19],andEssabiretal. reinforcedpolypropylenewithalmond
shellsbyextrusionprocess[20]. Lashgarietal. studiedtheeffectoftheloadingamountofnano-clay
andcontentofalmondshellpowderonthestrengthandpropertiesofpolypropylenecomposites[21].
Duetosuchstudiesintoalmondshellutilization, thereislimitedknowledgeofalmondshell
structure and chemical properties. Caballero et al. studied the kinetics of slowing the thermal
decomposition of almond shells, and analyzed the pyrolysis of lignin and whole cellulose [22].
InthestudiesofEssabiretal. andElleuchetal., itisshownthatalmondshellsareabsorbentand
environmentallyfriendly[20,23]. Thisarticlefocusesonthebasicchemicalcompositionandphysical
structureofalmondshellsinordertomakebetteruseofthislargequantitybio-resource.
2. MaterialsandMethods
2.1. Materials
The almond shells used in this study were purchased from Anhui Liang Zhong Liang Food
(Huai’an,China). Poplarwoodparticles,asacontrol,werepurchasedfromJinanYuanfangWood
Trading Company (Jinan, China). Both almond shells and poplar particles were screened into
40–60meshand60–80mesh.
2.2. ChemicalComposition
The main chemical composition of almond shell particles of 40–60 mesh were measured
accordingtoChinesestandardGBT35816-2018(StandardMethodforDeterminationofStructural
CarbohydratesandLignininBiomassRawMaterial). Thecontentsumofhemicelluloseandcellulose
wasdeterminedbyusingglacialaceticacidandsodiumhypochloriteasasolvent. Afterrepeated
washing,thepolysaccharideinthealmondshellswasdissolved,thendriedandmeasured.Thecontent
ofcellulosewasdeterminedbyusingnitricacidandethanolassolvent. Othernon-cellulosicmaterials
including lignin, hemicellulose, and other materials in the sample are eluted to obtain cellulose.
Thelignincontentwasdeterminedbysulfatemethod. Afterthesulfuricacidsolventwasremoved,
theresiduewasmeasuredtodeterminethequalityoflignin.
Particles of 40–60 mesh almond shell were used to measure extractives according to GBT
35818-2018(StandardMethodforAnalysisofForestryBiomass-DeterminationofExtractivesContent).
Extractivecontentofalmondshellwasmeasuredaftertheshellsweretreatedwithcoldwaterfor
48h, hotwaterfor6h, 1%NaOHfor1h, orbenzenealcohol(Vbenzene/Vethanol=2:1)for6h.
Inaddition,thebenzenealcoholextractivesolutionwasdilutedto0.1mg/mL(Vbenzene/Vethanol
= 2:1), and its chemical composition was measured by GC/MS (7890A-7000B, American Agilent
Corporation,SantaClara,CA,USA).
2.3. InfraredSpectrum
AlmondshellsandpoplarparticleswerescannedbyFourierinfraredspectrometer(Nicolette
6700,AmericanWaterCorporation,LosAngeles,CA,USA).TheKBrdiskmethodwasemployedfor
thesample,andwavelengthwas500–3500cm−1ataresolutionof5cm−1.
Materials2018,11,1782 3of12
2.4. X-rayDiffraction
Almond shells and poplar particles of 60–80 mesh were measured by X-ray diffraction
(D/max-2200VPC,Japanscienceco.,Ltd.,TakatsukiCity,Osaka,Japan)intherangeof2θ=5–40◦
at scanning speed of 5 rad/cm. Two samples were repeated. The X-ray source was a Cu target
(CuKα=1.54056),andanickelfilterwasusedtoexcitealpharadiation. Thecrystallizationindexof
thesamplewascalculatedaccordingtotheprotocolFormula(1)asfollows[24]:
I −I
CrI(%) = 002 am ×100% (1)
I
002
whereI istheintensityat2θ=22◦,andI istheintensityofbackgroundscatterat2θ=16◦.
002 am
2.5. SurfaceElement
Almond shells and poplar particles of 60–80 mesh were scanned by an X-ray photo-electron
spectrometer(THERMO,AmericanThermoelectricGroup,Waltham,MA,USA).Sampleswereexcited
withmonochromaticAlKαrays(1,486.6eV).Thesamplebindingenergy(EB)chargecorrectionwas
performedusingacontaminatedcarbonC1s(284.8eV).TheX-raybeamwassetat6mA,andthe
passing energy was 50 eV. The sputtering ion gun was 1000 eV, and the scanning step was 0.1 eV.
Twosampleswererepeated.
2.6. ThermalStability
The thermal stability of almond shells and poplar particles was measured by high-precision
thermogravimetricanalyzer(TG209F1,NETZSCHScientificInstrumentsTrading,Bavaria,Germany).
The temperature was increased from 0 ◦C to 800 ◦C at the rate of 10 ◦C/min. Two samples
wererepeated.
2.7. MicroscopicMorphology
Thestructureofalmondshellswasobservedbyastereomicroscopicevaluation(JSZ6S,Jiangnan
YongxinCompany,Guangzhou,China),andthenbyscanningelectronmicroscopy(SEM)(QuanTa200,
DutchFEIcompany,Hillsboro,OR,USA).Thecutcross-sectionofthealmondshellwasthensprayed
withgoldandobservedattheaccelerationvoltageof12.5kV.
3. ResultsandDiscussion
3.1. MicroscopicMorphology
Almondshellshavewell-developedporestructure,asillustratedinFigure1,wherearowoflarge
holescanbeseendistributedinthecrosssection. Diameterofthebigholesis300–500µm(Figure1b).
Theareaaroundtheholesisrelativelydense;however,itisfullofsmallhollowballs. UnderSEM,
almondshellsappeartobecomposedoftightlycompactedballsfromtheviewofcrosssectionshown
inFigure1c. Thediameterofthesehollowballsisabout40–60µm,andthicknessoftheballwallis
20–40µm. Whenenlarged3000times(Figure1d),tinyholesarefounddistributedonthewallofballs,
andthewallisvisiblylayered. Thealmondshellwallisfullofholesofvarieddiameter,makingit
lightandpotentiallyeasilyabsorbed.
Materials2018,11,1782 4of12
Materials 2018, 11, x FOR PEER REVIEW 4 of 12

Figure1.Almondshellmicro-topography.(a)Overallview;(b)Cross-sectionofshell;(c)Densepartof
Figure 1. Almond shell micro-topography. (a) Overall view; (b) cross-section of shell; (c) dense part
aolmf aolnmdosnhde lslh;(edll); H(do)l hloowllobwal lbianllt ihne tahlem aolnmdonshde sllh.ell.
3.2. ChemicalComposition
3.2. Chemical Composition
Thecontentofcelluloseinalmondshellsis38.475%,whichislowerthanthatofpoplar(containing
The content of cellulose in almond shells is 38.475%, which is lower than that of poplar
44.12%cellulose),buthigherthanothershellsexceptpistachioshell(Table1). Thisindicatesthatthe
(containing 44.12% cellulose), but higher than other shells except pistachio shell (Table 1). This
mechanical properties of composite prepared by almond shells might be higher than that of most
indicates that the mechanical properties of composite prepared by almond shells might be higher
biomassnutshells.
than that of most biomass nut shells.
Table1.Proportionofcellulose,hemicellulose,lignininsixkindsofbiomass(wt%).
Table 1. Proportion of cellulose, hemicellulose, lignin in six kinds of biomass (wt %).
Sample Cellulose Hemicellulose Lignin
SaAmlpmloen dshells 3C8.e47llu±lo0.s3e9 28.8H2e±m0i.c2e5llulose 29.54±0.11Lignin
Poplar 44.12±0.23 30.21±0.11 21.24±0.31
AlmonCdoc sohneultlss hells 3348..1427± ± 00..2309 22.362±8.18.247 ± 0.25 28.04±0.5279.54 ± 0.11
Walnutshells 36.38±0.05 27.85±0.31 43.70±0.57
PoCphleasrt nutshells 2414..4172± ± 00..2273 16.283±0.02.135 ± 0.11 36.58±0.2261.24 ± 0.31
Pistachioshells 43.08±0.19 25.30±0.46 16.33±0.41
Coconut shells 34.12 ± 0.20 22.36 ± 1.47 28.04 ± 0.57
Note: Thedataofalmondshellsandpoplarweremeasuredbyauthors,andtherestofthemeasurementsare
derivedfromliterature[25].
Walnut shells 36.38 ± 0.05 27.85 ± 0.31 43.70 ± 0.57
LigniCnhiessatnnuatm shorepllhs oussubsta2n1c.e47w ±it h0.o2u7t fixedstruct1u6r.e2;8h ±o 0w.3e5v er,itisthre3e-6d.5im8 ±e n0s.2io6n aland
highlybranched. Ligningenerallysurroundsmicrofibersandlargefibers. Thecovalentbondbetween
Pistachio shells 43.08 ± 0.19 25.30 ± 0.46 16.33 ± 0.41
ligninandpolysaccharidegreatlyenhancesthebondingstrengthbetweenthecellulosefiberandthe
ligninNmoatetr: ixT,haen ddatthau osfp alalmysonadr oslheeilnlsb aonndd ipnogpalanrd wsterreen gmtheaesnuirnegd. Tbhy ealuigthnoinrs,c oanntde ntthoe fraelsmt oonf dthseh ells
is29.5m4%ea,suhriegmheenrttsh aarne dtheraitveodf fproompl alirte,rwathuirceh [2c5o].n tains21.24%. Ligninmaybebeneficialtoimprove
compatibilitywiththermoplastic,andithasacertainflame-retardanteffectwhichisimportantfor
Lignin is an amorphous substance without fixed structure; however, it is three-dimensional and
composites being used as building materials. The special ring structure and hydroxide structure
highly branched. Lignin generally surrounds microfibers and large fibers. The covalent bond
ofhemicelluloseproducesareactiveactivitygenerallyhigherthanthatofcellulose. Thecontentof
between lignin and polysaccharide greatly enhances the bonding strength between the cellulose fiber
hemicellulose in almond shells and poplar is similar, and higher than other nuts listed in Table 1.
and the lignin matrix, and thus plays a role in bonding and strengthening. The lignin content of
Thisindicatesthatalmondshellsmayhavemoreprospectsformodification.
almond shells is 29.54%, higher than that of poplar, which contains 21.24%. Lignin may be beneficial
TheextractivecontentofalmondshellsandpoplarispresentedinTable2. Extractivesfromalkali
to improve compatibility with thermoplastic, and it has a certain flame-retardant effect which is
method were the highest, followed by benzene and cold water. This result is related to solubility
important for composites being used as building materials. The special ring structure and hydroxide
in different solvents. Cold water extractives of almond shells were 3.14%, and poplar was 0.11%.
structure of hemicellulose produces a reactive activity generally higher than that of cellulose. The
Thisindicatesthatalmondshellscontainmoreterpenes,phenols,hydrocarbons,andestercompounds
content of hemicellulose in almond shells and poplar is similar, and higher than other nuts listed in
thanpoplar[26]. Terpenesandphenolsarethemaincomponentoffragrance,thusalmondshellscould
Table 1. This indicates that almond shells may have more prospects for modification.
potentiallybeusedasarawmaterialforcreatingessence. Thecontentofhotwaterextractwashigher
The extractive content of almond shells and poplar is presented in Table 2. Extractives from
thanthatofcoldwaterandthisisduetothedifferenceintemperaturefromsolubility.
alkali method were the highest, followed by benzene and cold water. This result is related to
solubility in different solvents. Cold water extractives of almond shells were 3.14%, and poplar was
0.11%. This indicates that almond shells contain more terpenes, phenols, hydrocarbons, and ester
compounds than poplar [26]. Terpenes and phenols are the main component of fragrance, thus
almond shells could potentially be used as a raw material for creating essence. The content of hot
water extract was higher than that of cold water and this is due to the difference in temperature from
solubility.
MMateartiearlisa l2s0 21081, 81,1 1, 1x, FxO FRO RP EPEERE RR ERVEIVEIWEW 5 5o fo 1f 21 2
MaMtearitaelrsi a2ls0 1280,1 181, ,1 x1 ,F xO FRO PRE PEERE RRE RVEIEVWIE W 5 o5f o1f2 12
MatMeraiatelsr i2a0ls1 280, 1181,, 1x1 F, Ox RF OPREE PRE ERRE VRIEEVWIE W 5 o5f 1o2f 12
MaMteraitaelrsi a2l0s1 280, 1181,, 1x1 F, Ox FRO PTTREaTa ETPbbaREallbe eEbRl Re2l2Ee ..VR2 EE2.EI .ExxEV EtWtxrIrxEata rtWc crattacii vcvt iteevi v ceceo oc nncoottneentnnettetn noot tffo oddf fiid ffdffiefeiffrrefeeernnretetn neetx txe ttexrrxatartccrattaciiocotitnnoio nmmn m eemttehhetoohthddoossd d (s(wws ( w(ttw %%t t%) )%.. ).) . 5 o5f o12f 12
MMataetreiarilas l2s 021081,8 1, 11,1 x, xF OFOR RP EPEERE RR ERVEVIEIWEW 5 5o fo f1 21 2
TabTlaeb 2l.e E 2x. tEraxctrtiavceti cvoen ctoenntte onft doiff fdeirfefenrte enxtt eraxctrtiaocnti omne mtheotdhso (dws t( w%t) .% ).
ExEtxrtarcatciotino nMT aMebTtleahebt oh2led.o E 2dx. tErxatcrtaivctei vcoe nctoennAAtte AllonAmmftl lmdooomfinnof dofdndeinrf d SfeSde nhSh rSteehe enhllexltle sltsellr xlsa s t cr t ai ocnti omne mtheotdhso d(ws t( w%tP)P .% oPoP)ppo.o lplapalrrla arr
ExEtrxatcraticotnio MTnTa Mebatlbheel toe2h d.2 oE. dxEt xrtarcatcivtiev ec ocnotnEEetxEnxAeEtttnxr lrxottamaA trfoccra ldotfatcm iiidncvtvftiifdoeeifvefvn r eeCSCeedr nhCoe o CtnSenno etolhtnt lxeenesettxnnr teltaelt nrtsc n at tct i ot ino nm metehtohdosdEE s(xExw E(ttxwrrtxta a%ttrc cra%Pta)tci.ioc )vtv.tipP eeivvlo eCaCep rCo ol Cannoortnt enetnnteetnt n tt
ExtErxatcrtaioctni oMn eMtheotdh od
ExAtErlxaAmtcrltomainvcotdein vCSdeho SCnehltoleensnl tlte s n t ExtErxatcrPtaiovcPpteio lvCaperol aCnrto enntte nt
CECoxlodEtlr dxawt crwataitacoettrnie o erMn xet xeMrtatrhceatotcihdotion od n AAlmlmo3no.n3d1.d4 1S 4Sh helellsl s P0Po.po01p.l11a l1ra r
CEoCExldotxr ltawdrca awtcittoeainrot en eMrx Meterxatethcrthaoticdootd nio n ExEtrxatcrtaic3vt.e1i3 v4C.e1 o 4Cn otenntet nt ExEtrxatcrtaic0vt.e1i0v 1C.e1 o 1Cn otenntet nt
MaterCialosCl2d0o 1wl8d,a 1wt1e,ar1t 7ee8xr2 terxatcrtaiocnti on EExtxrtarcatci3tvi.1ev34 eC. 1Co4no ntetnent t EExtxrtarcatci0tvi.1ev01 eC. 1Co1no ntetnent t 5of12
HHoto wt wataetre er xetxrtarcatciotino n 4.46.46 4 8.86.46 4
CHoCoHldto o wlwtd aw awtteaeartr te eeerxrx e tterxrxaattcrcrattaiciocotntinoi o nn 34..164344..6 1 44 08..168014..6 1 41
CHCooloHtdl wdo wt aw awtetaeartrt eee rexr xe tertxrxatatrcrcataitcoictontinoi on n 43..361.4441. 46 4 80..061.8411. 16 4
NNaOaOHH (1 (%1%) e) xetxrtarcatciotino n 141.40.30 3 202.05.65 6
NHaNoHOta HowOt H a(w1t e%(ar1t )%ee rex) xte retxarxtTactratcraiabtcoicltonetinoi 2o n.n E xtractivecontent1o44f.16.d4044i.3f. 6f0 e43r entextractionmethods(wt28%0.26.)85.04.6. 65 46
NHaHNoOtoaH twO w(aH1ta%e t(re1) re %e xex)tx tretrarxacatctrctiatioiocnontn i o n 144.4.610.4643 4. 0 3 280.8.625.4606 4. 5 6
BeBneznezneen ea laclochoohlo el xetxrtarcatciotino n 8.80.00 0 7.75.05 0
BeNBnezaNneOznaHeeOn E aH(ex1l tca %r(ola1ch)c% otoeih)oxl onteerlxxa Mettcrrxetaatitccorhattnoiicoo dtnnio n AlmondSh184e.l.1080l4s0.30. E 00x3 t ractiveContent Poplar2E70.x.2575t00r.6a5. 5c06t i veContent
BeNnBNzeaenOanzOHee Hna (el 1c( %a1ol%hc) oo)e lhxe eotxrxlta trercaxatcitctortianoiocn nt i on 1841.0.4080.30. 0 30 2702.5.0570.65. 5 60
Coldwaterextraction 3.14 0.11
BBBBeBeeBeBnneBnneezzneznzneezneeznznennzeeeeneenen Hen a aeeaa loel allcacatc cloaoloclowclhchohhcooaoohoohothlleohllo o r eleoeel lxe xxl exex etttxetxrtrrxrtxrataaatrartccrcaccartattttcaiciiiicotocotootiintnnoninoio o n n oonn ff o oafaf lla mmalmloomnnooddnn d sds hh sseehhllelle l88wlwl. l.800 wa8a.w000s.sa4 0 0 a .s808 6s . .48 008.000.0%%00%,,% aa, , allai itt ltitlltilettetl elhhe ii hgghihhgigeehhrre erttrh h taathhnnaa 7 n7ttn..h 7h55 t7.aat0h05.h8tt 5 a0 . a6o0t ot 4 ffo opfpf o popppoolplaaplrral..a r TrT. .h ThTiihsshi sis
iinniddninidiccdBiaacietctaeenaBtssteze estetnshh nt zaatheehNtta n aatttaehth lOtc etehaoHh elahace ll(oao mm1allh% mlooemo)nxnole otddnexrn xda tssdrtc hahrs tcsaeiehtohlcliellontesslinll o saloasn nnfa addnoan dl fppmd aopo oplppomnolpladapolrrn al sahrhdhr aah ehsvvalhaleev ev wesslel iias m mswis1mi i4imal8l.aai0s.li0rr3 al 80 aara.%r m0ma a0,mo om%auuo ,onl uniautttn stnsllt ietsoots tffo hl oecfcif o goc hclhlooiooeglrrolrheoe rddetreher d mm dat nm haam atttattnhaetett arr2tet t eh0crc ro .oao5c ftcnn6o otoptnenefotnn teppettn,ln,o tasspt,r u,us .l sacucTuhrhch.c h aahTi sssa h a sis s
ippnhphdpillhnioohclbdbBolaBoaiatbeBecbeppBnaneasahpheznzt pteeneehezhhsBnnnnzeea eeeeetennethnn,n , ee atazaette ,hlael ata, ctc e nnanltatoo ceahlnnanhhconeailinoohonmnln chiallo,,ni o ol onelfefm,h anl ax,xefo ttdtofaetx,l,rar xtn teawawst,rtx d,chcarw atatwt acerisixxaacotloha il ctxnanosaeixt oni nn la aooolandd nsnnffno d doarfradae n efllr ap smsmrdealioiemsn lnoosppmi..ninno l onTaTo.dndp .rhTnh d lTssehdaeh hhh s ra effe hseeiv ihnhlfn leelfilade ldn i vwlnwsli dilinewnd maai wggnisssan8 ii g assl.ms8g80a shh.s. 08r 0i0sooh8l .0h0a0aww.o%0%m0orws 0s%wa,, o % stmta,asuh h , t aa noalthlai hitttutalt satittlttntl lhit hoetettt lete thsf elhhh r ree coeeiehi rogfg hreii ilhehgscso iig oe hersipphrslre eoo po dertptrtto hrh eeeotm tahandtntehnneata tnimain n tatatttnti hlhelaait aarfhatfltot o7lhttacfe .rrfoao5toro o t0ar anffoc r l lota ofpmpmae flnopomnl oomptppotenno,olpl noadadsnplntrur ad l,s..sd arc s hhT.Trsh u se.ehhTh hclalTeilhilhessssslhi l l saslis s s
pititnonohit dnd toiblpbonoid iehecbc dbib a alecuuiaoett caspeuse batueesshesatd ds eestepte h sd hnihtid nanha teei ht t nai,tn t nathttth eht ha tetteh, enheh t etph p neeaaa repr inllapono mmrnaldrd,om liooofumdnuadnnoc,ucto dundtt,fci nia cd owtosstdtin hnoh,isa o ew nhsexoonhll e flflao ae sls odxdlfn l sf aal ydyd sandnae eyn adndyr eidien den n pps id grgniioponen rrgppposeg.er oilpdldTrneaapelidihr.raeedl iTearnhnhei rehtahtafn snsihvevatn..ts a evefds. vi e.ssni e niisdmm gisimi niimsllgaihalir raols arawah rmmao samw oomthuuosoa nunttuhtnt sstnat h sottoe sffto r h ocfce eofo c irlcloseooo l prroileesoord dertpee d momdn tmt aeamitnatattlattee ittfrraeto lerccr rofo c oancnolrotnmt eeantnnoeltmetntn,,n t doss,t un u,ss cduschhuh ces ch lahalh sssea alsl ss
tppohph pbtlhloooehlb boT TlbuoaabhThespbTpa eeehuahBphh d NeNpseheee eNhni nnaeaNndeeOnezOa n,at,eieO H hHnOtent,a aeH , te tH (n(n aht1p1 annn(a e%%r(1ninil 1on%npcn))i%d o, n,reie ) unofhf)x ,xea a d,coetftx ttratrfxul,,tiaa at otrwcw,ctecra nt,twatx icaaii wocottooxxartinnfn ao ixaa ao xd nc ooonnan t fyffadoind ooeadnaf d fr nlrlydaim meeanrel ssmleorg ooimiiesnfnrnnnoise.on.gdiadn dnTnT.rl d sims.ehdThe h hdTsen heoseehih tehlenflfesleil ine d.nf lnw w llitfd lndsiw aasnw.idi shnsnadi a 1egnsg1isln 4 4 g1l ss1.g.4 0h0hs4w .33ohso0.0%h%aw3wo3so%w,,s%s waa 8,stt n,nah. sh 0atddn ahatn0 d httwaw%d a tttw ah ha,twt sseheata a hrmrsmeese erml a aemriiitise isatnin a lsipiplelni syynopo l p hyltctocyeeoo iotcn gnecmtmoethntoiminpaptemaitrlolpoai pafslfsoto oeolehfs rdrodsfea oer ad anood rlla f mfom al otfffmhlllof omafa anflnovvaltodnadoovnvo dn nossdof ohonhsn iieohspeddohllieolsldsieslsdp,,l s l ssll, sa , r.
tataoonnta oattbtnbohnh Teebt rtrhT hb eahuaurhei qqrsusas Teaeuueuqs iqhdNdiesnuinnuee d diiaio doninnN Oininn oc n itotaeaHnenh hnOtsts eehee t,,e(s Hh se1sppp,pe %, rtp rhp(h hopop1r)eehad %dorhnenetouduexoon)dtnc tuclleohrituitocxcaciliecotilo,t,cc ii trnnatcoa,iaai o,l n non coamona ndtdnffoi n o ood dfoddln lnf faydya dl dcaeceoyaltalt y cfeoismoic nten ahnnito golngoeieenmnrnrglnsseleeg.dro.ess d dersn A.Asaeid i.ed heAdnnniAnne edisttnetnlthnhhslstnt prt.reh.ws ta halor.slq qara.p wa usuqlq ai1uiannur4siooni. h1n0nno43aoeen.%vn0ssee 3 e,sa as% asrr anieea,mr d areaaen i wnln adaattnar iniwbstbtai aambiambccsataat comeeictrnurteaiielnraayirilntlai scallaayo lonn am cafddnonpc d mdhoho la ahspohvevaoradeevesv edeotted hfh tm efteholh aefaeee v ftff ltefofaeeefenvfrfccfeootetccssincotd tsonooss ift ,fod e ofsnf , t ,
ahhneehhtmmaehsenmoruomTTtashscohThqtothrsTaeaheusatsh sa taeNiqNiainses ssuNsai ao pNsiiaaOOnasn hnn aaOeoHHladOdnosnnH , d b(H (eddd11p a s(e de% %p1,h(dt t1e%hooep)e)%t xnexetohe)oni xoi)xxeeff xetiletinxicirfric,xctofiaaaatrcit,lcatc ctaraiiitatanaccotoiin,ticotnon noiitdnoanio,i,nn on n n aooa,,ln d, asfsfo af a ca oaasfwwltst l flaao,m wm eaeclwnwmltlloeolemloea lnnsoanllax.o ldnds se ana Aa ds ssesends. h hln ls ede eAeehsetlvvhhlellernlelaavere l wvtwtlatslah iilawiqntna anrwtiugsagsnia.n iq a1 sg1Tnddg su44 1ho i di.1.i4aa0dne0ni4.rr33ai0eofi.rra%0%rs3hnhnrr 3%ere,eh,ad% haasaare,i ene nn,aaaa aa adndg nrna an de awdnswdnd n hw td aa aidddwonb ssaiw di at uamudsmiic ssbrurimt aueaeametrisihsarcernniieatiiassslanelsii.yty.ns rli l stA yi.Aclch aa.y o oAlclnleA m mmcmordlaoemlmoopn mpmhinndooposoadpdns sopnvehe od sosddesdaes hht e svd eootseehdeh nfhflole l eltofeffstslil l lhfl afa aesl mlmflesvv afl m ffaovoaamoeevnynoycafroafo nto yaeasayniio cl dldl aomsiostasdslsoiofsl,d,o s s oo,sno ,fd
hahahnenaaahhmatvnthvahhnaseteevorhhrv t metaatsherehh qtqartlo ailithauqusssshsqi iu tiisfitfnansusuou i sfon oinafuninbnnousnccneo enentdtacsnisieucont o,,est id snndoi,sppeo e.,.n dhp h tnd.opehe .ei xhnnnetioeonoftnixllohciiioclcaefi,l,itc ipcic,aaoa r,nnan toiadnd,do n d anuldl sa,ac l ctcaawlittascoooe ctnnnwotlloeneo ensasefl..sels d .sAAa ey.A slneneA tnetvihhnnltaerhrtgtavahirrnqaqareautgqudiq inuiindneugioninoi anntndorsoeneir.anshser eesraa sahrra eeeaar a ernaa e dnana n atntdiindbtbiit auabidcbcraitetacueesctrrreitiesieraa.sir llaiiA salaa. ll nnam Aadndoln d mnhdh dahoa hvvn asaevedh v e tetes hhlht lehetseh elemele sffe ff aefeemyffccef tatecassyctl sst oo saoffo l osfo f
hhhaehevhmmheeemaoo mTTvtssohhTehttoTsai aeehtstsThs sha teifihaeosios sus ise r ros naiagogf srNnucnaara gtagdnnndanianoaO cdi incdcdnndt i Hi edc.ie o cccd tten ooo(ocet1.cmxxmoo t%ooiixmffppmxii)ifcocpoieifpaaucuoixttocaniuntiaoturoddnitannonisdsco,n,d t snia,acsc o ,s osoa cn acnsnowwo sottnw anaefewtililtaeanlnlae il leenilamaln dldsesa eo d aseedni si llnen deeiel nivvelnsbb aeavh evtebtaeibinnaentnleizltzngnginewezn gnznddega eeenidi sna a deir1eraaa irr 4alrlahhccr.ral0oeohercl3hahcahoe%o eoaohaaha l,lonn a oaladndee lnn x dx eddddettx rrxidi wtauaudtriccrrauraitateuecssrscsste r mtsiiessfssf irsr. .asf o iofriA.sAmn rmo.Ao lllmAmmy mlmaa lcoom lloamnnmoalmodndmloomn d pnnsosd oohdhdns snehse d edhlless dllhes lshsl l osesehlmmh slflelml esaflaslmll yyaaslwswa v ya aywo eelwla snsrraeloeoeoeslr o sriedeo s ,
hahananhaaahavvananalaelveayyanT v letztzyltheh hyethez Tiehidztdsresh hie a d sffoibdbequ su fry y b unungfb o yuicmnacmynr tntnc mgioiaamcotoiansicstannonsi aseso.n . isc ss scsns.o, p p s.mp secpepochceptetmecrorcntoouptromrmonoolmiudeemcttnse,rre tdyyatrc.srn.y o y TdT.n .ch ThtoTlaeehanhi cenrtreta eeeo rissrdennuues eeslulitdstunsls. tl tsooiAsb nff o e nocfcnbf too chzeclloelrnloeelanzllccqeleetetcu iincntnaiteinggnil nc o gaottgnh hlh tceeethoohs elchce aooo cermcmolexo mtppmearoxaponptucuotrotinunasbudc dnantfsdcssrd t sowwes fmr wriiwitota hihmltia thtatlh h mhn taeethdolh mehhne hii hdogghain hvhgisgdeeehhh sseetttessh lhsctlcet soeo c lncenolwosfttnfr rneetaawtrrcssraettatess srtt eo f
aaanrraeeaaar rlehnppye TeTarpr zmpelheTherysTsreehdeoezeeh s e nesnseboeo tedttn yarerone gtgso dbdrtemiaager ysd igninda ann aaminii s cc nninTsiTn ac d iaTa cccs sTbobp soadca lmlcmboeeesebocmlpt pelp3tom3eer op.ox.3 o c p3uAuoiA.tmfi .ronunA llocAumemdndmaltnmlsdsrtoom di eysnonoctc s.odrn dno ocTny ,nd cnos.hsdoa tn thhTeas asntseeh iihathrnlwnlealieeleesnesli sell nd dresulmlmesel d lm sdtaiaai musnni siia nln n aoitienlblnsib fylyn eeleb oc ylnbcvnceyof ooezan zc lcnclnenteozeoiontnztnencalaneenelttgiieitan nennaciadea nitg11l nliaic cn7a7a1 ltoo1 crg hl7khkrhco7 e hioitokh on nhkehclilod dnie aooln sede smlcad x xesooonsptet xfmrfor dx ot oaaofrotupcf cdarrro ttnaogcogissructdua ra gstgrnnsnff saer ari dinfwoscocnrfsii m morcisci ccot wm.oo hc mmcmAoai a ottml lahphlpmmmmal eopomtlpo oumhouohnononneuniodund gdddnhnn d hsdsidssd,s e,g sh hh swsswh,e teh,sewe ilhlilwectlsltlshesoilshtlti l n s thmlcmmhww sto r m awoneomaewyrrtrrsoereeoeeterara rerelsees t o
aararirinnarnneraianaag gninhlplrna-y-ygeaablrbgzzy- elvaa-pbyeezsbsesadrdzeeeaeesten d ddshsebbdte e d iyecybc dsnob d o yc mtfmmcym o euiom dnmaanpmpms sacoTpiossatsnpu u aiosss osonb sunTppnsu lddnaepsee.nsbpdcsc ed,3,tlte sc re1r.1s,ct oo 0,r0A1t3 mmo1 r 0n.nlo 0mm eAaeanm ntptpeaolrraemthpyhynrptt.th.yrdo h hhyTt.Tn e eth.shThh ndnheTeheei inechs c nelrir h elh ciheesrce sysy her lmuhudlesdysyluslrdra ttudomslosirt nlc rcostooaoala scfyiforc ran ob bafccrcl foorooybco bnlnclo onllcooselsentoln,lc,ace s lntttstie,cwiwni t,ctntn atwi toognw1giin n 7o glltot iig h1phplk t il7ehieipitidndp h eikccsddsie oiod,c, ns s mtmcots ,hdho o,mt pprsrthmfeh eoporooeeprueuorf e eoo onguneo lulaodnd ereonnlsgdfsfeli idi easnfnwcwfi sn ssniw cinii,,wt soct thtish, wmtw i,c th tttowthoop hwhmt ooechectohy up yech hccen coyihiyl lgducgiihiccclhnshgiil--,cgieohdeo c-whsslels-oetetoe,s li f fetslctcwiie hntofnoc fii snncsonitmn,,ohtnts ararsn,o ta an,mnratr sasadrdentotans d rtsd e t
ratatwiwrranteetwarrogow eirp p -one kbokrpr g iea peikrn-nksssebirdeedneiTesanndnsesdshsd et n tesecoeeons tdodfd feoot m oe dc rfmmiifgd on np miamo om n oiTnTnnno upoiaTao oncnTobnbaccocudaloylbyceoebnscclcy me,yll33ld cie i1.c.c3clps 0il A3 ,A.coi aa.c1nA u llrr 0aAmamoonal rpmnmlrmdooomhoamnsnoaamtpodnhdcttahinioa de ctcstsndtin hhchishth cie eahsecy yhnhli lehhldnldyieslsycyreldr l s domlmdodhr scrmcory aiaoamaoncdiiracrcannbrabaibarlnoloiroyberynclbnbnn o yalcocosyzsn roon.c.en b s nncosnT.sToo t.nt,e hanTha nttTiiaiswiahtnsnsh,laii c n otsiii1i1owsn n n7l7 1hi iddnio 1 p7onkki di7 ilclcdiikdi inanaepkciistdcxntdaiie,eandt sdtsstsrte ds h sa eoos,tt srcs fhfothe t t hoasofoaeth rhftr trofao e gargotrtetlot ahagerh tmognnfeaethilhai ni neeccsansei fs hlhc icisc,mnc seoehotc hlswlmomecoll,e o l nmotlclpcpmw dl oo ocpcocnnopyosuuooht tcnonucnaanleutydiinditalcnnncalsdsi-sslsni,do,is n wcswlw,sffs e- u,uwoe ffiiwnftunirtlnhuiheeccntifs nht ttacmimi,ihnc ontoamti osnoanmoin,orlroa andayeenolrlan z eralede ld
trgrgwiirrrgnnogiorotrgngiwurbuo n--gokpybupbog-uisaapsb -mnp s bksasdaaeseaa isnnnsd dasesa dsddne d occnd d ss oofcdaa p mmcococm aeotmatfccpipi mocvtvtmopotirneevipouuovo o emonucncecn uhhdyn dceocneehcsdtschmrml,d,eys i ye11cm,sc.i im0 0,1ccl Ta ii1 a0annccihr0lc la anoa e aalpnpppma lrra rhpprhoepoaopthrtsmtphrhpohuitoeceheapetlp thnrnrteeshtiteeinirciiccyorente i tidcsfhhshiei.c .ecryyhsy sooIh.Idddy n.ncly Irrdlr aI neoodoTnrTrc cccorb atTaaaoaicTobbnarrrcaanlbblbbgareebsoooblr t.elbnn3n o3he To,ss,n s3e .,3nh,i,si c tt,tt,sTi wi wo s,tticch mwt taoaoi ciwnnsc n opall adoi i n oiplpbnb nii ulcipei eibdddnapb ieistdssdseic e,de,e ss as stetes,seth h wne,nteet rhreht s nieehtnr tta ehehhter tth eae taohothaet tthlaloh e teaotetl tefft hehtlii thhenfnetehsifihersnhsrgiee, ne,eser h s tt r,selwheaw ael,t s rewr atocoteeawlro l oc rcec mnomeo yc yc tnmocccyoaomltnylcririroincteclcoearia-l -s srceiooin netc-n lfloa -anaeuesonlpprf afenlieaifhphefnncupiftpthstnsnhihhi,rn,tos ceetehaa,snhtn snnen,aie aeoiinadndcncnlnni d tciadec ld
gththwwrytyhowhtdgodoywuyi rr odrnpkodokoo riuscikr cTonn oakapiacadndrcirabsnnbbasds rl ddo roaebsoobnn snof3faoo sdsn o.cfn m m si itfnsan Aim iov ocm nitltnnetnohm hio otn ovetehcncocohe h eayoya ncee lcclccya dmmmhalyllciimlecclcosiomi cml hcnnoiaaac oeddnrilra nlc oo da lrpassdsmmor hlhrso mmoseaehapmhlplttearlaliiesaesloctcill,i,nr t ps lc itshshs,lc ei oy,oyehy s r s hsodtdyiicoi.tt yr dero i hoIdhtoisnrnt c.acoahr t hasoasacIaT rnar caisttbanbsah r htbo Tobreteh1blnnhoa ee7pposnbse .on.po 3lsk pet.sTt,oTi e eo.nthTi h3nntetdTi,he ittn ssichsinii a taastiitiilo l snnain cai tftl dndaoi olbnot nidi tocebcbrdo ia a gecbebi sttbca a eeeeeuuaten s esestus s i neuseecetts sd hdhseet tcea nhad htoaadhtt a asm s at att tat h sa hathpst a t eahe hrtortah a aeeur sstwew rrahhhnsa ew eehs edw mmhlrlae sllem e rla ,am lceclt twaalo eoeca rtmrncnroiteeitieotntra aohaarinmltlraii ia tamnefnfloaio ol snsf irnorr fon es o frfafr sf uueurp uf nf nunfehfuearuucncliltpe,tn,nthec liihoog,cotloe ,itrtro-n nnohi o btrotainaeorca onlltna s toalioe cld
hgpgpyrrrgpropeogedhrrpupucorreryeooapoupapdpumrcrspasreeaa p rosp a rarec sccebnon ao oac oaudndscsronnmobnm d sadassodm eec mca nisttttaenci,isiiectcvtcv 1tiitsitsecvie0hni..c s v ee snc.cte .hhhaa c eepchlem hmmheaemtoliihmmccniaeacdoinllca n ailsppc dlhrp r heoposrlyphporldsoeepe,prlrr elsottesrioic,etre iatsssieirt.o.es bh .sIIi onn.atI n n sIhTTsn at,aT ahstTbbae wtlalb heepobl e eol33 le tpi,,3 ep o3,inii ttt,dt i eticicsna ta,ac ltntn caithaa n orlbbn ebteeb eo be es s oe buees leeesees nenfieeud en nsttn eshhat d,ashatt httawaa ats tt rohth ta aehetcw hrrryeeaee rc m werlaaie car ra m-eetaroe eramlrme etim aefioomrlnrro ifeeaosro ,lerrn nea f aonfa nunpprad eahphfltputht,wh hheotehleotr,hnn e otkeinioccrinin ctidoc s
phryehdppoyrrafoedrpcmreaoa rocrcboenao srocmbnocosyse nmcitnislcie cisttnh.ia c etrsh o.a emlm aalotmincodhn sydhd esrhlolesc,la lsrsob, soiotn hsit.a hsT athhsi seth ipneo dptieocnattetineastli attohl atbote t bhuees eusdshe eadlsl aacs or ana wtraa iwmns amftuearntieacrtli iafooln rfa oflurg efrulo, eoul,rp otsora tnod
hhydydrorcoacrabrobnons si nin t hthe ea lamlmonondd s hshelellsl,s s, os oi ti th hasa st hthe ep potoetnentitaila tl ot ob eb eu usesded a sa sa ar arwaw m mataetreiraila fl ofro rf ufuele, lo, ro rt ot o
prepparecatprieav rceeoc schmoesmemtiiecctsai.lc sp.r oTTpaTaTbebarallbetebli e3el3e .s.3 C.C3. .IoCo nCmmooTmppmaoopbpuuolonneuuddn3n ds,sdh his teeshlhclell ae lccllno olc nncobottneaantiiastnnaeiiininnenigngnin geetgx hxe tteaxrrxattartcctratthacsscet osotrs ffeo oaafa lflam mralemloommnnooddnon dssrdh hes eeshnlhlellasesl.lp.l s lsh. . thenichydrocarbonsin
pprerpeparaer ec ocsomsmeteitcisc.s .
thealmondshells,TsoabTiltaehb 3la.e sC 3to.h mCeoppmoouptneodnu tnsihdael slthlo ceolbln ectoaunisnteaindingai nesxgat erarxactrtwsa comtfs aaoltfme arolimnadlo fnsohdre sflhluse.e lll,s.o rtopreparecosmetics.
ChCehmemiciacla l MMoloelceuclualra r StSrutrcutcutruarla l ChCehmemiciacla l MMoloelceuclualra r StSrutrcutcutruarla l
ChCehmeimcailc al MTaoMbTlleaoecbl ue3lecl. au C3rl. oa Cmr opmoupnoudSn stdhrS eustlhcrlu tecuclolrt nauctlora anilnt ainingi negx teCrxahtCcretahsmc eotimsfc aaoilclf ma allo mndon MsdhoM esllhelosecl.lu elscla.u rl ar StrSutcrutucrtaulr al
CCCoCohCmmoCeompmpmhoopeipuucomoannuliuddn cn a ddl MTFFTaoooFMbFlraroemmTlborocearmluul uemb3ell lu.claa3a ueuClr . a l l3Coa a. morC mpoopmuopnuodnSu dFFstn hroosFdSuFrehromtclmoesrrlt hrlmuuuculme corlclultaanaoulull tncal raao tai annli tinaniignn gien xCeCgCtxroCotehCamrmoxcCeaotmtpmcprmshtao opseoicpuu comftooa nsnuafliu ddoln camn af ldmdlao lnomdnoM dsFnF hsoodoFMehlFrrolesemmlorohcslrml.uuleusm el.lllu lcaaausulr .al la a r SFFtrooFSuFrromtcmorrtrmuuuumcrllutaaauull al ra a l
CCohmCCeopmhmoeiumpcnaoilduc a nld MFooMrlFmeoocluruemllcaauu rl laar SFtorSurFtmcrotuuurcmlrtaauu lr laal CCohmCCeopmhmoeiumpcnaoilduc a nld MFooMrlFmeoocluruemllcaauu rl laar SFtorSurFtmcrotuuurcmlrtaauu lr laal
CCyCCcoyClChmocehlopopmemepoCmnieupcthnianoacetnludaam eln n ,id ec, a l MFMMoorFloomeollceeruucmclluuaaull raal arr SSFttSorrtuurFrmccuottcruuumtrlruaaaur llal al CCyCCyCCccyollyCChocmoCclhehhoolphmoeemehoxhexmeiupamaecxinnxonaaciealuedanc ,n,aln 1e1 el,,d,1,1 ,, MFMoorFloMmeolcerouucmlllueaaucl raul arl ar SFtSSortturFrrmcuuotcrcuumttlruuaaurr laal all
CCCCyyyCCccCCcolllyeyemoeyoootctctppcmpehhhlplleCoeteoeeyyoyohptnnptnphlopllhuyo--tt-etemy e aa ylnuann-nlnnln dn-ptt-t eeaea a do,,n,n n u eeen,,, d FoCCFFCroo77C7mHHCHrrC7mmHu71117H444Hlu u 1a41ll1 4aa4 FFooFrrommrmuulluaal a CCC22yCy2yC--C-ccCc2yddCdoll2l-y2Ccoyoiiomiod-mm-lcmhhcdhocomcdillpiemeiiomeeheoseicsmxxopmxt-htci-tehehh psaah iuaoexees-tenynyonynxuh -atxth leleuleanhydna---,,y,,n,n1e,ny1l 1d -le,,,dle,,- 1- ,,,,1, 1 ,, FoCCFCro88C8mFHHCHrC8moHu81118rH666Hlu m 1a61l1 6ua6 la FoFFroomrrmmuluuall aa
CCycTyTleceoooTtltTlCeplohohuuetoepyylyheetulnclehlnuyn-e-ltney el eoean-tt ln pn hae-e ee ny ,nel -t, ane, CCCCCC777C7HHHCCH777HH17H17884H4H 118441 8 4 CCC222yy-Cy-C2d-CdccCcd2-yyleilidely-omyocimoctcdtcmccielhhhclhhiimioeloietsesclsyeoemyeehtoh--tih-tccexhxl hsth xlh yhie-ieh--etaasyaes yy xh lex-tynn--xnllh alxy a --le-eae na-y,nl,,, n, ,- n el e,c-e ,e,,i 1, s, ,- CCCCC88C88HHHCHC88CHH811811H668H66 1 1H6611 661 6
TolTuoelnuee ne C7HC87 H8 CyCCcelyyotchchlleyeootlxhhh-a eeynxxl-eaa ,nn ee,, C8HC186H 16
TTooTlTlouuoleeulnTnueoeeen l neue e ne CCCC77HHC77HH878 H 88 8 CCycyeelcottelhhhoeetyyhehttlhhxlye--ayy xl -nlla --en ,e , CCC88HHC8CH18168H6 1H61 61 6
CyCcyloclhoehxeaxnaen, e1, ,13,-3- CyCcyloclhoehxeaxnaen, e,
CCCyyddydCCccCiciidmmllmlydyoyodoicmciehehcehimllmtlteoteoeoeh1hhCxxehxhte,hyyy3ahtayaeteelhl-lnnhyxnc--x-xdy,,el,eyalae a oi-clc,,cnl,nm,- n ihi -i 11,s1seces, ee -,-e,ci-,,,c33, 3 sx it 1i1s---1h-sa -,,-,3yn 33 --le--,, CCCC88C8HHCHC88HH81118H666H 116161 66 111CCC,,,1111yyy11,,,1,CC3Cc13cC3,c,,11l-l,-1ly-yyo3yotto,,t,3rc3rcc-rh3hchiilt--lill-mmeoerotmtoeotrrixxhrxhhhmiieeeiaammaeeemetttnnxnehhxxhxeeeteaeeayayayhtt,,nt,nnhlh nl l hy eeeyyeyl,,, ,ll l CCC99C9HHCHC9CH91119H8898H 1H811 881 8
CCdydciyidmmldciomleiehomtteehhhxeteyyhtaxlhlyn-a-y,l,en -clcc,,e- i ii1,scss, -i--,c1s 3 i-,s-3 -- CCC88HHC8H1816H6 161 6 11C,,111Cy1,,,133cy,1,-l-3cott,rl3-rhotii-mrmehtirxmeieeamxttenhahetenyyht,elhl y ,yl l CCC99HHC9H1918H8 181 8
CyCcyloclhoehxeaxnaen, e1, ,11,-1-
CCyyCcCclddlyoyoicidhcmhmdllieoeom1iCexehxmh,tta1yaeehhene-xntcyxdyhtelaehaloliy,n-,-m nyh 1l1e-ele,e,, -1,1 x t1-1-ha,,1ny1-el--, CCC8C8HCH88HH811H66 11616 6 EEttEhhEEtyyhtthlhlybbyyleebllnbnbezeeznenneznnzzeeeeen nn eee CC8C8HCH8CH811H080 1H01 01 0
CyCcdlyoichmldeoeixhmtahenexyetalh,-n y1e,l,1- 1-,1- C8HC186H 16 EthEytlhbyelnbzeennzee ne C8HC180H 10
CCycyddlcoiidlmhmodiehmeiexmetteahxhetnayyhtenlhly-,-e y l 1,-l ,1-1 ,-1- CCC88HHC8H1816H6 161 6 EEttEhhEtyyhtlhlCybbylieCebslnn-bieszzne-eenznnzeeene nee CCC88HHC8H1810H0 101 0
CyCcyloclpCoepynectnlaotnpaene,n1e,-t1a-ne,1 Cis-bCiicsCy-cisl-o[4.2.0]
MCCCeeettyyatyehhhCtMCcecCcteeyyyllhtrlyytoayolholilhy-act-c-p-pcpye33ll3yelllsroe-eo-l-eot- il3-mm2nahnmp-np3p-30ltytestme-eee1a-ea amnln2mt8ntnt-nnehh0th3,tte eeatea1ey1ay-yht,,nm8,tn11nlh1l1lhy,-,-e-e- -e y- e1y xl,,,-1lt11 1l -Fh,--- - O yx lRF-O PRE EPRCCCE C8E8CR8HHCHRC8E8HH81 1V18RH666H I 11EE6161V 6W6 IE W bbbiiibcccbybyiycicicccyclllytCtoCyocCoaacl[oc[it[iCnionl4s4sat4lscoCC-eoa[-i.e.-n.t2s24[2 ni[a i4-es...4s.n0e200.- -.2] .]e2]0oo.o.0]0ccco]]ooccc CCC88C8HHCHC8CH81118H4484H 1H411 441 4 6 o6f 1 o 2f 12
(Z Cee2) t(Ct-y-e hZhHmtecyy2yh)ltec-eol-hlyH-lxm-tp-(oy3l3h-Z2-ee-p3l-e3y-m-)mxn-tme3--leh-mHtbn-ee3naeymuttt-eneytahlhethbxteeln-ynyh -yt2u,(el3hy1lyE-l-t-,-b-ly -1l e) 2-u(--ln E--t y-)2l-(-E) CCC1C11CHC881HHCH1811H8181HO16H6 81162O18 6O 22 bbiiHbccbHiymyec4iccxyce-ellttymHaxtcmootaaalhnca[t[nnoeneel4an4yettoxet[eeta.n.,aelh42h2 3a[ -nen,4..y4.-ny320e 0m.e-l-e2l.] ]e 0-o,o.e4n30]ccto--e]hoc-ycl- CCCC888HHHCC8CH1811848H64H 1H41 1416 6
enoeantoeea ntoea te memtheytlheynlee-n e-

CyCclyochleoxhaenxea,n1,e3,-1,3- CyCclyochleoxhaenxea,n e,
dimdeimtheytlh-,y cli-s, -c is- C8HC186H 16 etheetnhyeln- yl- C8HC184H 14

ButBauntoaincoacicidac,2id-,2-
CyCclyocpleonpteanntea,n e,
memtheytlh-,y1l,-2,-1,2-
dimdeimtheytlhpyrloppryolp yl C10CH1200HO220 O2 (1-(1- C8HC186H 16
memtheytlheythleytlh)-y l)-
esteers ter
CyCclyochleoxhaenxea,n1,e4,-1,4-
dimdeimtheytlh- yl- C8HC186H 16
3.33. .I3n. fIrnarfreadr Sedp eScptreuctmru m
ThTe hFeo uForiuerri-etrra-tnrsafnosrfmor imnf irnafrreadr e(dF T(FIRT)I Rsp) escptercat roaf pofo pploaprl aarn dan adlm alomndon sdh eslhlse lsles esne einn Finig Fuigreu 2re a 2n dan d
TabTlaeb 4le a 4re a areli kaeli,k ree,f rleecflteinctgin thg atth taht etyh esyh asrhea sreim siimlaril achr ecmheimcailc caol mcopmopneonntesn, tws,h wichhi cahre a mrea minaliyn clye lcluelllousleo,s e,
hemheimceilcluelllousleo,s ea,n dan ldig lniignn. inT.h Te hpee apke arka nrgaen gaen dan sdh asrhpanrpesnse sasr ea rdei fdfeifrfeenrte natn dan idll uilsltursattrea tteh et hceo nctoenntte nt
difdfeifrfeenrceen coef tohf etihre cior mcopmopneonntesn. tFso. rF oexr aemxapmlep, lteh, et hceh acrhaacrtaecrtiestriics tpice apke aokf 8o9f 08 9c0m c−m1 f−o1r f opro ppolaprl aisr sihs asrhpaerrp er
thatnh aanlm alomndon sdh eslhlse.l lTs.h Tish iiss tihs et hceh acrhaacrtaecrtiestriics tpice apke aokf ocef lcluelllousleo,s ien, dinicdaitcinatgi ntgh atth pato ppolaprl acor nctoanintasi nms omreo re
celcluelllousleo tshea tnh aanlm alomndon sdh eslhlse l(lass ( aTsa bTlaeb 1le). 1T)h. Te hceh acrhaacrtaecrtiestriics tpice apke aakt 1a5t 8105 8c0m c−m1 a−n1 dan 8d2 08 2c0m c−m1 o−f1 aolfm alomndon d
sheslhlse lilss sish asrhpaerrp earn dan sdtr sotnrgoenrg ethr atnh apno ppolaprl,a gri, vgiinvgi negv iedveindceen cthe atth aatlm alomndon sdh eslhlse lclso nctoaninta imn omreo rlieg lniginn in
thatnh apno ppolaprl.a Trh. Te hceh acrhaacrtaecrtiestriics tpice apke aakt 1a7t 3107 3c0m c−m1 o−f1 othf et htwe tow soa msapmlepsl ewsa ws asism siimlaril,a irn, dinicdaitcinatgi ntgh atth taht et he
hemheimceilcluelllousleo sceo nctoenntte nist misu mchu cthh et hsea msaem [2e7 []2. 7].

FigFuirgeu 2r.e I 2n.f rInarfreadr esdp escptreac.t ra.
MateMriaaltse r2i0a1ls8 2, 0111,8 x, 1 F1O, xR F POERE RP EREERV IREEWV IE W 6 of 61 2o f 12
MaMtearitaelrsi a2ls0 1280,1 181, ,1 x1 ,F xO FRO PRE PEERE RRE RVEIEVWIE W 6 o6f o1f2 12
MaMteartiearlisa 2ls0 21081, 81,1 1, 1x, FxO FRO PRE PEERE RRE RVEIVEWIEW 6 o6f o1f2 1 2
Materials2018,11,1782 6of12
(Z)-H(Ze)x-H-3e-exn-3y-le (nEy)l- (E)- HexHaneex,a3n-e,3-
(Z2)(--ZmH)-ee2Htx-hm-e3yxe-l-ebt3hnu-yeytn-llb2 y(-uEl t)(--E2)-- C11HC181O1H2 18O2 mHeeHtxhmaeyxnelae-tn4,h3-ey-,l3--4- C8HC16 8H16
(Z(2)2Z---Hm2)m2--eH-meeemextntehn-eh3exoetyoyht--anlaehe3lbytobntn-yeeuleauoy bl tnbtatlu-e- yu2t(2 teEl--t- -2()2E---)- CC1C11C1HH1111H118H8OO1812O82 O 2 2 Table 3. C ommnHmmteee.Hmmetemtxthmhtehaeehyexytntyeylhhtaleelthel-nyyhn,-n4y34lelye-e-el--,l-4-3n-e4 - -en--e - CC8C8HCH81H816H6 161 6
eneonaCoteah teem ical Molecular Structural mmetChehtyheleymnleeinc-a el- Molecular Structural
CyclCoyhcelxCoahonmeex,pa1on,3ue-,n1d,3- Formula Formula CycClCooyhmcelxpoaohnueexn,a dne, Formula Formula
CCddydCyCiciicdmymlmdlyoicoemidechlemhCotltitedohheemhhyxeihtyxyeymchtaeaellhlxln-y-toxn-e,ay,h,e l hate cn-cly,chn-,e,i1iei 1sl,syxcse, --,-,3c-i1,al3 , s i-1-,cns--,3,i- 3ecs- ,i--1s -,3- CCCC88C8HHCH88HC1H18166H6 81 1H661 6 16 CCyCyeeCCcecyttltlyyhohechoeecctehleehthtollennhehooneehtyxyeehhhyxnealnlnaeele-yx-n-y yxxn n alela-aleyn-- ,nn, le -ee, ,, CCC88C8HHCHC8C1H181484H4 8H 1H41 41 144

ButaBnuotiacnaociidca,2c-id,2-
ddBdBiiuimdmummBmmdBtituameemeideaueemmntttttntitetahdhheheeBmomhhaoeesntytsiyyyiuynythtmmihtcteoeellelchlhtelol-apy-ytptis-aapree,ey,ryhhcic,1tll r1rnc cs1ttr-apelleiyyo,oh,hi-t,aopd,o22rcsd1r2el,lppyycp 1--riit,p-o,r-,2dc,iye2ylol,2y 1pdrp2-a-r-l,pl-o,,l2 -y,c r12 2ypo-il,-d-2 lyp -,ly2 l- CCCC11C1001C0HHH01C01H2H20200H10OO20O2H00222O0O2 O2 022O 2 2 C CmCmm y(yCyme1eCCeccmct-tyltlChmhlyyemoohcoetyccyypl(py(htpe(oel1l1llhc1eleooteyeet-p(-elhn-ynhptp(1tnolteh1hyelttyh-eept(enaa-tylya1lnnyhteennteln-lhattlnt)y)tee)aahe-y-nht-,l, n n, ay ) ley )-eenl,-l ) ,,) e- -, CCC88C8HHCHC8C1H181686H6 8H 1H61 61 166
esetesrt er
CyclCoyhCceylxocahlnoeehx,ea1xn,4ae-n,1e,,41-,4-
CCyCyCccdydldlyocioiidcmmhlmhdolieoeemidehexmhxtteitdahhemaehxenityyxnymahteelalhenl-y-t,-ne,1 y he1 lte,-l,y,h4-1 4,1l -y,--4, l4--- CCCC88C8HHCH88HC1H18166H6 81 1H661 6 16
3.3. 33I.n.33f..r aIInnreffrrdaa Srreepdde cSStpprueeccmttrr uumm
3.33.. 3In. fIrnafrreadr eSdp Secptercutrmu m
3.33.. 3I.nT IfhnraefTrrT aFehhdroeee uSd FFr pSoioeepcuurter-rrctiiuterermarru-n- mttsrrfa aonnrssmffoo rirnmmfr iainnrfferrdaa rr(eeFddT I((RFFTT) IsIRRp))e cssptpreeacc ottrrfaa p oooffp pplaoorpp allaanrrd aa annlddm aaollnmmdoo snnhdde lsslhhs eesllellses nsse eieennn F iiinng uFFriigeg uu2rr aeen 22d aa nndd
TabTTleaaT b4bhlT leaeehr 4F4eeo aaaFurrloeirekui aeaerlrl,ii i-ekrktreere-fa,t,l nrreraescenflftfoilsenerfccgomttr iitn mnhignga fi ttnrt hhtafharrateeat ydrttheh s(deeFhy yT(aF srIsTeRhh Ia)asR rirsme)ep sseispliicammetrrc iiactlla rhaoarref mc ocphhfoi eecppmmaollap iicccrloa aaamlrln ccapdoono mmadnl ppmeaoonlomnntnseeo,dn nnw ttsdsshh,, siewwchlhlehhs la iilsccsrehhe se eaamnerr eiaenn i mmn iFnlaayi gFii nncuigellryyluel u rcc2eeel o lal2llsnuu eadll,noo dssee ,,
ThTeh Fe oFuoruierrie-trr-atrnasnfosfromrm in ifnrafrraerde d(F (TFITRI)R s)p sepcetrcatr oa fo pf oppolpalra arn adn dal amlmonodn dsh sehllesl lsse seene nin i nF iFgiugruer 2e a2n adn d
hTeaTmbhhalieebec mmel4el l iia4uccr eeleaoll rllasueuel lila,oko lasseikeen, ,e,rd e,aa frnnlleieddgfcln etlliiciinnggtgi.nnn Titignnhh ..ta ehtT Tatphhth eeteeah ykpep s eyehra aasakkhnr eagrr raeasen in masggnieiemdl aaa irlnsn ahcddrha cersshpmhhenaaimercrpsapisclnn aceealos srcsmseo apamdrroieepfn foeddenrniiefeftffnnsee,ttrr sweea,nn hnwttdi chaa hinnicl addlhur easiillt rlmlreuua samstettirnr aaatlihytntee elc y tet chhcloleeeunl llctcoueooslnnnoettt,s e eenn, tt
TdhaieTfhbmfadedleberimiic lfef4efefnie e cla4crlrerue eealen llnro oucaecfsell e oeiat koh,slo iefeefka,, it netrhrha ,dece nerfo ielidrlermfi cclgceloptnoiicgmonmitnningpnp.ie notgonTh.n n tthaehsTete.na h n tFtthpets ost e.ehr.py Fa Feee koysoxa rh rakrs aemahe xrnrxaeapaagr mnlsemeeig mp,sp aeitlm nhilelea,dea,int rl tchad hschreh he ascac erchhhrmahpaeacarmnirtpcreaeaairncscclites asetc stelroai sriccm rsio seatpimtp rceidecoapp inkpfdoefe enaieonfakrefftke ens8on r,to9fe stw0fn ,8 a8w9thc n90miahc0dcnh− i c1mcd i mhafl lo−r uia−erl11slr upmfetforos omaarrtptr ippeanala oiotlnrteypph l illyctesaahe rrsclce hleiio usslacnll ruossotphhnelsoeaneatsrer,rt epn p,ete rr
hehmemiceiclleullluolsoes, ea, nadn dli glinginni.n T. hTeh ep epaeka kr arnagneg ea nadn ds hsahraprnpensess sa raer ed idffieffreernetn at nadn dil liullsutrsatrtaet eth teh ec ocnotnetnetn t
tdhiadffnttiehhf rafaaeelnnnmre caaonellnc mmoedf oo otsnnfhh ddeteh ilssrlehh sic.ereo lTlcmllsohs..pmi sTTo phihnsoiie ssntn hieitssens .tttc hhsFh.eeo aF rcrco ahhercaxa terareaxamrcacistpmtetelirrepcii, sls pettthii,e ccate hp kpce eeho aacafkhk rc aaoeocrflfatl eucccretelieollslrlstuuiieslcl,too ipiscsneee pd,a, eiikicnna aodkdtf iii ocnc8afag9 tt80 iit9nn hc0ggma cttt −mhhp1 aaof−ot1tp rfpplo aoporrpop pcpllaoaolrrapn rcltc aaooirsinnn isttssaha ismiannhrsospa rrmemepr o eorrre e
dctehidfltaflihuecncfaefrel eeoalnllrlnlsu uemaeclnll oeotomc shsnoeeeaof do n tntt hfh hsda ahtae lhnsmneirhel a laioeclsrlmlno. ml cmsdToo.o hnmspTnihdoshdpe nis iolsssheln hs neit ese(hlt nlalstesls.ths s (Fc Tea(.h oa saFcasrbohT rTelaraaex abcre a1abtlxeem)cla.ret1 miepT s)1r.lht)piei.Tsec, ltT e hticp,chheh e teepahca hrcceekahhaa ccorkaahtafrr e aocaarctrfcciee asttclrteecleiiutrrscleiitll ssripoucttiseliisoccpeat is,ekpp ceia een,apk aatdiekn ka1ia tcd5akoa1i8tf cto5 01ia88nf 5t9c 0g8i8m0n9 c0 tgcm0− hc1m tacm−ahmt−n1 1a−p 1d−fta 1oo a n p8fnprdo2o dlpr0ap8 o r8pl2c ap2m0ocrl0op ac− cncm1rlo a mtoinar−sf i− t i1n1saas holos ismn affhm sraaoa pllomnrmmerpdroeooe rrnne dd
thtahna nal amlmonodn dsh sehllesl.l sT. hTihs iiss itsh teh ceh cahraarcatectreisrtiisct ipc epaeka ko fo cfe clleullluolsoes, ei,n idnidcaictaintign gth tahta pt oppolpalra cro cnotnatinaisn ms moroer e
scheecllelssulhlhsll oueeilslsllloe ssss thieihssa ta srhsnphha eaaanrrlr mpapaleenomrrdn oaad nsnn tsdddrho ssesnhtltrglresooel ln(nrsa gg ts(heea Trras a ntTtbhh aplaaebonn l1pe p)p l.1ao oT)rpp.,h Tllgeaah irrcv,e,h i ggcnaihirgvvaa iiencrnatvggecir dteeievesvrtniiiidsdccte eeipcn nte cphcaeeaek att t ahkhata al a1mttt5 aao18ll5n0mm8 dco0o m nsnchd−md1e asl−sl1hnhs a edecnll ol8ldssn2 8c0tcao2 oci0nnnm tct aa−mm1ii nnoo−1 frm m oeaf olo lmairrgeleomn lnliioingdgn n ndiinn
ctshehclaselenuhttllhlhl elsupoaal llosninsosep sp ipsltesahoho rtspaaph.hn rllTaapaa narhrre.lp. eram TT e lcahmrohhn eneaaod dncrnc ha dshdscta ahr tsrsroeetaharrlncleciosgtstlne ltee(srigarrc ii( ess stap trhtTis iecta caaTh nbpkpaa le bepneaaa l ot1kepk p)1 o1.al7a )Tapt3t.r 1hl0T1,a7 e 7hrgc3 ,3cmei 0v0hg c− ciiac1hnvmr moagian−rf c− aeg1t1t evch ooetriefedivf srtteittihwdhisnceeteco i npect tws c ewptaeahoeom kta as hstpaka aat lamam te1l tsma5p p 1lw8lolm5e0en8as soc0 sdwnmw scdsaima−hm1 ss se −ahis1slnl iliaeamsmdlnr l ,cisdi8 loli a2a ncn8r0rod2t,, naci0iicnmint ncaaddmt− ii1inminc c−o aa1gomf tto riiatoenfnhl rmaggaleli tm gtto lhhtninhogaaidentnnt dt ithnh ee
shsehllesl liss issh sahraprepre ar nadn dst rsotrnognegre trh tahna np oppolparla, rg, igviivnign ge veivdiednecnec eth tahta at lmalmonodn dsh sehllesl lcso cnotnatiani nm moroer eli glinginni n
hthetamhhnhaie ecpnmmeo lpliipuccoleelapollrlllsu.ua erlTl oo.ch sToseeenh cctceehoo ncnanhtrtt eaaeisncrn attmtec iirtsusies mcrmthiisucu tt cihcpchhee p attshekhaae emak sst ea aa1 mtm[7 213e7e70] [3[. 2 2c07m7 ]c]..−m 1 o−1f otfh teh tew tow soa smapmlepsl ews awsa ssi msiimlairl,a rin, dinidcaictiantgin tgh taht atth teh e
thtahna np oppolparla. rT. hTeh ceh cahraarcatectreisrtiisct ipc epaeka kat a 1t7 13703 c0m cm−1 −o1 fo tfh teh tew two osa smamplpesle ws wasa ssi msimilairla, ri,n idnidcaictaintign gth tahta tth teh e
hehmeimceiclleulllousloe sceo cnotnentetn ist ims umcuhc thh teh sea smaem [e2 7[2].7 ].
hehmemiceiclleullluolsoes ceo cnotnetnetn its ims mucuhc hth teh sea smame [e2 [72]7. ].

FiguFFriiegg u2u.rr eIen 22f.r. aIInnreffrdraa rsrepeddec sstppraee.cc ttrraa..
FigFuigreu r2e. I2n. fIrnafrreadre sdp sepctercat.r a.
FiFgiugruer 2e. 2In. Ifnrafrraedre sdp sepcetrcatr. a.
Materials 2018, 11, x FOR PEER REVIEW 7 of 12
Table 4. Absorption band assignment in the infrared spectrum of almond shell and poplar.
Functional
Wavenumber (cm−1) Vibration Type Cause
Group
3300~3500 –OH stretching vibration cellulose, hemicellulose
2900~2935 –CH stretching vibration -
1640~1735 C=O stretching vibration lignin, hemicellulose
1580~1605 benzene ring stretching vibration lignin
Materials2018,11,1782 7of12
1455~1465 –CH3O stretching vibration lignin
Table4.Absorptionbandassignmentintheinfraredspectrumofalmondshellandpoplar.
1320~1430 –CH bending vibration -
Wavenumber(cm−1) FunctionalGroup VibrationType Cause
1221~1230 C–C C–O stretching vibration lignin
3300~3500 –OH stretchingvibration cellulose,hemicellulose
2900~2935 –CH stretchingvibration cellulose, he-micellulose, and
161400~2157~315035 C=O C–O stresttcrheitncghvinibgra vtiiobnration lignin,hemicellulose
lignin
1580~1605 benzenering stretchingvibration lignin
1455~1465 –CH O stretchingvibration lignin
3
13280~8154~38095 –CHR2C=CH2 benbdeinngdvinibgr avtiiobnration - -
1221~1230 C–CC–O stretchingvibration lignin
disubstituted
1025~1035 C–O stretchingvibration cellulose,hemicellulose,andlignin
810~833 benzene ring -
885~895 R C=CH bendingvbiebnrazteionne -
2 2
810~833 benzenering disubstitutedbenzene -
3.4. X-ray Diffraction
3.4. X-rayDiffraction
The X-ray diffraction curves in Figure 3 show that the diffraction peaks of almond shells
TheX-raydiffractioncurvesinFigure3showthatthediffractionpeaksofalmondshellsappeared
appeared near 16.6°, 21.48° and 34.67°, indicating its cellulose crystals belong to cellulose I type. In
near16.6◦,21.48◦ and34.67◦,indicatingitscellulosecrystalsbelongtocelluloseItype. Inaddition,
addition, using height method [28] to calculate the crystallization, the crystallization of almond shells
usingheightmethod[28]tocalculatethecrystallization,thecrystallizationofalmondshellsis32.88%
is 32.88% lower than that of poplar (48.166%). Crystallization is mainly caused by cellulose, so low
lowerthanthatofpoplar(48.166%).Crystallizationismainlycausedbycellulose,solowcrystallization
crystallization may result in a decrease of mechanical properties. However, compared with other
mayresultinadecreaseofmechanicalproperties. However,comparedwithothercommonlyused
commonly used nuts, crystallization of almond shells is higher, for example, crystallization is 23.25%
nuts,crystallizationofalmondshellsishigher,forexample,crystallizationis23.25%forchestnutshells,
for chestnut shells, 26.85% for peanut shells, 29.11% for melon shells, 30.61% for macadamia shells,
26.85%forpeanutshells,29.11%formelonshells,30.61%formacadamiashells,and23.69%forwalnut
and 23.69% for walnut shells [29]. Combined with cellulose content, almond shells may present
shells[29]. Combinedwithcellulosecontent,almondshellsmaypresenthighermechanicalproperties
higher mechanical properties than other nut shells, which is beneficial in the preparation of
thanothernutshells,whichisbeneficialinthepreparationofcomposite.
composite.

FFiigguurree 33.. XX--rraayy ddiiffffrraaccttiioonn ssppeeccttrraa..
3.5. X-rayPhotoelectronSpectroscopyCharacterization

AsshowninFigure4,bothalmondshellsandpoplarhavestrongpeaksnear532.39eV/285eV
inX-rayphotoelectronspectroscopy, whichisthepeakofO1sandC1s, respectively. Inaddition,
thepeakpositionofNwasdetectedat398eVinalmondshells,whilethepeakpositionofSiat101.8eV
wasdetectedinpoplar. ThisindicatesthattherearemoreNelementsinalmondshellsandSielements
inpoplar,andtheNmaybecontainedintheprotein.
Materials 2018, 11, x FOR PEER REVIEW 8 of 12
3.5. X-ray Photoelectron Spectroscopy Characterization
As shown in Figure 4, both almond shells and poplar have strong peaks near 532.39 eV/285 eV
in X-ray photoelectron spectroscopy, which is the peak of O 1s and C 1s, respectively. In addition, the
peak position of N was detected at 398 eV in almond shells, while the peak position of Si at 101.8 eV
Mwataesri adlse2t0e1c8t,e1d1, 1i7n8 2poplar. This indicates that there are more N elements in almond shells a8nodf1 2Si
elements in poplar, and the N may be contained in the protein.

FFiigguurree4 4.. XX--rraayy pphhoottooeelleeccttrroonns sppeeccttrroossccooppyy..
TTaabblele5 5 sshhoowwss tthhaatt tthhee mmaaiinn cchheemmicicaal leelelemmeenntst scocnontatianiende dini nthteh aelmalomnodn sdheshlles lalsrea eresseesnsteianltliya ltlhye
tshaemsea mase thasosteh oins eotihneor tnhuetrs.n Cuotsm. pCaormedp wariethd twheit shhtehlle osfh CehllinoefsCe hcihneesstenucht,e psetnanuut,t,p Seuannfulot,wSeurn, flHoawweari,i
Hnauwt, aainidn uwt,aalnnudt,w aalmlnount,da lsmheolnlsd psrheesellnstp trhees ehnitghtheesth ciognhteesnttc oonf toexnytgoefno, xayngde nre,laantidverleyl altoiwve lcyarlboown
ccaornbtoenntc. oCnotemnpt.arCedom top aproepdlatro, npuotp slahre,llnsu gtesnheerlalsllyg ecnoenrtaalilny lceossn tsailiincolens asnsdil imcoonrea nnditrmogoerne enlietmroegnetns.
eAlelmmeonntds. sAhlemllos nmdigshhet ltlhsemreigfohrtet hhearveefo ardevhaanvteagadesv ainn tfairgee sreisnisfitraenrcees wisthaennc epwrehpeanripnrge pcoarminpgocsoitme, pdouseit eto,
dtuhee tfolatmhee flinahmabeiitnahnat bciatpanabticlaitpieasb oilfi tNie.s ofN.
TTaabblele5 5..S Suurrfafacceec chheemmicicaallc coommppoossitiitoionna annddr erelalatitviveec coonntetenntto offn nuutta annddp poopplalarr( w(wtt% %).).
Sample TypSea mpleTypen C nC n O nO nsin si nN n N
Chestnutshells 80.26 17.28 0.85 1.61
Chestnut shePllesa nutshel8ls0.26 74.16 17.282 1.72 0.340.85 3.78 1.61
Sunflowershells 78.86 18.13 0.42 2.59
Peanut shHelalsw aiinutsh7e4ll.s16 79.16 21.721 8.92 0.260.34 1.67 3.78
Walnutshell 78.84 19.32 0.16 1.67
Sunflower shellsP oplar 78.86 74.56 18.132 0.93 4.510.42 - 2.59
Almondshells 72.27 22.88 0.87 3.87
Hawaii nut shells 79.16 18.92 0.26 1.67
Note:Thedataofalmondshellsaremeasuredbyauthors,andtherestarederivedfromreference[29].
Walnut shell 78.84 19.32 0.16 1.67
The software XPS Pesk wasused to fit the peak ofthe curve for Figure 5, andC , C , and C
1 2 3
Poplar 74.56 20.93 4.51 -
was used to represent the different states of carbon. The main form of carbon in almond shells is
C ,C ,andC aslistedinTable6. Thecharacteristicpeakofbindingenergy284.38eVwasmainly
1 2 Al3m, ond shells 72.27 22.88 0.87 3.87
producedbyC–HbondinFigure5. Itselectronegativitywassmall,sothebindingenergywassmall.
Note: The data of almond shells are measured by authors, and the rest are derived from reference
Thecharacteristicpeakofbindingenergy286.08eVwasmainlyproducedbyC–OR,inwhichbinding
[29].
energywashigher. ThebindingenergyofC (287.79eV)wasmainlyproducedbyC=O.
3
In Table 6, C content of almond shells was higher than that of other biomass nut shells,
The software X2PS Pesk was used to fit the peak of the curve for Figure 5, and C1, C2, and C3 was
indicatingthattherearemore–ORgroupsinthealmondshells. ThisresultisconsistentwithTable1,
used to represent the different states of carbon. The main form of carbon in almond shells is C1, C2,
showingthatalmondshellswerelikelytocontainmorecellulose. ThecontentofC islowerthanthat
and C3, as listed in Table 6. The characteristic peak of binding energy 284.38 eV wa3s mainly produced
ofotherbiomassnutshells,whichillustratesthattheC=Ointhealmondshellwaslessthanthatof
by C–H bond in Figure 5. Its electronegativity was small, so the binding energy was small. The
otherbiomassnutshells.
Materials 2018, 11, x FOR PEER REVIEW 9 of 12
characteristic peak of binding energy 286.08 eV was mainly produced by C–OR, in which binding
energy was higher. The binding energy of C3 (287.79 eV) was mainly produced by C=O.
In Table 6, C2 content of almond shells was higher than that of other biomass nut shells,
indicating that there are more –OR groups in the almond shells. This result is consistent with Table
Materials2018,11,1 s,h1o7w82ing that almond shells were likely to contain more cellulose. The content of C3 is lower than 9of12
that of other biomass nut shells, which illustrates that the C=O in the almond shell was less than that
of other biomass nut shells.

FigureF5i.gHurieg 5h. -Hriegsho-rleustoilountioCn C1 s1sm maappss ooff aalmlmonodn sdhesllhs.e lls.
Table6.XT-raabyle p6.h Xo-troaye lpehcottrooenlecstproenc stproecstcroospcoyp(yX (XPPSS)) tteesstt rreessuultslt osf oalfmaolnmdo snhedllss hCe 1lsl.s C1s.
Binding Energy (eV) A (%)
BindingEnergy(eV) A(%)
Sample
Sample
C 1Cs1 1s CC2 11ss CC3 11ss CC1 11s s CC2 1s 1s C3 1Cs 1s
1 2 3 1 2 3
AlmondAslmhoenllds shells 284.23884.38 282866.0.088 228877..7799 5555.8.88 8 323.235.3 5 11.7161 .76
ChestnuCthsehstenlulst shells 284.2884.8 282866.2.288 228866..9933 6633.1.18 8 171.770.7 0 19.1129 .12
Peanutshells 284.8 286.24 286.79 48.93 16.34 34.73
SunflowePresahnuetl lsshells 284.2884.8 282866.2.254 228886..7097 4681.9.93 9 162.534.9 4 34.7132 .07
HawaiinSuuntfslohweelrls shells 284.2884.8 282866.2.255 228878..0770 6514.9.59 8 253.094.8 5 12.0174 .57
Walnutshells 284.8 286.25 287.10 55.22 23.17 21.61
Hawaii nut shells 284.8 286.25 287.70 54.58 30.85 14.57
Note:Thedataofalmondshellsaremeasuredbyauthors,therestofthedataisderivedfromreference[29].
Walnut shells 284.8 286.25 287.10 55.22 23.17 21.61
3.6. ThermalStabNiolittey: The data of almond shells are measured by authors, the rest of the data is derived from reference
[29].
ThepyrolysisprocessofalmondshellsispresentedinFigure6. Fromroomtemperatureto200◦C,
3.6. Thermal Stability
almondshellsandpoplarhaveasmallweightlosspeakduetothewaterlossstage. Intherangeof
200–350◦C,botThhep poyprolalyrsiasn pdrocaelsms oofn adlmsohnde lslhsedllsi sisp plareyseantwede iing Fhigtulores 6s. pFreoamk rwoohmi ctehmipsermataurine ltoy 2f0o0r medby
°C, almond shells and poplar have a small weight loss peak due to the water loss stage. In the range
hemicelluloseandlignin. Weightlossofalmondshellsoccurredearlierthanpoplar,however,andthe
of 200–350 °C, both poplar and almond shells display a weight loss peak which is mainly formed by
peakoftheMaahtleermimalosi c2ne0l1dl8u, sl1oh1,s exe l FalOsnRdw P lEaiEgsRn siRnhE.Va WIrEpWeie gr htt hloasns opfo aplmlaorn.dT shheelhlsi gochceusrtreldo sesarplieera kthsano fppopolparl,a hroawne1dv0 eaorfl, m1a2n odn dshells
appearedatth3e0T 0ph–eea5 ck0a o0rbf ◦othCneiz. aaTltmihooenn ppdh osahpseella losr cwchuaarsds s hatfahtreepr eh5r0 it0gh ah°Cne spatonpdpl eapray. krTohalyets hi3si5g ih0s eb◦satC slio,csawsl lpyhe icaloekmst ophfle eptaoedplm laatro tanhnidds sastlhamgeoelln. dp eakwas
at338◦C.TPhosuhpse,ll atlhsr ea’ spcuppreveaear eokdf inasut wt3r0iie0dn–te5 br0i0oa m°nCda.s Tss hhaefat eprrpo 5pe0lr0a r°t Chh aatednn tdahsle mt oh oibgneh dgeesnts htpleee.al Ilkns .actoT n3h5cle0u r°smCio,na w,l thihniele tte htrehprem raealtml asottainobdin listhoye fllc ellulose
andligninoifs ppefooapkrl mawr eiassd s aubtp y3e3rv8io o°rC ltao. t Ptihloeapstl ,aorfm ’asl ampienoanlkyd i ssr hewelyildlsien, rbg uanto cdno smthhpaeraprpeedry twrhoiatlnhy soailtmsheoornf ndcu ets hlslheulelllsol.s s,T ethhe[er3 tmh0e]a.rl miTnahtle esrtpahrbeiigtlaihttyieo rn peaksof
of oafl mceolnludl osshee lalsn dis lbigetntienr , ifso fro erxmaemdp bley, tvhoel ahtiiglehse, smt payinrolyly rseilsy tienmg poenr athtuer ep yorf opliysstiasc hoifo c sehlleulllos sies 3[3307] °. CT,h e
poplarindainchdai tgcehasethrh epaweta niktus tco sofh npeotllapsi linasr s3 i1nm8d °oicCra,et ew cthehialclthu i tils oc losonewt.aeirn tsh mano rthe ec ealllmuloonsed. shells (338 °C).

FigureFi6g.uTreh 6e. rTmhearmlgalr agrvaivtiytya anndd ddeerrivivataivteiv theetrhmeorgmraovigmreatvriicm. etric.
4. Conclusions
In this study, the physical structure and chemical properties of almond shells were determined.
The following conclusions were obtained.
1. Observed by microscope and electron microscope, almond shells have the diameter of 300–500
μm for large holes, and 40–60 μm for small holes.
2. The elements of almond shells include C (72.27%), O (22.88%), N (3.87%), and Si (0.87%). The
main chemical constituents of cellulose, hemicellulose, and lignin account for 38.48%, 28.82%
and 29.54%.
3. The alkaline extract content of almond shells was 14.03%, and benzene alcohol extraction was
8.00%. The benzene alcohol extractives of almond shells mainly contain 17 types of organic
compound including benzene ring, methylene, carbon three bond, and other multi-functional
groups.
4. Thermogravimetric analysis shows almond shells mainly lose weight at 260 °C and 335 °C. This
shows that its pyrolysis temperature is lower than poplar; however, it is higher than pistachio
shells and cashew nut shells.
5. X-ray diffraction spectra showed that diffraction peaks of almond shells appeared near 16.6°,
21.48° and 34.67°. Cellulose crystals belong to cellulose I type. The crystallization of almond
shells is 32.88%, which is lower than poplar; however, it is higher than chestnut shells, peanut
shells, melon shells, macadamia shells, and walnut shells.
6. X-ray photoelectron spectroscopy showed that almond shells contained more N than poplar and
five other kinds of nut shell (chestnut shells, peanut shells, sunflower shells, Hawaii nut shells,
and walnut shells). There was less Si in the almond shells compared to poplar.
Author Contributions: Conceptualization, W.W. and X.L.; Methodology, X.L.; Software, J.H.; Validation, X.L.;
J.H. and Y.L.; Formal Analysis, X.L. and Y.L.; Investigation, X.L.; Resources, X.L.; Data Curation, X.L. and Y.L.;
Writing-Original Draft Preparation, X.L. and Y.L.; Writing-Review & Editing, X.L. and W.W.; Visualization, X.L.
and W.W.; Supervision, X.L. and W.W.; Project Administration, W.W.; Funding Acquisition, W.W.
Materials2018,11,1782 10of12
Thecarbonizationphaseoccursafter500◦Candpyrolysisisbasicallycompletedatthisstage.
Thus,thecurveofnutrientbiomassafter500◦Ctendstobegentle. Inconclusion,thethermalstability
ofpoplarissuperiortothatofalmondshells,butcomparedwithothernutshells,thethermalstability
ofalmondshellsisbetter,forexample,thehighestpyrolysistemperatureofpistachioshellsis337◦C,
andcashewnutshellsis318◦C,whichislowerthanthealmondshells(338◦C).
4. Conclusions
Inthisstudy,thephysicalstructureandchemicalpropertiesofalmondshellsweredetermined.
Thefollowingconclusionswereobtained.
1. Observedbymicroscopeandelectronmicroscope,almondshellshavethediameterof300–500µm
forlargeholes,and40–60µmforsmallholes.
2. TheelementsofalmondshellsincludeC(72.27%),O(22.88%),N(3.87%),andSi(0.87%).Themain
chemical constituents of cellulose, hemicellulose, and lignin account for 38.48%, 28.82% and
29.54%.
3. Thealkalineextractcontentofalmondshellswas14.03%,andbenzenealcoholextractionwas8.00%.
Thebenzenealcoholextractivesofalmondshellsmainlycontain17typesoforganiccompound
includingbenzenering,methylene,carbonthreebond,andothermulti-functionalgroups.
4. Thermogravimetric analysis shows almond shells mainly lose weight at 260 ◦C and 335 ◦C.
Thisshowsthatitspyrolysistemperatureislowerthanpoplar;however,itishigherthanpistachio
shellsandcashewnutshells.
5. X-raydiffractionspectrashowedthatdiffractionpeaksofalmondshellsappearednear16.6◦,
21.48◦and34.67◦.CellulosecrystalsbelongtocelluloseItype.Thecrystallizationofalmondshells
is32.88%,whichislowerthanpoplar;however,itishigherthanchestnutshells,peanutshells,
melonshells,macadamiashells,andwalnutshells.
6. X-rayphotoelectronspectroscopyshowedthatalmondshellscontainedmoreNthanpoplarand
fiveotherkindsofnutshell(chestnutshells,peanutshells,sunflowershells,Hawaiinutshells,
andwalnutshells). TherewaslessSiinthealmondshellscomparedtopoplar.
AuthorContributions: Conceptualization,W.W.andX.L.;Methodology,X.L.;Software,J.H.;Validation,X.L.;
J.H.andY.L.;FormalAnalysis,X.L.andY.L.;Investigation,X.L.;Resources,X.L.;DataCuration,X.L.andY.L.;
Writing-OriginalDraftPreparation,X.L.andY.L.;Writing-Review&Editing,X.L.andW.W.;Visualization,X.L.
andW.W.;Supervision,X.L.andW.W.;ProjectAdministration,W.W.;FundingAcquisition,W.W.
Funding:Thisresearchwasfundedby[NatureScienceFoundationofChina]grantnumber[31670573]andthe
2017SpecialProjectofSustainableDevelopmentforCentralUniversityInnovationTeamoftheMinistryEducation
grantnumber[2572017ET05].
Acknowledgments: The authors would like to acknowledge the financial support by the Nature Science
FoundationofChina(31670573)andthe2017SpecialProjectofSustainableDevelopmentforCentralUniversity
InnovationTeamoftheMinistryEducation(2572017ET05).
ConflictsofInterest:Theauthorsdeclarenoconflictofinterest.
References
1. Ahmad,M.;Lee,S.S.;Dou,X.;Mohan,D.;Sung,J.;Yang,J.E.;Ok,Y.S.Effectsofpyrolysistemperatureon
soybeanstover-andpeanutshell-derivedbiocharpropertiesandTCEadsorptioninwater.Bioresour.Technol.
2012,118,536–544.[CrossRef][PubMed]
2. Lan,J.;Guo,S.;Xia,H.;Zhang,L.;Zhang,L.;Peng,J.StudyonpreparationofactivatedcarbonfromHawaii
nutshellviasteamphysicalactivation. In7thInternationalSymposiumonHigh-TemperatureMetallurgical
Processing;Hwang,J.Y.,Jiang,T.,Pistorius,P.C.,Alvear,G.R.F.,Yücel,O.,Cai,L.,Eds.;Springer: Cham,
Switzerland,2016;pp.575–582.[CrossRef]
3. Martínez,M.L.;Torres,M.M.;Guzmán,C.A.;Maestri,D.M.Preparationandcharacteristicsofactivated
carbonfromolivestonesandwalnutshells.Ind.CropsProd.2006,23,23–28.[CrossRef]