This articleisprotected bycopyright.Allrightsreserved. Accepted Article
article as doi: 10.1002/ differencesbetween version lead to this may been through the copyediting, typesetting, pagination andproofreading process, which This article hasbeen accepted for publication andundergone full peer review but has not o hi iprat datgs oprd o ovninl ims acid biomass catalytic production for platform molecule. materials the ofthis conventional of synthesis the to explores work present compared The techniques. impregnation advantages important their to due investigated being are catalysts acid solid over processes thermochemical via (LGO) levoglucosenone as Several such chemicals valuable of production the products. for methods energy and biofuels to compared value added higher much their to owing valorization biomass for alternatives interesting are Biochemicals BACKGROUND: Abstract a b Instituto deINQUISURInstituto del Química (CONICET- Sur, Planta Piloto de Ingeniería Química, PLAPIQUI (CONICET-UNS), FloridaPlanta deIngeniería Química,PLAPIQUI7500, Piloto (CONICET-UNS), [email protected], phone number: +54 0291 4595101 ext. 3592 phonenumber:[email protected], ext. Solid phosphoriccatalysts mesoporous based acid on silica for J. A. SantanderJ. levoglucosenone production via cellulose fast pyrolysislevoglucosenonefast viacelluloseproduction *Corresponding author, José A. Santander,José A.address: e-mail *Corresponding author,
jctb.5795 Bahía Argentina Blanca(8000), a * Blanca (8000), Argentina.Blanca (8000), , M. Alvarez
and the Versionof Record. Please cite this a
, V. Gutierrez V. , ), Av. Alem 1253, Bahía Av.Alem1253, UNS), b , M.A. Volpe , b . . This articleisprotected bycopyright.Allrightsreserved. Accepted Article mesoporous silica, grafting.mesoporous aluminum KEYWORDS: LGOinlower of levels bio stability H leachable In anhydrosaccharide. target SBA over grafting Aluminum CONCLUSION: be correlatedfound to withthe the in levels the therefore and surface H of concentration the decreasing of phosphates, formation aluminum the to led catalysts (SPA) acid phosphoric solid in Al of presence support silica the on increase an deposition produced Al synthesis Post pyrolysis. fast cellulose in NMR acid phosphoric Aluminum RESULTS:
, NH ,
ic deactivation since 3 - - loaded
TPD, N TPD,
3 GC PO Solid phosphoric acid, cellulose pyrolysis, levoglucosenone, levoglucosenone, pyrolysis, cellulose acid, phosphoric Solid
4 - MS detectable liquid products ( products liquid detectable MS
aayt wr prepared were catalysts mut wih s eial fo te on o ve of view of point the from desirable is which amount, 2 SBA
adsorption, adsorption, of bio of - 15 -
oil
G lvl. T levels. LGO s any asd by caused mainly is - . - 15
mesoporous silica and the corresponding solid solid corresponding the and silica mesoporous oil yield and LGO LGO and yield oil
amount of freeH amount of SPAs is an effective way to increase the increase to way effective an is ICP - AES te rsne f Al of presence the ,
e Ps rsne rltvl hg L high relatively presented SPAs he and titration of “free of titration and caatrzd y E, FT TEM, by characterized , 3 amount PO up to 85 to up H 3 4 PO
in the solid catalysts. in solid the catalysts. 4
in pyrolysis products. The products. pyrolysis in leaching,
peak area peak
3
PO eue the reduced H 3 4 PO
selectivity to the to selectivity but species in the the in species %) 4 ”, and tested and ”,
also led to to led also which - R MAS IR,
catalyst
easily
was was GO
This articleisprotected bycopyright.Allrightsreserved. Accepted Article ih ils of yields high is cellulose pyrolysis cellulose of classified be and problems environmental building wastes solid municipal materials acid phosphoric of pyrolysis via obtained conveniently be also can Levoglucosenone applications other petrochemical replace bio a as useful is (Cyrene), carbohydrates synthesis 2 L of production optimized an much Biomass Introduction basis - evoglucosenone u levoglucosenon oe i a aube chemical valuable a is lose) - rae nwpit n ohr at ppr a cellu as papers waste other and newsprint treated ).
higher added value compared to fuels and energy products energy and fuels to compared value added higher
motn ise t tk it acut hn considering when account into take to issues Important - . - . derived chemicals chemicals derived [ otiig a materials raw containing lc from block [ 10 4 ,
f wd vrey of variety wide a of 6 , to use polar use to 11 , 7
] ]
. Considering that Considering LGO [ 2 A , 3 atraie prah to approach alternative n ,
4 . (LGO; 1,6 (LGO; ] i te iud product liquid the in e [
5
] a be can The hydrogenated form of LGO, dihydrolevoglucosenone dihydrolevoglucosenone LGO, of form hydrogenated The G cn e selecti be can LGO - derived NMP and similar solvents in synthetic ch synthetic in solvents similar and NMP derived available available ,
[ aprotic solvents such as THF and THF as such solvents aprotic 8 ]
i dsra pouto o ti ueu ad aube chiral valuable and useful this of production ndustrial
- band ih hs methods these with obtained are anhydro - chemicals based polar, aprotic solvent with with solvent aprotic polar, based p
aper products are one of the main components in components main the of one are products aper attractive commercial possibilities owing to their their to owing possibilities commercial attractive ht a be ue a a as used been has that waste
pharmaceuticals with - 3,4 pwr and power ,
-
dideoxy cellulosic material could solve some some solve could material cellulosic s as green chemistry green as ey rdcd rm ells pyrolysis. cellulose from produced vely iea acids mineral
can producing
e civd i imp via achieved be - β - , D
- natural natural glycero biofuels
or this anhydrosugar from from anhydrosugar this
sulfolane u t 5% n molar a on 51% to (up
b . i nc liquids onic [ - idn bok o the for block uilding 9 lose hex
] rdcs n rare and products
High concentration concentration High n biorefinery a in
-
- in the the in h potential the 3 containing raw raw containing . h ue of use the [ 12 - enopyranose , 13 regnation of of regnation emistry and emistry ]
context Relatively Relatively ro to prior
the the . to to of of [ 1 - ]
This articleisprotected bycopyright.Allrightsreserved. Accepted Article as than yields, with mixed mechanically biomass of pyrolysis and cumene components Zhang gasoline to produce to propene isobutene and with propene of benzene oligomerization of alkylation ethanol, to hydration (SPA) called is solid resulting the acid, phosphoric is support the material carrier a of surface the over cat acid solid different the Among regeneration simple a of feasibility the including to compared when advantages several of moun oxides, metal mixed zeolites, catalysts acid solid liquid methods, impregnation acid in chemicals previously oxides aluminazirconia,(namely, titania,and
ois c a ais ne rato conditions reaction under acids as act solids solid the yields reported in literature in reported yields the
. acids
. [ particularly for H for particularly eaain f h ctls fo te ecin mixture reaction the from catalyst the of separation 19 t al et SPA
, 20 superacid ,
described ] the slow reaction in solvent in reaction slow the
s o desirable not is s .
[ for recycleuse 15
are ]
xlrd the explored s fiin industrial efficient appear as appear
methods eg slae mtl oxides metal sulfated (e.g. 3 PO . 4
[ - 14 c rm n niomna pit f view of point environmental an from impre niuu production ontinuous a promising alternative. promising a are the requirement of requirement are the ]
p in the latter case latter the in Moreover, s rod alysts, supported acids consist acids supported alysts, gnated SBA gnated cin of uction ted acids, mesoporous materials mesoporous acids, ted
for .
[ s and s 18 catalysts catalysts When the When
different kind different ] ) , and, olid not acidcatalystsare corrosive
the need of pretreatments of pretreatments of need the homogeneous levoglucosenone comparable - SPA 15 mesoporous silica, mesoporous 15
for the i the mineral mineral
, .
[
16
high processes such as ethylene ethylene as such processes lessor non reusable c S s
mpregnation , In 17 tlss Te obta The atalysts.
ld cd catalysts acid olid of ] ) this r reaction er
acid used to impregnate impregnate to used acid solid acid catalysts such catalysts acid solid and
with Solid Phosphoric Acid Acid Phosphoric Solid aayi substance catalytic type of type n te osblt of possibility the and
bare metal oxides oxides metal bare rm aayi fast catalytic from nanopowder metal metal nanopowder
of an of . In this context, context, this In . of
catalysts , the surfaces surfaces the , temperature biomass wi biomass
were acid sprea acid ined ined
- cellulo reusable reusable present present
higher higher ; LGO e.g. .
. [ se se 14 th th s s d , , , ]
This articleisprotected bycopyright.Allrightsreserved. Accepted Article product was washed was product stirring continuous 12 for vigorously i dissolved 50 to 10 from isopropoxide aluminum method. SBA loaded Aluminum Catalysts preparation Experimental assessed acid Al of influence the as well as silica mesoporous 15 amounts variable products support the materials silica mesoporous fast SBA solid study, present the In denoted as Al denoted as and
pyr - acnd t 400 at calcined 15 catalysts. olysis
. mesoporous omril SBA Commercial [ . 21 n
, , 22
30 mL of n of mL 30
nacn i ti way this in enhancing ] /
towards LGO production LGO towards
SBA The aim The .
n tpcl procedure typical a In Issues related to stability under reaction conditions are also also are conditions reaction under stability to related Issues
h.
of
- 15 Then n the and
aluminum
repeatedly repeatedly ° (y) iia ee prepared, were silica fr 2 for C - of this work this of hexane (Merck, 99%) (Merck, hexane - Al(OC , , 5 aayt wr prep were catalysts 15
where 1 g of SBA of g 1 - 15 phosphoric of the of lry a sird for stirred was slurry
2 mesoporous h on the structure and catalytic performance performance catalytic and structure the on H
with “ 7 y n air in )
” 3 MCM
refers to the Si/Al is to evaluate the effect of the incorporation the of effect the evaluate to is ( - the n Aldrich, 15 - . Te Al The . te eie aon of amount desired the , hexane cd aayt bsd n aluminum on based catalysts acid It
-
was added was 41 bio is known is
type - silica characterized oil
98 and the resulting the and ,
- dried at room temperature for 24 for temperature room at dried containing yield % produces an increase in increase an produces rd y post by ared ( . The ). lrc, 99% Aldrich,
2 h. 12
that gradually to the to gradually
presence in presence molar and and
aluminum S
After LGO LGO /l oa ratios molar i/Al and tested in cellulose cellulose in tested and SBA ratio
solution was solution - ) - filtration . levels 5 catalysts 15
ytei grafting synthetic
h alkoxide the was grafted with with grafted was solid phosphoric phosphoric solid incorporation incorporation
solution under solution in t ,
acidity of of acidity pyrolysis pyrolysis he solid solid he of - grafted
stirred varied varied
SBA were was
to to of h -
This articleisprotected bycopyright.Allrightsreserved. Accepted Article Scientific In were between kV. magnifications 100 at operating equipment CXII obtained were images (TEM) microscopy electron Transmission method Quantachrome were areas surface Specific Shimadzu9000 atomic simultaneous M Characterization Al/SBA as and h 12 for treatment ultrasound an by followed concentration a of amount Al method S wavenumber range at a resolution of resolution a at range wavenumber olid tl otn ws eemnd y nutvl coupled inductively by determined was content etal frared spectra of the of spectra frared / SBA PO
dispersed inethanol asonicator. using p - - hosphoric x
15 15 / for the according to a procedure described in literature in described procedure a to according Al (y) / ioe i5 FT iS50 Nicolet SBA samples then
phosphoric acid phosphoric
and SBA n h sld (theoretical solid the in
analysis NOVA 1200e apparatus 1200e NOVA - 15
calcined at calcined a (y) cid or
-
catalysts were prepared were catalysts . 15 samples,respectively catalysts n PO and
SBA
10000x - -
5 ae support bare 15 500 °C for °C 500 R spectrometer IR aqueous solution aqueous x
measured /SBA were recorded at room at recorded were n 270000 and
during
emission - 4
15 for the phosphoric acid impregnated impregnated acid phosphoric the for 15 lmna phosphor elemental cm 2 h in ai in h 2 , using the using ,
- h suis ee are ot using out carried were studies The
1
3
y N by and by averaging over 64 over averaging by and
x h wrig in working , Pir o h aayi, h samples the analysis, the to Prior . were impregnated with the desired desired the with impregnated were spectrometer.
. The catalysts were catalysts The . in order to obtain to order in . r by
.
2 The SPA The
incipient wetness impregnation impregnation wetness incipient Brunauer dopin t 77 at adsorption . [ 15
temperature on a on temperature lsa (ICP plasma ]
Typically, 400 mg of the of mg 400Typically, catalysts catalysts s content us
- h 4000 the Emmett
a sn JO 100 JEOL using
13 dried at 80 °C °C 80 at dried were -
Teller (BET) Teller -
wt E) n a on AES) scans. The scans. – of K 400 %
denote wt 4 Thermo Thermo
with a a with H
3 cm PO %) - d 4 1 ,
This articleisprotected bycopyright.Allrightsreserved. Accepted Article h, was g) NH of desorption programmed total The ICP by determined the NaOH containing solution room into submerged then and a phosphoric F Al(NO experiments p scans. 8192and time, repetition s spectrometer. NMR) Solid thewholefrom infrared wafers supporting samples performed with a with performed acidit For atmosphere. inert same le 5 s eeiin ie and time, repetition s 55 ulse, e popoi acid phosphoric ree then purged for 0.5 h in helium helium in h 0.5 for purged then titrated H titrated - state 3
) a pcr wr rcre a recorded were spectra treated at 300 °C under °C 300 at treated
3(aq) queous
pcr wr otie b sbrcig h sml background sample the subtracting by obtained were spectra were were number
27 and H .
3 cids that was leached when the catalyst was catalyst the when leached was that cids Al PO C 27 pre
spectrum. of shifts hemical and and Al solution 4 10% NH 10%
- 3
respect to t to respect treated at 400 °C during 2 h in air before being before air in h 2 during °C 400 at treated - PO MAS NMR spectra were recorded using 1 μs excitation pulse, 1 1 pulse, excitation μs 1 using recorded were spectra NMR MAS f cd ie o te ape ws eemnd by determined was samples the of sites acid of (2 AES h ece hshrcais was acids phosphoric leached the 31
4(aq)
P wt percentage . .
ctls i KBr) in catalyst % magic angle spinning nuclear magnetic nuclear spinning angle magic
,
3 The term The respectively.
in he total content of phosphoric acid in the samples samples the in phosphoric acid of content total he He 3
( flow NH
stream - temperature room t flow and cooled down to room temperature in the the in temperature room to down cooled and flow 27 eprtr wtr o tn minutes ten for water temperature 31 maueet, dopin f moi was ammonia of adsorption measurements, y 0 scans. 40
a determined was 3 Al ing P “ - free free TPD
MAS NMR spectra were recorded using 5 μs μs 5 using recorded were spectra NMR MAS and and
10% H 10%
( 20 mL min mL 20 ) H . Prior to Prior . 3 31 PO n pae i a ape holder sample a in placed and wr externally were P
2 S /N 4 ” inn rt ws 0 H fr all for kHz 10 was rate pinning
2 refers to the to refers
gas gas the
− 1 y irto o te fraction the of titration by
flowrate)
analysis, t analysis, mixture then n a on
first ground first
titrate Bruker Avance 300 300 Avance Bruker mass percentage of of percentage mass (
for 1 h 1 for 30 mL min mL 30 eeecd o 1M to referenced
he sample (0.050 (0.050 sample he pressed into s into pressed eoac (MAS resonance ih 1×10 with d t ,
emperature
. powder into followed by by followed [ 23
spectrum spectrum ] − Filtered 1 ) .
for 1 for - 3 Net - elf
as as M of - -
This articleisprotected bycopyright.Allrightsreserved. Accepted Article The condenser was weighted before and after pyrolysis in order to determine the determine to order in pyrolysis after and before weighted was condenser The 150 cm b cooled condenser experiments. all for min 15 was where reached was temperature experiment desired the When resistance. of tube preheated catalyst cellulose reactor experiments pyrolysis Cellulose Reaction tests (TCD). NH evolved of amount The increased was a iud rdcs amount products liquid purge for 0.5 h in h 0.5 for purge
an appropriate amount of glass fiber glass of amount appropriate an
3 (see Figure 1) Figure (see /min 5 m 15
1 w% catalyst wt% (15 ( purchased from from purchased ecin eim Te eco cnitd f a of consisted reactor The medium. reaction s)
, flowrate internal m
the mixture of catalyst and cellulose wa cellulose and catalyst of mixture the from 30 to 700 °C at °C 700 to 30 from
y an ice bath ice an y
flowing . . In a In .
diameter which was heated externally by an electrical electrical an by externally heated was which diameter prod
Biopack usual
n h feedstock the in 3 helium (30 mL min mL (30 helium
was cd n h rato. B reaction. the in uced At the reactor outlet, reactor the At
were . N . pro ) measured
[Figure itrogen were cedure, 500 mg of mg 500 cedure, a rate of rate a
performed
mechanicall
was placed was
was used as an inert gas, supplied at at supplied gas, inert an as used was 1 )
]
sn teml odciiy detector conductivity thermal using 10 °C min °C 10 and − 1
). o a aoaoy scal laboratory a n Then, the Then,
subsequently the vapors were collected in a a in collected were vapors the s dropped into into dropped s y mixed with 75 mg of solid of mg 75 with mixed y
as high purity purity high − vertically arranged arranged vertically 1 io a
under helium gas flow. gas helium under - support. oil was diluted with with diluted was oil
sample temperature temperature sample
35 C o all for °C (325 supplied m
the glass tube glass the Reactiontime icrocrystalline fixed e o the to glass - bed bed
This articleisprotected bycopyright.Allrightsreserved. Accepted Article Chemical Resultsand discussion software. B with fitted were tests pyrolysis points data values, experimental the in trends identify clearly to total the to respect area peak of library. NIST the to according identified were peaks chromatographic The port. injection the into injected was Bio min). initially was oven GC 10 for (held °C 280 to ramp °C/min 10 The a by followed min, 5 for °C 65 at maintained program: temperature follow the with performed 35 m/z the within eV 70 at ionization electron under recorded were spectra Mass respectively. °C, 280 and °C 160 at maintained mL/min. 1.0 of a and 1:20 flowrate of ratio constant split a with gas, carrier a as used was Helium thickness). 0. m, 30 dimethyl)siloxane, diphenyl/95% poly(5% HP were an Analytes by spectrometer. separated mass quadrupole 5977 Agilent an to connected (GC 3 products a obtain to order in 99,8%) (Aldrich, acetonitrile - MS )
- .
oil was and d and was oil were compositionand properties textural The analys The
analyzed es were performed on an Agilent 7890B gas chromatograph gas 7890B Agilent an on performed were es - (gln) fused (Agilent) 5 issolved in 4.75 mL of acetonitrile prior to analysis and 1 µL 1 and analysis to prior acetonitrile of mL 4.75 in issolved
by a crmtgah culd to coupled chromatography gas LGO peak area% was area% peak LGO area of peaks in the mass chromatogram mass the in peaks of area - spline functions available in the data analysis analysis data the in available functions spline D - tco ad injector and etector silica capillary column (stationary phase phase (stationary column capillary silica
– 0 rne GC range. 400 calculated as the percentage the as calculated 25 mm i.d., 0.25 µm film film µm 0.25 i.d., mm 25 wt concentration % mass spectrometry spectrometry mass temperature – MS analysis was was analysis MS resulting from from resulting . L . In order In were were iquid This articleisprotected bycopyright.Allrightsreserved. Accepted Article diameter ofabout3.5nm structure mesoporous sh are catalysts the of images TEM † * PO PO PO PO PO Al Al Al Al SBA Catalyst T withaccordance theexpected values phosphorus of load nominal procedure. was value cases, calc the of composition elemental The
able 1. Determined by ICP by Determined Not determined /SBA /SBA /SBA /SBA x x x x x /Al /Al /Al /Al /SBA - 15 idctn ta te lmnm de va the via added aluminum the that indicating , completely completely /SBA /SBA /SBA /SBA - - - -
the 15 15 15 15
Elemental composition and physicochemical properties of the the of samples. properties and physicochemical composition Elemental - 15 (50) (30) (20) (10) - - - - Si/
The catalysts of the of The catalysts 15 15 15 15
Al molar ratio molar Al (50) (30) (20) (10)
noprtd in incorporated - AES
consists Si/Al*
49 37 16 11 47 30 17 10 , as , ∞ ∞
determined
seen inFigure ,
PO of of P (wt%)* the o the to 4.6 4.7 4.9 5.1 4.8 symmetrical pores of cylindrical geometry cylindrical of pores symmetrical x - - - - - /Al/
[ measured .
Figure 2
own in in own
ined materials is materials ined SBA
by ICP by oi material solid Surface Surface (m -
area area 345 312 287 269 291 523 510 466 563 550 15 2 2 A. iue 2 Figure ] /g) -
series AES analysis AES
otn o ti element this of content
alkoxide Al
were prepared with the same same preparedwiththe were n.d. n.d. n.d. C . IV IV 15 39 37 30 30
- - presented in Table 1. 1. Table in presented (%)
†
meca SBA ommercial after after
27
Al MASNMR was near the nominal nominal the near was rcro Al(OC precursor Al the n.d. n.d. n.d. V 10 14 17 3 8 - - (%)
post
-
Al
synthesis - being 15 silica silica 15 n.d. n.d. n.d. VI VI 82 51 50 62 53 - - (%)
with a a with
2 all In H
7 in ) 3
This articleisprotected bycopyright.Allrightsreserved. Accepted Article ih Si with incorporated Al the mode cm 960 the that note to interesting cm Si the asymmetric cm 1070 at observed The FT The aluminumCharacterization surfacestructure, of andphosphorusspecies arrange remained unaltered specific the pyrolysis poi the from desirable the of structure the of distribution uniform nm. 9 approximately are pores The concentration of concentration
- 1
registered registered
ee srbd o edn vbain o te mentioned the of vibrations bending to ascribed were - [ /SBA 28 O - - H rus t groups; OH IR spectra of spectra IR , - . 29 Si Although ]
decreased - surface stretching of Si of stretching ymtia srthn md could mode stretching symmetrical 15 on
disposed (10) signals
the the silanol parent
the impregnation the area sample. mesoporous channels mesoporous
e ihr h aon o auiu add te oe the lower the added, aluminum of amount the higher he alu
iue 2 Figure t f iw f cesblt o t of accessibility of view of nt in - are 1
groups remaining at the surface the at remaining groups
in a hexagonal hexagonal a in
minum intensity with the additi the with intensity of the of ln wt a hudr t 20 cm 1200 at shoulder a with along SBA
- typical of a siliceous a of typical
O as eoie material deposited D - - Si bonds Si
C 5 support 15 seen inFig rn te post the uring - silica support (Table 1 (Table support silica modified SBA modified
shows - 1
with phosphoric acid phosphoric with ek orsodn t te Si the to corresponding peak . arrange [
24 that , ure 25
surface via surface ] fe auiu deposition aluminum after
S s - Al/
- ignal 15 catalysts catalysts 15 2 , with a center a with , ytei treatmen synthesis
on of aluminum to almost zero for zero almost to aluminum of on B and2D material. A very strong band was band strong very A material. be identified, while while identified, be
SBA and s
e ecat during reactants he - at 806 cm 806 at 15
), the ),
reaction of of reaction retained . (10) [ 30 .
produced a reduction in in reduction a produced , 31 are shown in F in shown are mesopores
] - sample to An analogous effect effect analogous An - 1 - ,
-
1 center dis center
bonds the mesoporous mesoporous the trbtd o the to attributed corresponding to to corresponding t, aluminum is is aluminum t, the - OH peak
presented a a presented Al alk Al , .
hexagonal [ 26 stretching stretching hc is which cellulose cellulose s , tance of tance 27 igure igure
t 455 at ]
oxide It
3 is is .
This articleisprotected bycopyright.Allrightsreserved. Accepted Article pce of species tetra the of proportion relative the by evidenced network silica the into atoms bond Si bulk to corresponding 4 (Al at signals three Solid Si hydr the minimizing by the mesoporousframework of hydrothermal stability silanol groups species phosphorus treatments groups observed. cen band the of intensity the in decrease a where with impregnation after occurred coordination sites octahedral at resides atoms ) The A). – VI OH groups OH groups , ethda (Al pentahedral ), - state
groups due to their interaction with H with interaction their to due groups decreas s o during post during
mspru silica mesoporous n . It Al [ lmnm In aluminum. 32 27 . is known the known is [ IV 35 , l A NR pcr o te Al the of spectra NMR MAS Al 33
by water molecules by water ]
] e
ek 5 ppm) (50 peak During - C . 3, 28 and 50 ppm attribut ppm 50 and 28 3, It is worth mentioning that the that mentioning worth is It onversely - are grafted grafted are synthesis Al V
ad tetrahedral and ) calcination, P calcination, 2
O ape cnann ol Al only containing samples
interaction between H between interaction 3
t , phase phase . e eaie mut o Al of amounts relative he
[ 30 treatment ] onto the onto
exhibited .
h suc The [ (65 ppm) (65 34 n zoie aeil af materials zeolite and phosphoric acid and subsequent calcination calcination subsequent and acid phosphoric [ ] Figure 3
– ,
O while –
Si bonds are formed by formed are bonds Si and a possible incorporation of aluminum aluminum of incorporation possible a and surf (Al
es f h gatn poes could process grafting the of cess ed
ceia sit ifrn from different shift chemical a suggesting IV 3 ] PO ace and ace
/SBA
) 20 to aluminum atoms with octahedral octahedral with atoms aluminum to -
3 coordinated reduction in the amount of surface of amount the in reduction coordination - 4 PO 30% are found in tetrahedral tetrahedral in found are 30%
leads to an improvement in the the in improvement an to leads - 5 aayt serie catalysts 15 4 2
ee at tered O and the surface isolated OH OH isolated surface the and the 3 both
hs, 70 phase, IV
concentration
n Al and
, and hexa and the formation of Al of formation the
r 960 960 setvl ( espectively ter ter dehydration Vl - cm post 80%
were not so so not were - s - coordinated 1
- presented presented
of Si of synthesis was f the of olysis of olysis of Figure ,
– thus thus also that
OH OH - be O Al -
This articleisprotected bycopyright.Allrightsreserved. Accepted Article trbtd o 6 to attributed nuclei treatm thermal zeolite of interaction strong coordination reduced t NMR the phosphorus, of addition the After domain a disordered highly a as aluminum of concentration the since pen of amounts significant hexa varie different presence of penta presence of he n
alumina domain alumina nest of intensity - d oriae aluminum coordinated spectrum evidence spectrum
s between erhdal coordinated, tetrahedrally .
.
framework for
hshrc acid Phosphoric atoms
h Al the s tate - ent
od c fold l peaks Al 30 to 40 to 30 with - .
[ coordinated aluminum
33 o form to /SBA . after after [ 36 H ] odntd lmnm A ek ek t pm ugss the suggests ppm 6 at peak weak A aluminum. oordinated
pentahedral coordination pentahedral 3 ] The
PO The shoulder at 65 at shoulder The i nterface connecting a silica or silica or silica a connecting nterface - % for % d the formation of Al of formation the d
5 samples 15 an bevd eoe mrgain ih H with impregnation before observed 4
e aymti sga a 3 ppm 36 at signal asymmetric new ta interacted with Al can even lead to the dealumination of dealumination the to lead even can Al with lmnm phosphate aluminum
Al impregnation with phosphoric acid and and acid phosphoric with impregnation ( - see coordinated V tetra
pce in species
while Table - coordinated aluminum and from 50 to 60 to 50 from and aluminum coordinated [ Figure 4
appearance hr the where wi
n inte an h lmnm species aluminum th . 1) [ 37 - Al . ] 70 ppm 70
ue alumina pure
- n h ohr hand other the On ] O supported
have - nse P bonds P s ocnrto o te Al the of concentration
. of new signals in the in signals new of It has been reported that the the that reported been has It
can been suggested to be present present be to suggested been signal
be att be h previous the (see
s ut limited quite is appear - alumina domain with with domain alumina Figure r
ibuted to the to ibuted eades f their of regardless 3 corresponds , the presence of of presence the , PO ed 4
a
4 was
A) at observation subsequent subsequent , whereas , 27 H -
. 9 ppm 19 strongly Al MAS MAS Al species [ - 35 ZSM
] % Al
to T 2 for O he - Al 5 3
This articleisprotected bycopyright.Allrightsreserved. Accepted Article lower increasing acid H acid phosphoric H free The Acidity coordinated Alspecies the coordinated tetrahedrally is phosphorus of shell coordination shoulder The species. four to bonded atoms phosphorus to assigned be phosphate aluminum to attributed o support sample substrate modified not is acid phosphoric of nature [PO acid phosphoric sharp A hyd rthophosphates 3 PO oye ad hs a be can thus and rolyzed 4 27 s ] 3 4 l A NMR MAS Al - condensation condensation
in the catalyst catalyst the in amount , there is there , characterization characterization groups similar to those present in ortho in present those to similar groups
verified signal at signal . [ 38 condensation ]
3 According to the to According PO
provides an indicationthe provides of
by the dr the by
- 4
an evident an mrgae slc, PO silica, impregnated ece fo te aayt hn umre i water in submerged when catalyst the from leached
- and 0.6 ppm cou ppm 0.6 eemnto ivle te quantification the involves determination
degree pcr of spectra
were h appearance the at
- i.e., astic reduction of the signal at signal the of reduction astic degrees - 8 pp 28
; namely, ; interaction between phosphoric acid and acid phosphoric between interaction
detected ortho 31 l PO d be identified be d titrated P MAS NMR spectrum of the PO the of spectrum NMR MAS P idcts ht at f alumin of part that indicates m s - .
- x [ 37 pyro , /Al fe te acnto process calcination the after
, . 39 ortho
/SBA
. [ ] 23
The of ] x
/SBA -
- tri ,
hs metho This -
condensation a hn mrgae on impregnated when 15 and pyro and p
hos phosphoric phosphoric (10) ra band broad i - - n the n
15, n plpopoi ais with acids, polyphosphoric and phorus signal at ca. at signal phorus - ,
and five and where orsodn to corresponding 31 - phosphoric acids phosphoric P MAS NMR spectra of the of spectra NMR MAS P hs lo en sd to used been also has d
- 0.6 ppm corresponding ppm 0.6 degree acid
four - cente coordina . [ 37
[ y titration by - ] 33
five , This is in line with with line in is This m in um ] of the phosphoric of T .
e at red ( Figure x /Al the
he acids with with acids he ted alumin ted - the Al the
-
/SBA 22 ppm can ppm 22 n six and
, the monomeric monomeric
The . pure are easily easily are
- 4 21
- B) - second second loaded loaded f the of 15(10)
. silica silica - ppm free free The fold um um to to
This articleisprotected bycopyright.Allrightsreserved. Accepted Article the Al the programmed Total † Table 2. H acid phosphoric of amount of with interacts strongly decrea acid synthesis. the during support to the and support given a between deposit interactions the of strength the estimate t s el nw ta t that known well is It PO PO PO PO PO Al/SBA Al/SBA Al/SBA SBA
samples. Percent amount of leached H leached of amount Percent 3
PO the x x x x x /Al/SBA /Al/SBA /Al/SBA /Al/SBA /SBA - 15 4 /SBA
Sample
acidity hshrc cd mut ht a nt interacted not has that amount acid phosphoric - - - percentage ed ed
15 15 15 Acidic properties of the Al the of properties Acidic -
15 (30) (20) (10) H titratable - - - - - 15 catalysts when compared to the bare SBA bare the to compared when catalysts 15
15 15 15 15 3 e wt icesn A content. Al increasing with ses
PO
desorption desorption
(50) (30) (20) (10) f h sld ws determined was solids the of 4 . [
40
is observed ] H vial fr titration, for available
In the present study, present the In 3 PO H he 3 experiments. The amount of desorbed of amount The experiments. PO
Free H 4 noprto o auiu va post via aluminum of incorporation . The higher the aluminum content, the lowerThecontent, aluminum higher the amount the 3 4 PO
t
o form A form o . Table
/SBA 4 7.2 6.8 2.6 0.7 5.0 3
PO - - - - respect to the total co the to total respect
4 - (%) 15 andPO 2
l phosphates l shows †
free free and
s previously As
H x ht h aon o fe phosphoric free of amount the that s rsl a result a as /Al 3 PO through /SBA
producing 4 ntent of phosphoric acid acid in the phosphoric ntent of (mmol
has been found to be related related be to found been has Total acidity Total - 15 materials. 15 - with the aluminum of the the of aluminum the with 1.554 1.540 1.270 1.430 1.582 1.342 1.456 1.335 1.171
15 support (see Table 2). 2). Table (see support 15
ammonia NH3 described erae n h free the in decrease /g -
a modification a ytei treatme synthesis NH
cat
)
3
was higher for higher was t emperature , aluminum in the in
nt - This articleisprotected bycopyright.Allrightsreserved. Accepted Article ute frain f lcprns ad te products detected other and glucopyranose of formation further oligosaccharides The aluminu Material. percentage ( carbaldehyde (l hex main The pyrolysis fast cellulose in tested were catalysts The Reaction tests POx/SBA in i acid Phosphoric in increase an produces shown inFigure evoglucosan, evoglucosan, total -
3 Al - is sae in stage first enopyranose /SBA
m and phosphorus. m
acidity - ecin rdcs a p a products, reaction iue 5 Figure 15 volatile - n eetbe iud products liquid detectable in
5 catalysts 15 sample
f T . urfural
6 , followed by the cleavage of the of cleavage the by followed , LG mpregnation of mpregnation .
e highest he
- ), reaction shows 2 , -
which ca ) ls ( ulose . 1,4:3,6
cellulose cellulose A detailed list of the identified compounds as well as their their as well as compounds identified the of list detailed A
series
oa in chromathograms ion total products cdt o SBA of acidity - l n evoglucosenone amount of desorbed ammonia was observed observed was ammonia desorbed of amount d ianhydro mainly
ossible untreated n the and at pyrolysis fast [Figure [Figure
were be attributed to be attributed
- ecin cee o bio for scheme reaction α
- SBA D
PO a b fud n h Supplementary the in found be can 5 1,6 - ] lcprns (G) y (DGP) glucopyranose
- ; x 5 eooos silica mesoporous 15 - /Al - 15 sample sample 15 anhydro LGO) o lvguoeoe production. levoglucosenone for /SBA β is the depolymerization to to depolymerization the is - 1,4
f samples of Br , - 15 - - glycosidic bonds and the the and bonds glycosidic ø 1,6 3,4 nsted acidsites . also oi popoi a phosphoric solid [ 46 - - a dideoxy ]
nhydro
According to the the to According led - oil formation is is formation oil
to an increase increase an to modified - - β β . - - [ 30 D D - , - . 41 glycero f [ glucose 45 uran , 42 ]
, 43 with with cid cid - for , 44 2 - - ]
This articleisprotected bycopyright.Allrightsreserved. Accepted Article Si have not does area% peak DGP l o production T sites acid of Furfural behaving catalyz formation deposition t dehyd and depolymerization hydrolytic of catalysis via proceeds with content aluminum 15 (mainly anhydro of formation D the of decomposition and dehydration The observed is Al of amount evoglucosenone he higher amount of acidic sites generated sites acidic of amount higher he e lgt nrae in increase slight he /Al aayt, Figure catalysts,
decreasing ais t o auiu cnet ad rsns h opst ted hn the when trend opposite the presents and contents aluminum low at ratios d ells pyrolysis cellulose ed furfural) proportion
also at the expense of LG of expensethe at n cd c acid in promote after Al deposition Al after LO gvn that given LGO, f as , respectively. , high Si under acidicunder environment a precursor
atalyzed pyrolysis reactions pyrolysis atalyzed /Al increased increases s
The . 7
h dhdain reactions dehydration the mono ratio shows furfural furfural . oe of role
sac Since
. of l of with de with An opposite trend was observed for for observed was trend opposite An Regarding the the Regarding . that
charides promote [ This 46 evoglucosenone
amount can can amount a definite a , 48 such
intermediary pyrolysis the ] [Figure [Figure
creasing creasing reaction pathway reaction without
d
LGO LGO ua is furan
(namely the decompositi the . [ 51 tendency since tendency
6
conducted ] on the catalyst surface surface catalyst the on
] Si ra percent area products distribution for distribution products
excluding . also [ /Al , 49 - of
. glucopyranose units lead to the the to lead units glucopyranose [ and , ] 49
pout f the of product a ratios. hl te omto o te 3,6 the of formation the While hs dianhydro this , G LGO LG, 50 be be ]
hence has been proposed for proposed been has
on eae t the to related The on of cellulose to furans. furans. to cellulose of on the
it n cdc environment acidic an rises
rises with decreasing with rises the the , higher
osblt of possibility DGP ration reactions ration
levoglucosenone akdy as markedly ua has sugar
ad furans and ) concentration concentration levoglucosan b pyrolysis of of pyrolysis the y aluminum y enhanced Al /SBA
been been DGP DGP acid
the the , [ 47 - - - ]
This articleisprotected bycopyright.Allrightsreserved. Accepted Article hshrc cd s peeust fr h ctltc activity catalytic the for prerequisite a is acid phosphoric hydration ethylene as such acids by increase observed be and products liquid H acid phosphoric content aluminum higher a with samples strongly de ratio seems phenomenon t behavior opposite an impregnated Concerning ( the Finally, DGP acids, of the decomposition is also D of dehydration the from DGP of ring anhydo activity of the phosphoric acid impregnated impregnated acid phosphoric the of activity Figure 3 PO 4 ).
creases on the SPA catalysts SPA the on creases 8
s The influence influence The ) interacts with phosphoric phosphoric with interacts
because of as
higher catalysts the the free the atclry n h frt case first the in particularly ; i.e. reaction
lmnm otn pr content aluminum bio
to be related to the decrease in decrease the to related be to ,
, a phosphoric acid phosphoric hshrc acid phosphoric - n Figure oil yield oil of ta observed that o
enhanced
h aon of amount the experiments 9 shows i s pres s cellulose [ [ cd rdcn A popae, hs o the for thus phosphates, Al producing acid ,
Figure Figure
(Table 2 (Table it has been found that the presence of presence the that found been has it
ented in Figure in ented that content
favored inacidicconditions. leached dcd sih ices in increase slight a oduced
odce oe the over conducted for re H free
the whe titratable of amount lower a is there 8 7
depolymerization ] ] ). h Al the
zinc oxide/titania, tin oxide/titania, oxide/titania, tin oxide/titania, zinc increases proportion As previously described, aluminum aluminum described, previously As re 3 when when PO
- lcprns i ctlzd by catalyzed is glucopyranose levoglucosenone levoglucosenone / free H free 4 SBA
on 10 umre i water in submerged .
- .
. 5 samples 15 [ the exhibits product each of
38 For 3 A clear correlation can correlation clear A PO ]
. The decrease in the the in decrease The
LGO LGO reactions catalyzed reactions 4
levels hshrc acid phosphoric
percentage area . bio as the the as h latter The - oil percent
( Si yield free free free
/Al /Al in -
This articleisprotected bycopyright.Allrightsreserved. Accepted Article n o te ufc o te aayt oen te composition the especially theLG/ governs catalyst the of surface the on and of concentration The products. of increased amounts variable with pretreated acid cellulose phosphoric of pyrolysis the in observed inhibited is LG levoglucosan of dehydration decreases, pyrolysis for available Al in observed levels levoglucosenone Al the of consequence POx by presented the a to leads which phosphates, aluminum of these of proportion smaller a is there products liquid of proportion as well as LGO of production the species those of amount the to has not species that phosphoric carriers acid niobic and zirconia
ecin rdcs distribution products reaction ,
there was a higher proportion of LGO LGO of proportion higher a was there acid amount . [ 10 n toe supports those and LGO anhydro ] /Al
As the concentration of phosphoric acid in the biomass was was biomass the in acid phosphoric of concentration the As interacted /SBA
n bio in - H 3 - PO 5 ape cmae wt POx/SBA with compared samples 15 .
As the amount of Al is increased is Al of amount the As - 4
oil increases. An analogous behavior has been been has behavior analogous An increases. oil
withaluminum saccharides – neato ad s h mi rao fr h lower the for reason main the is and interaction H
the cellulose depolymerization to obtain a great a obtain to depolymerization cellulose the
catalyz 3 was explained by the the by explained was PO se Figures (see [Figure [Figure . phosphor
4 -
ee te eut sget ht phosphorus that suggest results the Here, modified SPAs. modified oh n h cluoe ro t te pyrolysis the to prior cellulose the in both e
the dehydration reactions that increase increase that reactions dehydration the
lower 10 ratio – ] ic acid ic
assum . 8
bio
compared and and - oil
ing free that H species due to the formation the to due species
When the amount of amount the When
9 yield and a modification in in modification a and yield ) neatos ewe t between interactions .
h lwr oa acidity total lower The
to LG in the reaction reaction the in LG to in the SPA catalysts, catalysts, SPA the in f h products, the of - 15 catalyst is a a is catalyst 15 3 PO ; 4
therefore is related H 3 PO he er 4 ,
This articleisprotected bycopyright.Allrightsreserved. Accepted Article was necessary run. pyrolysis successive after eliminated atmosphere catalyst stages regeneration intermediate with interest considering PO bio of production and products volatile cat the of stability the determine to order In Stability tests differentrelativeof aluminum amounts species Al of spectra NMR H non their to perfo better a presented catalysts acid bio to 50% acid phosphoric I cn be can t x /SBA decr - oil .
The sample was subjected to five cons five to subjected was sample The - respect to that of of that to respect and ease 5 aayt ee performed were catalyst 15 oe that noted . In . the
3
carbon carbon
PO (see Table 1) Table (see to compensateto forlosses the regeneration the ueir aayi promne oad te anhydrosaccharide the towards performance catalytic superior a was not a determining factor determining a not was 4 2h treatment, and the recovered catalyst was used again in a a in again used was catalyst recovered the and treatment, 2h /SBA - impregnated counterparts. impregnated
mixture t e os f specific of loss he - 15 catalysts, it wasn´t found wasn´t it catalysts, 15
Al A
, the PO the , /SBA fresh fresh eann in remaining
step - 15 samples. make [Figure [Figure x , the carbonaceous residues were completely were residues carbonaceous the , /Al .
, rmance in LGO production LGO in rmance
PO - - /
hc consisted which oil SBA up catalyst addition of 20% at each stage each at 20% of addition catalyst up during the recovery procedure during recovery the x , /SBA
11 alyst in terms of the of terms in alyst series a surface
-
15
for bio for
]
the reactor reactor the and selectivity the towardsLGO. Finally,
On the other hand,solid other On the phosphoric ecutive pyrolysis tests ( tests pyrolysis ecutive - catalysts catalysts 15
- was ra fe th after area oil formation oil f es eprmns f the of experiments reuse of any correlation between the the between correlation any when considering when
selected for the analysis analysis the for selected n h calcination the in presented a presented t 5 ° 450 at
LGO levels in the the in levels LGO . Despite the Despite . when compared compared when dpsto of deposition e C . higher higher
Figure under air air under 27 Al MAS MAS Al of the the of yield
40 11
of - )
This articleisprotected bycopyright.Allrightsreserved. Accepted Article The hexagonal in tested and prepared catalysts acid phosphoric Solid Conclusion by an former the r a by explained be increasing the by presented distribution species acid phosphoric titratable Free PO run reaction consecutive tests. the of course the in decrease slight last the progressive a tests, the during can It f bio of x / acidity SBA
H
- interaction i yed and yield oil e bevd ht lhuh the although that observed be 3 PO experiment - phosph 15 sample 15
case mesoporous interaction of Al wit Al of interaction 4 induced by the Al deposition on the silica support produced an increase increase an produced support silica the on depositionAl the by induced uig h saiiy et f PO of test stability the during s
esrmns fe te last the after measurements
,
oric acid amount acid oric by of phosphoricacidof PO
. leaching dcini teaalblt o ratv popou species phosphorus reactive of availability the in eduction
levoglucosenone levoglucosenone (4 wt The x /Al fast fast
structure afterAl
with low condensation degree condensation low with / indicated indicated SBA % for thesample% fresh wt% and3 il t bio to yield pyrolysis of cellulose. of pyrolysis of - h 15 the low condensed condensed low the decrease was observed observed was decrease the deposited phosphoric acid phosphoric deposited the
,
catalysts thus indicating that the catalyst the that indicating thus bas c with a. -
oil d on ed fraction 25% percentage
- aluminum of the aluminum grafting andphosphoricacid treatments. showed x /SBA
experiment decrease t increasing at T e elemental he
Al in pyrolysis products. products. pyrolysis in - - 15 grafted grafted
The SBA The smlr eair presenting behavior, similar a
H of hwd similarities showed 3
PO in the in LGO maintained high high maintained LGO .
showed The trends The
4 - support. mesoporous
about 15% about species and in the latter the in and species aluminum aluminum - 15 support retained the retained support 15 for thespentcatalyst) phosphorus analysis . The .
80% reduction in in reduction 80%
loses mainly the the mainly loses
in the in
se content fe the after at the end of of end the at The specific specific The
silica results results with with content
products products s; levels levels those those were
fifth fifth can i.e., in ;
of
. a
,
This articleisprotected bycopyright.Allrightsreserved. Accepted Article yTécnicasInvestigaciones Científicas for thefinancial (CONICET) support. thank authors The Acknowledgements reaction products. the in fraction LGO the of reduction and deactivation progressive but slight a to led pyrolysis tests pres catalyst anhydrosaccharide. area was towards reactions dehydration has which acid phosphoric of fraction the the a of expense to phosphate aluminum of interacted in observed been either decrease area surface References a L % lower GO observed
in in the mass chromatogram mass the in
bio area percent area
with the Al the with amount of amount
-
ented the best performance and performance best the ented i production oil . eeirto in deterioration
However, the leachingHowever, of in
the
h H the n em o LO production, LGO of terms In
Univ - free H free
containing and the amount of free H free of amount the and GC s after after .
The presence of Al on Al of presence The ria Ncoa dl u and Sur del Nacional ersidad - 3
S detectable MS PO or 3 the addition of phosphoric acid phosphoric of addition the PO
in catalytic performance. catalytic 4 levoglucosenone - 4 mrgae samples impregnated
; th supports ), i.e. e
which is desirable for desirable is which G levels LGO ,
the easily leachable phosphoric acid, phosphoric leachable easily the phosphoric acid phosphoric ,
not interact not yoyi pout ( products pyrolysis which was which
reasonable stability after successive after stability reasonable . 3
; solid phosphoric acid catalysts acid phosphoric solid PO Relatively high Relatively
h highe the Al 4
was observed, was
- ed . A clear A re H free evidenced by the formation formation the by evidenced
P
from the catalytic material the catalytic from with opoi acid hosphoric a simpler a st
Consejo Nacional de de Nacional Consejo had no no had
3
PO ca aluminum correlation correlation bu 75 about proportion ayi activity talytic 4 - odd SBA loaded isolation of the of isolation
adverse effect adverse indicating that indicating promoted - 85 between between
strong of LGO of
at the at peak peak
has has - led 15 15 ly ly
This articleisprotected bycopyright.Allrightsreserved. Accepted Article [ pyrolysis.wood byfast Applicat [ Society, Washington (2003). chemistry:functionalization, synthesis, and applications. [ A review,waste: [ synthesis of( quinones naphthopyran [ Washington,pp. 21 Chemical Society, natural productschemistry synthons in levoglucosenoneits conversionnovel andto chiralderiv preparation the Zhao of Chung SandChangconvenientprocedurefor H, S,A [ (2014). a bio Duncan HuntRaverty W, AJand T,ClarkJH,Dihydrolevoglucosenoneas (Cyrene) [ levoglucosenone. [ levoglucosenone aschiral synthon. [ Washington,pp 81 Chemical Society, in [ chemicals [ 13 celluby catalytic pyrolysisproduction of 11 10 9 8 7 6 5 4 3 2 1 ] Trahanovsky] WS,Ochaoda Wang C,RevellWang Y, JM, KD,ArvidsonKB, Sherwood] Constantinou Debruyn J, M, L, McElroyMoity A, TJ, CR,Farmer Shafizadeh] Furneaux TT,Some Stevenson F, RHand SarottiZanardi] AM, SpanevelloRecentMM, SuárezAG, and applicationsof RA ] WitczakJZ, Levoglucosenone:A Chiral withaNew Perspective, Building Block Crocker] M, ] Chen] D,YinPyrolysis P, Wang HandHe technologies L, municipal for solid SwentonA facile into JN,Dalidowicz] entry JS,Freskos KernsML, Pand Chemicals ResourcesRenewable andMaterials from : 3306 : (2011). ] Kudo] S,ZhouNorinagaEfficientlevoglucosenone HayashiJ, Z, Kand DobeleRossinskaja] G, Dizhbite G, MeierT, Telyshevaand G, D Faix O, Witczak ZJK, andTatsuta - based alternative for dipolar alternative for based
ion of catalysts for obtaining catalystsfor ion of 1,6 . Royal Society of Chemistry,of Royal Cambridge,pp178 . Society -
) - Thermochemical conversion hongconin, Waste Manage Waste
Carbohydr. Res. Carbohydr.
J. Anal.Appl. Pyrolysis
vialevoglucosenone. anannelationreaction of The total
J. Org. Chem.J.
Carbohydratenatural products synthons in .
34 aprotic solvents.
71 Curr. Org.Synth. : 2466: – : 169 : - , ed by andK. , Witczak ZJ Tatsuta 97 (2001). 31 (2003). lose mixedlose ionic with liquid. - anhydrosaccharides from cellulose from anhydrosaccharides and
61 - - 2486 (2014). 191 (1979). of biomassliquidof to and fuels : 459 :
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: 401 : - 464 (1996). Chem.Commun.
9 – :
, ed byBozell, Ameri JJ. 405 (2005). atives, in 439
American Chemical reactions of - 179 (2010). - 459 (2012).
Carbohydrate
Green Chem.
50
: 9650:
American can
This articleisprotected bycopyright.Allrightsreserved. Accepted Article [ A: General CatalyticcelluloseMA, pyrolysis ofusing MCM [ MCM of presence Pyrolysis the in cellulose [ study. analytical cellulose: An pyrolysisoxideschiralevolved from distributionof anhydrosugars onthe of [ hydroxylactonebuilding anditsrole as block. oxides:nanopowder metal andcharacterisationchiralproduction a of [ (2014). solidfor levoglucosenone. catalysts acid [ Bioresour.Technol. produceand to biomass levoglu [ zirconia.prepare levoglucosenoneusing sulfated [ solid acid catalysts. phosphoric catalytic fastpyrolysisbiomasslevoglucosenone mechanically from of mixedwith [ BocaCRC Raton Press, [ withsomeacidicin sulfolane catalysts. [ Energy Sci. Environ. DehydrationGW, ofcellulose polaraproticsolvents. levoglucosenone using to [ oligomerization of propene. of oligomerization alkylati“solid catalystfor phosphoricacid” 23 22 21 20 19 18 17 16 15 14 13 12 ] Cavani and] Girotti G Effect F,Terzoni of G, waterin the the performance of Casoni] Nievas AI, ML,Moyano Diez EL,Álvarez M, Dennehy A, pyr the on study Analytical D, Fabbri and IG Lesci C, Torri ] Fabbri] D, CandBaravelli Torri V, ] ] WeiX,WangWu Jin Z, Y, YuZ, Fast pyrolysisand K, J Wu cellulose with of Lu ] DongQ, YeX,Zhang CandZhangY,Catalyticfastpyrolysiscellulose Z, of ] WangZ,L ZhangYe] Z,Lu X,Wang T, Q, Wang Xand DongSelective of C, production Hattori] H and Y, Ono Kawamoto] SaitoHatanakacelluloseand H,S,of W SakaS,Catalyticpyrolysis Cao] F,TJ, SchwartzKrishna McClellandDJ, SH,Dumesica JAandHuber Fabbri D, CandMancini Pyrolysisofcellulose Torri I, catalysed by
85
514 : 192 : u Q, Zhu Xu Q, Y,Catalyticfastpyrolysis andZhang cellulose to of : 235 : – 196 (2009). 196
171 –
8 240 (2016). 240 : 1808: : 10 : , pp 2 , Solid Acid Catalysis:from fundamentalsapplications to – Appl.A Catal., - 15 (2014). 1815 (2015). -
J.Anal. Appl. Pyrolysis
4 (2015).
BioEnergy Res. cosenone using magnetic SO cosenone magnetic using
- Effect of zeolites and nanopowder metal Effect ofmetal zeolitesnanopowder and 1 eooos materials. mesoporous 41 J.Wood Sci.
J. Anal.J. Appl.Pyrolysis on of benzene to cumenebenzeneto on of and for
97 Green Chem. : 177 : - 41 type catalysts.
8 : 1263: ChemSusChem - 196 (1993).
53
80 : 127 : – : 24 : 1274 (2015).
9 – – : 1374: 29 (2007). 133 (2007). 133 4 2
- /TiO
107 olytic behaviour of of behaviour olytic Applied Catalysis
4 – : 79 : 2 . nl Appl. Anal. J.
: 150 : 1379 (2007). – M andM Volpe
Fe –
84 (2011). 3
- O 154 4 . .
This articleisprotected bycopyright.Allrightsreserved. Accepted Article Science Publishe Recent Zeolite AdvancesIn Science synthesis modificationwithH andNMR Storek W B, Zibrowius zeolitecharacterization of H [ (2002). MCM [ SolidChem. State prepared bypost Jiménez [ J. and Blanchard [ Chem.Phys. matrixmetallophthalocyanines@mesoporous SBA [ catalysts. characterization SBA of [ (2013). polymerfor electrolyte membrane. silicasulfonicusedfunctionalizedreinforced phase amorphous acidas and silica [ (1982). silicatoward glass. gel evolving [ Attrition ofWhiteandYellow Sand. Silicaof byWetMechanical andCharacterization Preparation Nanoparticles [ Materials Chemistryand Physics characterizationandSynthesis surface mesoporous ordered SBA of silica [ mesoporous materials with post with materials mesoporous [ 33 32 31 30 29 28 27 26 25 24 34 Hag L Huang ] ] Kawi] S,Shen Chew Generation SCand Brønsted acid PL, of sitesonSi ] Gómez X Carrier PP, Man R, Hajjar J, Krafft E, Ambroise E, Rochefoucauld M, Baca ] Li J,Stepwise] Guo of situsynthesis LandShi andcharacterization in J, AzimovF,] Markova I Tran] Nguyen TN,Pham LeMLP, VM, TVA, Tran TPT, Synthesisof Bertoluzza] A,Fagnano CandMorelliRaman MA,andinfraredspectra on Akl] MA, Aly HF,SolimanAMEandAbd HMA,AbdElRahman Kokunešoski] Gulicovski B, M, Milonjić Matović Logar J, M,
Caro J,Bulow DerewinskiKurschner Karger HungerPfeifer H, M, M, J, M, U, - 41 by of grafting phosphorus species.
- López A, CharacterizationAl López A, andpropertiesof acidic J.Univ. Chem. Metall. Technol. - CazalillaMérida M,
12 - ad i Q Li and M : 5109: -
rs B.V., TheB.V., Netherlands,295 rs pp. MicroporousMater. Mesoporous synthesisa low alumination of
180 – : 1130: - 5114 (2010). 5114 (2010). 15 andTi , StefanovaSynthesis, VandSharipovK, and - - 3 , mrvmn o teml tblt ad cdt of acidity and stability thermal on Improvement Z, 1140 (2007). PO - - Journal Non of Robles JM, GurbaniRodríguezRobles JM, A, treatment of phosphoric acid, in acid, phosphoric of treatment
4 124 - , in , SBA Adv.Nat. Sci.:Nanosci. Nanotechnol. J Nanomed , ed byKlinowskiJ andBarriePJ.Elsevier,
: Studies inSurfaceScience 52: andCatalysis
1248 - 15 nanoporous materials forDME 15 nanoporous
47
– J. Mater.Chem. : 333 : 1252 - Crystalline Solids Nanotechnol - cost ordered mesoporous silica. ordered mesoporoussilica. cost -
- (2010). 340 (2012). 110 - 15 composites. 304 (1989). 304 (1989). : 232 :
–
241 (2008). 4 12 - - : 1 ZSM
SBA SK : 1582:
- Studies in Surface Surface in Studies
14 ( 48 -
- Elhamid AI, Elhamid and Phys.Chem. Castellónand E - - 15 materials 5 after post : 117 : 2013 –
1586 1586 Babić
- 4 - 128 15. 15. ). : 1
-
- B 6 ,
- J. This articleisprotected bycopyright.Allrightsreserved. Accepted Article (2010). JAR, [ aluminum, structural ofSBAmethods onthe performance andcatalytic [ Paris,pp. 953 Elsevier B.V, andTrends, TargetsChallenges, Alproperties of modified SBA [ A Appl. Catal., hydration ofethylene.catalytic performance impregnatedthe of phosphoricacidin [ 184 (2006). Biofuels to andBiolubricant.Conversion W, [ A Appl. Catal., hydration ofethylene.catalytic performance impregnatedthe of phosphoricacidin [ pp. 949 ElsevierB.V, Paris, and F. Babonneau Targets andChallenges Related Trends, Materials: formation of investigation mesoporousand of films powders, thin in [ 251 I. Physicochemicalthecatalytic of Pt catalystsmaterials. characterization JA, HydrogenationVeen and tetralinon JAR Lercher silica of [ Spectroscopies. Thermal Evolution TransitionalNMRandIR of AluminasFollowed by [ Elsevier93 M, Science pp. B.V, II Materials Nanoporous 129: Catalysis and Science adsorbed pyridine Lewis Brønstedacidityaluminated and of SBA [ 43 42 41 40 39 38 37 36 35 44
] GurinovAA,Rozhkova YA,andZukal Shenderovich A,CejkaJIG,Mutable ] ] MaJ,QiangTangWang J,X L, D, Effectand Tang Dragoi] B,BenniciAcidic Dumitriu E,andA. and Auroux S ad ] ] D Fougret] CM, Atkins MP andHölderichthecarrierInfuence ofon WF, the ] Mali MazajSolerM, Rangus G, M, FonféB,] WilliamsMF, SieversAbrahamA, vanBokhoven A, C, Jentys van JA, Pecharromán] Sobrados Iglesias C,I, González JE, H : 485 : Fougret CM, Atkins MP andHölderich carrierInfluenceon the WF,the of
esn J, oua D, aui PM, omn A ad a Veen van and AE Coumans PCMM, Magusin DG, Poduval EJM, Hensen 3 Formation of acid sites in amorphous silica amorphous in sites acid of Formation PO e AraujoGonzalez NMR LRR,Scofield CF,Pastura anddeAraujo
– 4 /Al 496 (2007). 496
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– 0 12123 (2011). -
Zeolites RelatedMaterials: and 6170 (1999). - - 15 as revealed by NMR of 15 asrevealed by 952 (2008).
- alumina. , ed byGédéon A,Mass , , ed by Sayari A and Jaroniec Jaroniec and A Sayari by ed , - of synthesis different CarreñoSanz TandJ,
- J. Catal. J.
15 modified by 15 modified – alumina sorptive sorptive
Zeolites and
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This articleisprotected bycopyright.Allrightsreserved. Accepted Article 149 anhydro [ FePO [ Carbohydr.Res. pyrolytic synthesisdec and [ withsomeacidicin sulfolane catalysts. [ phosphoric acid. of reactionsduring presence dehydration anddepolymerization pyrolysis inthe [ [ (1989). 2. carriers. Surface acidity andreactivitytoward olefins. [ 51 50 49 48 47 46 45 ] Shafizadeh] FandC XiaYan] H, Xu X,WangJ S,Yang Y, Ge andZuoS,Effectof L, Zn/ZSM Shafizadeh Acid] Furneaux TG, F, TTandCochran RH,Stevenson Kawamoto] SaitoHatanakacelluloseand H,S,of W SakaS,Catalyticpyrolysis DobeleRossinskaja] G, TelyshevaMeier G, D andCellulose G, Faix O, ] WangSand LuoZ, Ramis] G, RossiandBusca oxide PF,Lorenzelli GV,Phosphoricacidon - 154 (1976). 4
catalysts oncellulose pyrolysis. - 3,4 - dideoxy
61 Anal.J. Appl.Pyrolysis : 519: -
β - D hin PPS. Pyrolytic production and decomposition of 1,6 hindecomposition Pyrolyticproductionandof PPS. Pyrolysisbiomass of - 528 (1978). - glycero omposition of 1,4:3,6omposition of - hex
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- 49 enopyranos : 307 : . De Gruyter, Be De . Gruyter, - –
dianhydro 2015 317 (1999). (1999). 317
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FigureExperimental 1. pyrolysisthe setupschemeof reactor. For Peer Review Peer For
This articleisprotected bycopyright.Allrightsreserved. Accepted Article with phosphoric acid, C) SBA-15 after post-synthesis after withSBA-15 treatmentphosphoric mesoporousC) acid, D) with Al, silica support after Figure 2. A) TEM micrographs TEM Figurecommercial of A) mesoporous 2. SBA-15 support silica,impregnated SBA-15 B) Al deposition Al subsequentH and Review Peer For
3 PO 4 impregnation.
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Figure 3. Infrared spectra of A) the Al/SBA-15 catalysts Al/SBA-15 the A) Figure of spectra Infrared 3. series,PO B) For Peer Review Peer For
x /SBA-15 and and /SBA-15 samples. SBA-15
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Figure 4. A) FigureA) 4. 27 Review Peer For Al MAS NMR spectraNMR B) MAS Al and
31 P P NMR MAS catalysts. the of spectra
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Acceptedion Figurechromatogramsselected of Total 5. samples. Ref.: (1), 2(5H) Furanone; (2), 2(3H) Furanone, 3 Article acetyldihydro ;3 methyl ; (3), (4),2,4(3H,5H) Furandione, 2,5 Dimethyl 4 hydroxy 3(2H) furanone; (5), unidentified; (6),1,6 Anhydro β D glucofuranose.
This articleisprotected bycopyright.Allrightsreserved. Accepted Article FigureReaction schemefor6. cellulose decompositioncondensable involatile presencethe products to of For Peer Review Peer For Al/SBA-15 and POx/Al/SBA-15 and Al/SBA-15 catalysts.
This articleisprotected bycopyright.Allrightsreserved. Accepted Article FigureVolatile 7. products selectivity functionAl of insamples.a Al/SBA-15 content as
This articleisprotected bycopyright.Allrightsreserved. Accepted Article Figure 8. Bio-oil yield as a function of Si/Al ratio Si/Al Figureof inBio-oilfunction the 8. a yield as catalysts.
This articleisprotected bycopyright.Allrightsreserved. Accepted Article FigureVolatile 9. products selectivity functionAl solidof ina POx/Al/SBA-15 content as phosphoric acid catalysts. catalysts.
This articleisprotected bycopyright.Allrightsreserved. Acceptedyield % Figureand free of area Levoglucosenone bio-oilfunction 10. phosphoric to a acidfor POx/Al/SBA- as Article 15 catalysts. 15catalysts.
This articleisprotected bycopyright.Allrightsreserved. AcceptedFigureVolatile 11. products distribution forbio-oilPO and yield Article consecutive fast pyrolysis consecutivefast runs.
x /SBA- 15solid during phosphoric acidcatalyst