Hydrocracking of Oil Residue

International Conference
On Sustainable Environmental
Technologies (ICSET)

20 I 2

B2_17

Hydrocracking of oil Residue from Palm

oil Milt Effluent to Biofuel

and Karna Wijaya3
Hasanudinr*, Muharnmad Said2, M. Faizalz,M. Hatta Dahlan2
r Doctoral program of Environmental Sciences, University of Srirvijaya, Palembang 30662' Indonesia'
,O"prrr*"ni oiCt
f*rrttyof Eojin"ering, Iiniversityof Sriwijaya, Palembang 30662'

"iiJEngi*".ing,

3-


Sciences, University of Gadjah Mada'
Department of Chemistry, Faculty of Mathematics and Natural
YogYakarta, Indonesia
*Corresponding Authir. Email: ghasanudin@yahoo'co'id

Abstract

last few years, as a result,.palm-oil waste rvhich is a
The total paln oil production has increased in the
several
The palm oil production process in mills consists of
by-product of the milling process rvill also increase.
of
types
different
of
generation
tire
in

fresh fruit bunches of oil palnr-results
unit operations. The
rvaste for
harmful
most
the
as
considered
is
residue. Among the waste generated, put* oit miii"fnu"nt eOrr4p)
and
a thick brownish liquid that contains high solids' oil
the environment if discharged untreated. PoME is
POME
of
for POME treatment, since the direct discharge
grease. Several treatrnent te-chnologies have been used
oit igt .oit.r"sidue in POME, attempts have been made to
pr"r"*"
adversely affects ttre environment.bue to tn"

tt chemicars and biofuel. Recovery of oil residue
recover and convert it into varuable producis such as *"n
its altemative usage is exp]or1{r In a preliminary study'
from pOME is difficult and not economical; if,"."forr,
of liquid hydrocalbonr^fuel (biofuel) from oil residue
rve observed that it rvas possible to produce
poME has been catalytically hyidrocracked to biofuel with Ni/Mo-Zro2 pillared
from poME. oil residue frorn
of
reactoi. The data shorvs that the catarytic activity
monmorillonite (NMZM) cataryst in fixed bed micro
Ni/Mo
parent monmorillonite (M)' While' catalyst
pilared montmorilioniteiZtvt) is more active than

p;;.ld;f

;;;t

t;"t


Ze

of oil residue from POME into
were loaded on ZM can increase the catalytic activity ior hydrocracking
biofuel products consist of gasoline'
biofirl- The productrrn=." *uinf, gases, biofuel and iolid coie. The
kerosen and dieset oil fraction'
i"1:-"ota., biofuel, palm oil, monmorillonite' hydrocracking' catalyst
1.

I

r
I

Introduction
palm oil industry has resulted

residu' oil residues

sludge rvaste (PoME) u'hich contains amount of oil
oftreating palm
success
Th^e
energy resource'
processed
T
contained in the palm oiisludge could potentially
fossils and
from
oil
of
lueJ
oil rvaste sludge into fuel oil-will be very tig"i'nl""t in resolving-the-iependenceconduted
be
can
oil
fuel
qualified
inio

residu from PbMg
reducing environmental burdens. Processing of oil
called
or
hydrogenation
of
process
and
cracking

*

through two processes at once, that are pio".r, of
Hydrocrackinr*",

fuels s'hich is posfektif, have been
on catalytic cracking of vegetables oil into hydrocarbon
result
+1, soybean oil [5] and jatropha oil [6]' The
done, such as Candelilta oit 1r1. rapeseed "il t2i;;;l* oir t:,

into
be
converted
of trigiy;idis in u.gitibt.s oil -can
of these studies concluded that rhe *uin "o*.nt
sludge
waste
from
oil
p"rign otca'tatyst for procesiing vegetable
hydrocarbon fuel, gasoline and diesel nu.tio.r.
processing can
and rnust meet necessary re(uirements for its
important
very
is
poME
into gasorine fraction
of
the

investigated
been
have
inetal
both
of
form
take place. Ni and Mo metal both in the singular or combination
of
result
The
oil
crude
coal
of
[8]'
and hydrocracking
usage as a catalyst r"i loi t va.genation ofl"nrerr" [7]
hydrotreatment,
for

reaction
catalyst
a
as
uied
these studies concruded that Ni and Mo rnetal can be
it was intr|duced cracking catalyst material
hydrocracking and deoxygenation. tn the early *.nriot "TT'y,.
is not so high that is not good to be catalyst'
using acidified natural clay. Horvever, then# resistance of clay
good nature' Sefiction of pillared montmorillonite
Montmorillonite clay is kind of clay mostly piitur"a and have
ability to both as catalyst and supporting
as supporting catalysi based on ."s"ar"h .onducted has suffrcient
cracking catalYst [6, 8].

2- Hethods
2.1 The oil residue from POME

rvas obtained from PT' Sriwijaya Pahn Oil

The oil residue from poME-based fatty acid mixture residue
rnild.smell, lighter than rvatef and fi'ee of
Indonesia-palembang. It rvas received as dark trorun liquid, having
fatty acid mixture'
water. The pOME rvis extracted by soxlet extractor to find the

C*ntur-v Priik"

lltrttl.

ntal Tec'lrrroi.3'ics (iC
Llartg:L*li, I iruilairel: ?6-?? r\pril' ]t)l?"

!i li'

l')'

196

2012 International Conference


On Sustainable Environmental
Technologies $CSET)

2.2 Catalyst preparation and characterization

Naturalclayofmontmorillonitetypeitutl*u,precipitated'anddriedinoven.Itrvassaturatedbyusing

water to clean
Furthermore, the clay was washed.by demin
Natrium Chloride ,otutior, *Jr*irf"a fo.'j+ fro*r.
solution'
oxychloride
zirconium
by
was pillared
the chloride ion of the cray. This product (Na-Montmorillonite)
and
NiNOr
of
solution
in
ioaked
**
2M
This result is referred as ZrO2pillared *rtt*;;ii;;ii " 12tut1 11" rvas dried at the temperature of l30oC for 3
Mo
Ni
(Ng.r)eMozO 2afor Z4noro unairied. The ZU """t"irirg
'na of 350'C and the flow rate of 1'0 ccls for 3
g;
;tiliJtp"'utut"
O,
florving
by
oxidized
hours. Then, it rvas
temperature of
of oxidationivas reduced by flowing H2 gas.at the
hours. In order to get good catalyst, the result
montmorillonite
rtr," pi"ar", ir rgferred ut Nintao-Z.o2 pillared
350oc and the flow rate of 1.0 cc/s ror r noursl
area
foi its acidity by ammonia adsorption' The BET surface
catalyst (NMZM). rn"lutufrt rras characterir.a

andporevolumeofthecatalyst*"."*.u.,'"a_uvnitrogen.adsorptionusingAutosorbl(Quantackome
prior to
*# a"gut-ted for 5 h under uu"uum at 300"C
Automated Gas Sorption System). the samples
l'
Table
in
presented
i.'"1 character'istics of M, /tU ana NMZM are
physical ,"i

the

analysis. The

"i,"t
2'3isuinm"ei#f""ry;tTlf'"'ffi""""1]J"u,
*orpl:r,:.pressure in a continuous up

flow.fixed-bed
in the vertical
I I *rrlia.
microreactor. The reactor rvas a 400 *r. long,*l
(rveight hourly space
475oc and rvith a oil residue feed rate
tube furnace. The reaction ternperature r"ur'ir,
particle
ratio *ur o-zo. The catalyst (12.0 g) with
r t 6. stainless steer tube praced placed

oil residue

io'irti,-.rtirt"
"ututyriio
qrart, rvool supported with a stainless steel
"r
500 and 1000 pm *rs roua.J over I .0 g of
betrveen
size ranged
center of the
*onitored i'y u,ir".*o.orpre poiitioned in the
mesh in the microreactor and the temperatur"-*
bed and connected to a temPerature controller'
tt","

velocity, wHSv)

"u,utyo Hydrogengaswzrspassedthrough.thereactorforlhbeforetheoilrecoveryfromPoMElvasfedusing
in the reactor' the liquid product (organic and aqueous
a peristatic pu.p- Orr""1i*Jy ,t"t" h-ad reached
bulb' The
*tif"1t gaseous produtt *u' "oll""t"d in a gas-sampling
fractions) was collected in a liquid sampler
at
operated
fro*" ihe liquid product in a microdistillation unit
unconverted fatfy acid mixture .vas separateJ
residual
the
as
after the vacuum distillation lvas termed
200"c for 30 rnin under vacuum- The residue remaining
gas
chromatography'
using
fatty acid mixture u,'6 ,t product rvas analyzed

"

3. Result and Discussion

3.1 Characterization Oil Residue from POME
e;
PoME shorvs that the residue rvas dominated by a mixture
The result of oit analyst of oil residu from
oi
frorn
acids
fatty
of
constituent
main
i"rry acids. while the
free fatry acids in r"n"l Lnnor, 40-g0%

.in""

residue are shorvn in table l'

oil restidue &om POME
ids in otl
of fattv acids

Table

Percentage
65.93

Fa$y Acid

Oleic acid
Stearic acid
Linoleic acid
Palmitic acid
Lauric acid

'7.64

9.28

6.12
3.45

Lignoceric acid

2.76
2.42

Others

1.40

Arachidic acid

3.2 Result of Preparation and Characterization of Catalyst
at 10.000 times magnification are sho',.i'
The result of Sifuf unufysis of catalyst M, ZM and MNZM
^- I L?surface texture of nature montmorillonite dllfigure l. SEM f,rgure shows no change on structure and
piialled montmorillonite form

a layered

tAl

surface'

l"tsl

LUI

(B) andNMZM (C)
Figure l. Result of SEM figure of catalyst M (A), ZM
Tei:itttc'logir:s i li':; !.r'f i

{'tnirtti'l]aillllirl*i.i]i:trg!'t'li,l'li:'iiliittri:2r:-?7A]:ril'liil?'

!t

F.i

' S$

'

20l2 International Conference

En''ironmentar
il;;;;;;ie (lcsET)
Technologies

'fu'''
NilzM cataryst has more srnat particles
;t; Mo metal to the surface of ZM
"iili

-

on
ZIvr and NMZM cataryst shorv that
ie ce;nparison figure of sEM
Ni and Mo metal, attaching on the surfa-c"
,* r"t.f,*ge the topology of surface of ZM layer'

"i?ri1;;;;;;."

=

=
.E

Hidrocracking of Oil Residue
is shorvn in table 2' The data
calalysts Y,, zM and NMZIvI
using
by
residue
oil
hidrocracking
by using catalysts M and
Result of
liJ.o.ru.king pro.*r i"[tit*tan
.rrrl;r'"
to
ability
the
has
NMZM
n-," presence of
rorvs rhat catalyst
iov" ;"i"";i";""*1vJ Nir,,zv'
percentase
high
from
seen
be
trr. rt can
"f. tu,,, i"t""t"tf'e rvork of hidrocracking catalyst'
in-.ututy't
ircon- nickel and molybden'urri*.tut

2

";;;';;i"

able I R.esult of hrdrygfggki
r-^-werqion (%o)
Carah'st
JJ.6 /
\T

t2.37

54.43

Z\7

N\Z}I

51.40

82.38

gas chromatography
iauid oroduct is then analized by using
in figur
shown
is
t*,rt of research
;l;[,,;.

I

t4.6L

Coke (%)
2.71

16.98
l 5.03

o,tsu

F^. -"^drrct

o--reunicliquialrq$g(%L

(Yn)

t74

gasoline' kerosene
to characterize the fraction into

3i-00;

i

3;o,oo i
!

i::.oo i
€i
o

u'1J,00
3

1o,oo

pl

I

:.oo

oro

z\{
Cata\'st

n frorn hiclrocracking Prod*ct

hidrocracking oil residue
can be used as a catalyst for
catalyst
NMZivI
that
conclude
Based on the data, we can
80% and 307" of gasoline fractio,-

5. Conclusion

from P.ME by

.on'"#g "f**"1';n

scheme research grant
Acknorvledgements
Srirvijaya Universiry under STRANAS
and
DIKTI
Dp2M
the
by
The financial support

il.i;, ilo./Hqli'Lrzo

r

6) is gratetullv acknorvledged'

Biocrude
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198