M.

Yadav et

al. I

Awked Cstalysb A: Ce*eral 425-426 (2012)

10-

16

,,,'{ri

:r,::.;,.::i,.a::

: :., r:..t::: :.-1:;.:.4i.. ;,r.

....:.:

4...:

t",j :a ;.:

-::r:i

a:; :...:::1: :

:,:::.:::,,:.,,,a

a:,::.:

Fig. 6. EDX spectrum of the cataiyst Ru ( I.0Z)iNiO (5.0%

rqVeJt
ir-; t he

lhqplesen|e ol parirrles olsrle' 2.5nm, which correspond

Ru'fiir'iiles di spersed. on large. fi ake\ ; grav portionl'ol'-iiO.,1

\upport. Where;s.'figl 5iti-'' Aispl.:ys'the prrritles wiLh slighr ly

higl'ier :;iz+ iangc f icm

ic 12 nrn correspcnding to NiO particle j
interarted with TiO2 support. However, lhe presence o{'Ru particles
,toqgh the), are present along ivith NiO particies on the NiO-TiO;
idbirort could not be identified clearly. In order to corrfirrn their
sresencE EDll an.r[,,,iis'*;s calrieri n,.ii:ni. Lire speclrLriri rs p1esentd in Fig" 6. The spectrum uirdoitbledly :hows the presence of
- t dtdly)t ItrU I l.U'c]/l\lU
dll Llllrr LUlllpultf llL5 [tl, l\l dllU -'i]r',.
I I Ul tltC
.10

"

(s.oz)-Ti02l.
th-

rprl,,,-iiriiit,,

tt...<t.
vr ,nn
.,r\ rtt
LurrI.yJr.r
.y ^l

.., tt p*:*,)na.4

nrpn1ra.l
y.!Purr1,

LU

A mrin

pc.r!<

obsened al 378 'C (in curve b) is dr"re to con.:ersion ol Ni2* Lo Nio,

rrvith Richardson et ai. rindings as NiO ne,:r-!s
which is in
rer lempe ra I u[e 12,] l. On l he ol her ha nd, rhe
to reduce into
proliie of IRu (i
I (curve cj displayed a peak
at i50'C which is attribllted to the reduction of Ru3+ * Ruo and
the second peak at 360'C is due to the reduction cl Niz*--Ni0.
There is an additional peak observed at 42 5'C which is attributed to
ioi
r.,ori
u!luyL!r

ro,-i,,rr

ln-

^i

ntil+

- i\t;ll

I' ic rlarr

trnm

ho Tfrp rlrt r

hrr

i, :

:: :.
: ::a

'**':::':'.':.

:,,

...

:'

r *l
I i

::l:

j-l i(),

temperatllre o{ -ZAA"C is enough fbr the reduction of Ru3*

without affecting the NiO modified TiO2 support.

4.

Ruo

Conelusions

Catalytic liquid phase hydrogenation ofxylase to xylitol using

Ru catalyst on NiO modified TiO2 support was examined. A
varier-v o[ R-rl crr.alvsi-s wilh sredetermined c+mnosit-ions were
prepared and used to study the hydrogenation of xylose and
rhe results compared with Ni and oiher Ru catalysts carried oui

r drry 5truvv(u

/h
1+
-.: r - r\EU-r-r,
+ hKLl-flar dtlUi
Ure respef uve r LruLLruu ur t LtL,leulLlill Lt!tul
tue

:;ui-lace.

:::.*

. . ._::,8 t

under identical reaction conditions. The catalyst [P.u (1.S%)/NiO

iltlTftr)

the profiles oi ihe catalysts RrrlTiO;, NiO nrorlified TiO2 srrppori,

(NiO-TiO2) and RLrlNiO-TiO2 are shown in ljig. 7. Two 1'l'R peaks
ollserved at 1 70'C and 320 'C irr reei profile irurve ;r) are attributed

iRu '-Ruu;oxiciized rulhcnium on Tiu2

" : :..:

::..

ulrttltttillt

Lullvgt

5tutl ut AJtu5g

iss.s l *iirt #Evisflb9.7%)

andrhe sele.riviry ro xyliror (99.s%).

The order of catalytic activity was observed to be [Ru (1.0%)lNiO
{5.o%)-Ii0z1 > [Ru { 1.0%)iTioz ] > {Ru ( 1 .0%l/Cl > [ Raney Ni]. The percent NiO incorporated in mociified support (NiCI-Ti0z) piayed an
important role to minimize arabiflitol afld other by-products, which
generally [orrn during hydrogenation ofxvlose. Alrhough theiiiu-d
ofconversion ofxylcse, yield and seTectiviry to xylitol r+iith incorporation of 5.0wt% Ru in the .atalyst are maximum, the results
obtained with 1.A% Ru are close to 1AO% and hence is more than
enough for all industrial applications as metal Ru is expensive.

Acknowledgements

This work was supperted by the Institutional Research Program

{rnm
rha
rr
vrrr
Lrr!

nF rltuirT lei-1
rarl vJ
h', s: brurrr
artnt !12111 17r}-ln-n?-nn]
.Lv7n1i
r / srrg
vvl
\et

cooperative R&D Program lunded by the Korea Research Council

Industrial Science and Technology, Republic of Korea.

3rr[+NP

Bf+eBvo

'+

Referenceg

N,'

[1]

h,

[3]

[5]
{61

s{B

frH}

ffi

ii

S-i{ihojm,

Ciren Tecjfinj- Bjoterlrnol- 74 {lSSlil

J. Kuusisto,J.P- ]dild<ola, ]4, Sparv,.!- Wuna, H. Heildrila. PT- Salmi, Ind. Eng. Chem. Res.45 (2o06J 5900-5910.

Perala,J. VayryBen,

Fig.7. H|-TPR proflle of Bu (7-o%)lti02) (a), (Nio-Tioz) (b) and

J. Zhang, A Ceng, C. Yao, Y. Lu, O- Li, Bioresour. Technol" 7O5 QAU) E4-141.
C. Franeeschin, M. Sudiro. T- Ingram, I- Smirnova, G- Brunnei A Bertucco, Chem.

Eng. Res, Des. 89 {2A71) 631-ffi4.

[7] Y.Zou,KQi,)LChen,NMiao,J.-J.Zhong,J-Biosci.Bioengl09(2010)149-'1.52,"
l8l ,l- wjsaial<, M- He$hkffwjtz, s stejrr. lnd- Ing. r}lerr. Prod. Res Dfi/ejop. 13

sfl$

Temperature i"Ci
)-

Srjrrj.

Paraj6, H- Dominguez, J.M- Dominguez, Bioresour" Technol. 65 (1998)

[4] J-C-ls1-201-

fu'L+Su

l0*

T-

6s5-662.

E"u

&

)- t1u2 tL

51-55.

l?l lP- Mi]d.ala

fn-

lJ-v?o

P. Gallezot, N. Nicclaus, C.F. Gche, P. Fuertes, A- Perrard,J- Catal. 180 (1998)

{t974)232-236.

S-B- Kim. Y-Y lee, Biotechnol. BiEn& 15 {1985) 81-9O"

l"?.lll4i,k)da,T" Salmi, Chem. Eng. Sci- 54 (1999) 1583-1588[ 1 1 ] J.P. Mild<ola, T. Salmi, Catal. Today & t2a84) 27 7 -27 7.

[9]

Ru

O.anlNia

ll0l