Appiied Catalysis Ai t e\eral 425426(2oi2i

I Ii::

r j1

t it i-i

r'tt .tt

F.-- -larHlJrrLrr
,Artl'rrlptl

journa

*',,iii&-?=F.

::

tia i; : ;.,,:r

i! i: I lP!'st

f^L-7
I -Jt llr/(t\ -:LuLqrJJrJ

5{i;c

ArA'l.

h c nr e p a g e :'Ar 1i4d'.r/ e i s e v i e r.

1G116

f1r

ra --r

t^
-IsLllLrqr
-rrIrpI

co

c-r1 I o

i iti
--l
Jt

ca t I

ie

pcai

f-atatVtir hy<lr*g*naficn *t xlii*se t* xylitol using ruthenium {atraiyst on Ni*

m * ri i fi

,:

ai

ri

iiJ

9,.1.{:}r}

iii "{

Mrti:ilesl'r Yadarr, Dinesir i(umar Mrshra, Jin-Soo Hwang'

Biare.[int:ri Rc:t:aritl (?r(er, ]<ortu Eeseffdl Insfftsie of Aumiml'{tchnalagy tKNCn, Dilei.on 305-ffi0, Refltblk \)f Korca

ARTICLE

II{FO

ABSTRACT

Article listory:

Ruthenium

The activity of Ru catalyst on a fiew class of NiO modified Ti02 srpport, Rtr/(NiO-TiOz), was studied in the liquid phase catalytichydrogenation ofxylose to xylitoi. The TiOz support was modified by
simpie impregnai'ion method uslng nickel chioride precursor and subsequent oxidai'ion. Various caialysts l{'iah different targeted compositions of RL1 {1.0 and 5.0.;r't%) and NiO {1.S, 5.e a*d 10wt%} in
NiO-TiO2 were prepared. These catalysts were characterized by using energy dispersive X-ray analysis
(EDX/EDS), temperaftlre-programmed reductior: (TPR), inductively coupled plasma (lCP) rnass specromcn-y', fi-afismisiion e iectt ofi riricroscopy (Tflltvlj, X-ray po',vder diffi-action (X."rr) dnd CO cheiniso',ption.'l"nc
novel catalysts are evaluated for selective hydrogenation ofxylose and the rcsults conipared with those
obtained from convenrional Raney Ni, RulC and Ru[iOz caraiysts carried out rnder identicai rearrion
conditions. The effect of NiO additive in fhe catalyst Ru/(NlO-TlOz), clearly found to enhance the con-

Niorndi6ilTiA

rrerci..B

P.eceived 13 SepteElber 2011

Received isre'isd iern2 Mareh2Ci2

Ac.epted 3}darchz?lz
Available online 11 March2012
Keywords:

Hydrogenation
Xylose

Xylitol

rri+lr{ :-.1- <+l#isrihJ

tc arlitdt

Ei'-rth94.F-s+

thq er{s

*f ertrtr*:,c

rctirrirr

mrH he riv+*.

:< err

{1.A%JNLO(5.Y/")-TiOz>&u{1.A%)iryi02 >Rd {1.0%)/C> Raney Ni.The effects of Ru afid NiO Ioadingxylose

concenrrarion (2.5, i5 artd 30wt%) and tempemtuiE (100, 120 arrd 140'C) were studied. Although at
higher temp 140 oC, the conversion ofxylose was increased fo optimum level. xylose to xylitol selectivitl,
decteased dul tc farinarla, af bv-araducts.
O 2012 Elsevier B.V. All rights reseled.

'1. Introduction

rlJdlronallv aJrne(i

oLrt in a three-pirase siLrrry baith rcai-iorover

i I 2j. Tire prineipal aclvanLages uI ihe ii"c i;f
nickel catalysts .rre its lower price, ease cf use as suspended slurry

R;ne v nii

Tl're selectivr caLalvLic hydrcgena'.ion

.."^.',
ru;i.i

".^1,',-'.1,'.
riiu:\

,.,

rl.,'i"

ol nalurally cccurring

...,,^.."^,'.1:",,
i,..-pui ji.'r:::

.i.. ;r'r. ;

!,,,.
't-.L^1.

,..

.-

environmenL lrieniliy route ior ihe pr,:dri,:liorr ci.rlternalive

sr.^-,ee,-eners: soiid metrl-L.iseii e:t:iyst: Jrp,,:rl in rn rgueorrs
environment and the hydrogen addition is brought about through

!ng agents anr! the sr.rbseq,renl formation

!ad5rc

I r 1l
-. --:-l
ll,dLsr
idr I l _Jl.

\/.,r:r^l
nyrlLUl,

d PrliLd

cl

^--L^Ldr
uurl

inorganic salts
-..--)llgdl

-l^^L^l
dlluilul

as

..,1.L
vvlLli

interesting propertie-s, is an ercellent arlincial sweerener gaining

'lhp

itrop)nt,*tr::,t,'-it,re.pn:,,a:r

m.ried io he.rroirnij

$?-1C

tt.,-,,'.t.,1):;,lt

rri.-r

ic;r;.-

miiiion piiced at -$5lkg i;idicating its

significance in many fbod anci other value added chemical indusi,ries. [i is highl;,'solr"ible in -rdaier, does noi .aiamelize ai elevaied
L(lllprldLUl15, lt: )Vl'r(L(lllilB L.lpd( lly HX(rrtl) llldt (,1 SUBdl (lll(l
h:< inrrer inrrriin renrrirpment< thr:'l h:'ino ntnnr_i:!lrr.,rri:-rbln inr
Lrsage by diabetics. Over the last few years, Lhe demand fbr xylitol
har incretseri errormorrs!r.r i4-71. Xyl!tol alsn iin<i-s applications in
several other industries such as ln pharmaceLrllcal, cosmelrc, and

svnj:hetic resin iS-i.i l. The hSrdrogenaiion oi xyiose to xlulitol is

krl i atiiysrs

i^,.,-i,.-lH-,,.h.-.^'i^'.,

I-mal'l

address: jshwang@kricLre-E tl.-S-

0926-860X/$

see

fiontsiaatero

doi:1o.1O1 6fi .apcata.2a2.B3.W7

+82 42 ABa 7 67 6.

Hwlng)"

2012 Elscuicr B.V-.Ail iights reserued.

',.r;.,;,',"-.1

.,,1,',., l',1'.,ill

i'rom hrudrosenated xvliroi sallrtion when

,n,4..<tr,

,,;

t< ,tt-.!,,

lzi

Nld.,

ir..

,,;

...cn,-...:.

it is rrsed in the lco<l

,,.i-,;. r: ;-1. 1. !',,*1.--t

.r,.t.

since exprnsive piirifiiaiion sieps sLit:h as ion-exi:haiige, fiiteriilF;

and crvstailizalion are invoiveri I i5l. The past few years have seen
a variety noble (Pt, Pd, Rr-r) met.rls wiih scme srlpports, blit among
Llttrtll ItuLllrtllulll udSrll LdLdly5L5 vvliILil )!tuvv titLlLIl 1ts5) ul llu ut<tLri'.,:rinn h;'..r'hrIn
inr:nd 35 ai!.ernative tc Ni b;:r,d j'.i:.1!irsrc iflr

hyclrogenation processes

in tecenl years [.]7-211.

lnvestigations

pr{}gress ilr progrer metal-srrnport svslems lhr the riirect

'i
hydrogenaLron ol xylose-nch soluirons / \theme ) lercirrtg lo hrgh
.,..1:,^l
..-^1....1-.^
--l
^^l^^':.,:,.,
-^.i,.:...
'^.-,--l-.
ptuuuLtluil, .-,L:!-.
vvilrrr
dlLtvrL-v
dlru
5(r(L(rvtLy r-..,^I^
ttrvEts ruvvdtu5
AyilLUt
being Iess sensilive to the deactivation ofcatalvst surfa.e by fbuling

ire under

..-^-;^^
L^..-L
\l-'(-tlr5.n!tltullYilautiiliLijuaijdit
^lr

* Ccrresponding author. Tel. : f 82 42 8s0 7382 ; fa:

,'^-,1

ertheless, the major dr.r,Nback ot R.-rney Ni r.ri.-r13,-sls, usLraliy, is their

relativeiy f ast deacr,ir,arion d Lre to .rcc,-rn-: rii...tion o[' o 13an r,- i mp,-r ri iies (from the starling malerial) on rhe caralyst surface. leading to
iiniinnilo nf rhe :, rive sirps.:nri rnei;l i;:ihing I i ii- i ril Ctnsequenlly, ccnl"/ersion rates and process selectivity arejeopardized. ln
:, :.. .^^^^.
i--^-.^-.
,L-,
rr:
L,
.^-^-t^,
.l
-ll:,:^-^*^
duurrrurr.
rL r) rilus( ililPUt ldrlL Lrrdt r\t tr-..^,ju5L uc !uillprqttty^1., ,tiltuvcu

-.-^ dJiildri<uiiiiiudiiuittdriuti)u,
--,-;l-Ll^
^- .L^ --*l:^-.i^..-

Ru on aclivaled carbon and Ti02

<rrrrirr rrcino mnriifreri Tin. crinn^rr

^r'

lrlpport, there is no systematic