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Biofuels From Waste Fish Pyrolysis

Biofuels From Waste Fish Pyrolysis

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Biofuels from waste fish oil pyrolysis: Continuous production in a pilot plant
V.R. Wiggers
a
, A. Wisniewski Jr.
b
, L.A.S. Madureira
b
, A.A. Chivanga Barros
a
, H.F. Meier
a,
*
a
Chemical Engineering Department, Regional University of Blumenau (FURB), Sâo Paulo, 3250, Bloco I, Sala I-204, 89030-000 Blumenau, Santa Catarina, Brazil
b
Chemistry Department, Federal University of Santa Catarina (UFSC), Santa Catarina, Brazil
a r t i c l e i n f o
 Article history:
Received 28 October 2008Received in revised form 24 January 2009Accepted 5 February 2009Available online 28 February 2009
Keywords:
Waste fish oilPyrolysisBiofuelsHeavy bio-oilLight bio-oil
a b s t r a c t
Fast pyrolysis of waste fish oil was performed in a continuous pyrolysis pilot plant. The experiment wascarried out under steady-state conditions in which 10kg of biomass was added at a feed rate of 3.2kgh
À
1
. A bio-oil yield of 72–73% was obtained with a controlled reaction temperature of 525
°
C.The bio-oil was distilled to obtain purified products with boiling ranges corresponding to light bio-oiland heavy bio-oil. These biofuels were characterized according to their physico-chemical properties,andcomparedwiththeBrazilian-fuelspecificationsforconventionalgasolineanddieselfuels.Theresultsshow that the fast pyrolysis process represents an alternative technique for the production of biofuelsfrom waste fish oil with characteristics similar to petroleum fuels.
Ó
2009 Elsevier Ltd. All rights reserved.
1. Introduction
Biomass resources are abundant all over the world and can beeconomically,sociallyandenvironmentallyviableasanalternativeforthereductionandgradualsubstitutionoffossilfuels,promotingsustainable development[1,2]. This energy source has theadvantage of being carbon dioxide neutral in contrast to fossilfuels, but it is often challenged since it requires the use of landpotentially available for food crops[3]. Agricultural wastes andby-products, and wood processing and food industry wastes, witha high content of organic compounds, are potential sources of energy recovery and environmental protection[4].The utilization of biomass is centered on the fact that it iscomposed of cellulose, hemicelluloses and lignin[5,6], althoughit also contains triglycerides and fatty acids[7,8].Theuseoftriglyceridesandwastefattyacidstoproducebiodie-sel using the esterification/transesterification reactions is the sub- ject of many recent research studies[7,9–12]but several factorsinhibit the use of this technology, mainly when the raw materialsare biomass wastes based on triglycerides. The major factors arethevariationoftheacidindex,thesolidscontent,heavyequipmentfor large-scaleproduction, theneedto usealcohol inexcessanditsrecovery, and, in some cases, the purification of biodiesel[11,13].According to the Food and Agriculture Organization[14], theworld fish production in 2006 was 141.6 million tons of fish, andaround 50% of the total fish material processed becomes wastematerial. This represents 70.8 million tons of fish waste, of whichthe amount of oil varies from 40% to 65%[15].Most of the known technologies for the use of waste from thefish industries are not economically attractive, and sanitary land-fills and effluent treatment ponds are not recommended due tothe unpleasant odor they produce[15].In this regard, pyrolysis can be used as an alternative to upgrade this oil.In the development of technologies for biomass conversion, thefast pyrolysis process is one of the most important techniques, dueto the possibility to produce directly liquid fuels[2,16,17]. Theliquid product of biomass pyrolysis is commonly known as bio-oil and it is composed of a complex mixture of hydrocarbons withdifferent chemical groups and molecular sizes[18,19].According to the source material, biomass for the fast pyrolysisprocess can comprise cellulose, hemicellulose and lignin[3,4,6,16,17,20], or triglycerides[2,7]. During the First and Second WorldWars,pyrolysisofvegetableoilsplayedanimportantroleinliquid fuel supply[21]. Since the petroleum crisis at the end of 1970s, several studies on the cracking of vegetable oils and fatshave been conducted and the results indicate the technicalviability to produce fuels similar to petroleum-based fuels.In1983,Alencaretal.[22]conductedexperimentsinapyrolysisbatch reactor using palm, babassu and piqui oils, typically fromnorthern and northeastern Brazil. The reactions were carried outat atmospheric pressure in the range of 300–500
°
C, and the majorproductsidentifiedinthebio-oilwerealkanesandalkenes.Besidesthese compounds, aromatics and carboxylic acids have beendetected by Schwab et al.[23]in a destructive distillation processof soybean oil and high oleic safflower. A tubular reactor forthermal cracking of canola oil, in continuous operation, with and
0016-2361/$ - see front matter
Ó
2009 Elsevier Ltd. All rights reserved.doi:10.1016/j.fuel.2009.02.006
*
Corresponding author. Tel.: +55 47 3221 6054; fax: +55 47 3221 6001.
E-mail address:
meier@furb.br(H.F. Meier).Fuel xxx (2009) xxx–xxx
Contents lists available atScienceDirect
Fuel
ARTICLE IN PRESS
Please cite this article in press as: Wiggers VR et al. Biofuels from waste fish oil pyrolysis: Continuous production in a pilot plant. Fuel(2009), doi:10.1016/j.fuel.2009.02.006
 
without steam, has been studied by Idem et al.[24]. Thermal andcatalyticconversionsofusedsunfloweroilwerecomparedbyDan-dik and Aksoy[25]who obtained products in the gasoline fractionwith lower aromatics content in the catalyzed oil. The pyrolysis of vegetable oil from macauba fruit produces carboxylic acids, alde-hydes, alcohols, alkenes and alkadienes[26]. In other studies, soy-bean, palm and castor oils were processed in a batch pyrolysissystem showing formation of a bio-oil composed of paraffin, ole-fins, carboxylic acids and aldehydes. This bio-oil, when purified,leads to fuels with physico-chemical properties comparable withthe traditional fuels obtained from petroleum[27]. The use of lardin a fixed-bed pyrolysis reactor has been investigated by Adebanjoetal.[28]andHuaetal.[29]whoconfirmedtheviabilityofobtain- ing fuels from animal fats. The optimization of the thermal crack-ingofcanolaoiltomaximizetheproductionofolefinsusingalargenumber of experimental data and an analytical semi-empiricalmodel hasbeenperformedbySadrameli andGreen[30]. Theeffectof the catalyst/palmoil ratio, temperature and residence time con-ditions in a transport riser reactor at atmospheric pressure on thebio-gasolineandbio-gasyieldshavebeenpresentedbyTamunaiduand Bhatia[31].Despite the advantages of the pyrolyticprocess, pyrolysis of tri-glycerides is not well technologically established and the use of vegetable oils and fats has been concentrated on the alkali-cata-lyzed esterification/transesterification process[32]. According toMaher and Bressler[33], most studies have been performed inbatch systems, on laboratory scale and with small amounts of bio-mass. The reaction optimization, product analysis and scale-upstrategies are opportunity study areas.Thus,inthisstudy,apilotplantforthecontinuousfastpyrolysisprocess was used to perform experiments on the thermal crackingof waste fish oil under steady-state and isothermal process condi-tions. The experimental data acquired enabled the calculation of the mass and energy balances to determine the product yields, aswell as energy consumption analysis. The bio-oil and bio-gas gen-erated were quantified and analyzed. The bio-oil was distilled toobtain purified products in the boiling ranges of gasoline and die-sel. Following Brazilian-fuel specifications, these two fractionswere physically and chemically tested and the properties com-pared with those of gasoline and diesel obtained from petroleum.
2. Experimental
 2.1. Waste fish oil
The waste fish oil (WFO) used in this study as the triglyceridefeedstock was collected from the waste treatment unit of a fisheryindustrylocatedin the southof Brazil, after flotationinthe aerobictreatment unit followed by separation in a centrifuge, and it wasused as received without any pre-treatment. The waste fish oilwas characterized by visual aspect according to ASTM D 1298and by water content using the Karl Fischer method according toASTMD630407.TheacidandiodineindexeswereevaluatedusingASTMD974andprEN14111,respectively.ThedensityoftheWFOwas determined in a pycnometer. The solution fed to the reactorwas an emulsion of waste fish oil, with 5% of water added to in-crease the heat transfer efficiency.
 2.2. Description of the experimental apparatus
The pilot plant for the continuous pyrolysis process can be di-vided into the following sections according to the schematic dia-gram inFig. 1: (1) feed system section; (2) pre-heating section;(3)tubularreactor;(4)condensationsection;(5)storageandemis-sion section; and (6) instrumentationand control section. The feedsystemhas a reservoir and a positive displacement pump allowinga constant feeding of the waste fish oil. The oil flows into a 316stainless steel serpentine (6000
Â
18mm) inside a fixed-tempera-turepre-heatertobevaporizedbeforeenteringthetubularreactor.The first thermocouple (T-01) in the reactor checks the pre-heateroutlettemperature. Thecylindricalreactorismadeof316stainlesssteel (2310
Â
67mm) and is composed of 12 electrical coils, 1kWeach, arranged in four PID control networks (CN), as shown inFig.1. Thegas-mixtureflowstowardtwocondensersinseries,con-nected to distinct liquid reservoirs. The gas phase, separated fromtheliquidphase,flowstoavolumetricflowmeterandthentoagastreatment unit. The instrumentation and control section of the pi-lotplantiscomposedofatypeKthermocouple, pressuresensors,avolumetric bio-gas flow meter and a registration system for thepower consumption in the pre-heater and in the reactor. SCADAsoftware was responsible for the user-machine interface and stor-age of all variables, including temperature, pressure, flow and theenergy measured in the process, which were recorded in adatabank.
 2.3.Mass and energy balances
The WFO pyrolysis process can be considered according to thefollowing general reaction scheme:
--
 ⎯  ⎯  ⎯ 
CokeSludgeOilyoil-BioHeavy oil-BioLight oilBiogasBioOilFishWaste
Energy
ð
1
Þ
The biomass is converted to gas (bio-gas; BG), liquid (bio-oil;BO) and solid (coke; CK) fractions. The BO fraction can be ex-pressed in three products according to the carbon numbers inthe chain: light bio-oil (LBO), heavy bio-oil (HBO) and oily sludge(OS). It was possible to write the yields (wt%) for bio-gas, lightbio-oil, heavy bio-oil, oily sludge and coke as following:
g
BG
¼
Weight of BGWeight of WFO
Á
100
ð
2
Þ
g
LBO
¼
Weight of LBOWeight of WFO
Á
100
ð
3
Þ
g
HBO
¼
Weight of HBOWeight of WFO
Á
100
ð
4
Þ
g
OS
¼
Weight of OSWeight of WFO
Á
100
ð
5
Þ
g
CK
¼
100
À
g
OS
À
g
HBO
À
g
LBO
À
g
BG
ð
6
Þ
where
g
OS
is the heavier bio-oil yield;
g
HBO
is the heavy bio-oilyield;
g
LBO
is the light bio-oil yield;
g
BG
is the bio-gas yield; and
g
CK
is the coke yield. The weight percent values of LBO, HBO andOS were obtained by gas chromatography in terms of chain carbonnumber,as discussedinthenextsection. Themassof BGwasquan-tified by the volumetric flow measurement and the determinationof the gas density as a function of the composition, pressure andtemperature.Thecokeyieldisthedifferencebetweenthewastefishoil fed and the bio-oil+bio-gas.
To carry out a thermal analysis of the process, the pre-heaterand the reactor were considered as perfect mixture systems withisothermal and non-adiabatic conditions. Thus, for the mathemat-ical modeling, the following assumptions were adopted: completevaporization of the oil in the pre-heater and all chemical compo-nents of the vapor undergo reaction. Therefore, the mass and theenergy balances for the pre-heater section can be written asfollows:
2
V.R. Wiggers et al./Fuel xxx (2009) xxx–xxx
ARTICLE IN PRESS
Please cite this article in press as: Wiggers VR et al. Biofuels from waste fish oil pyrolysis: Continuous production in a pilot plant. Fuel(2009), doi:10.1016/j.fuel.2009.02.006
 
Mass balance in the pre-heater section,
dd
m
PH
ð Þ
 Ã
¼
_
m
ð Þ
À
_
m
V
ð Þ
ð
7
Þ
Energy balance in the pre-heater section,
dd
m
PH
ð Þ
pPH
ð Þ
PH
ð Þ
h i
¼
_
m
ð Þ
p
ð Þ
ð Þ
h i
À
_
m
V
ð Þ
pV
ð Þ
V
ð Þ
h i
À
D
V
ð Þ
_
m
ð Þ
 Ã
À
_
q
0
À Á
þ
_
q
S
0
À Á
ð
8
Þ
where
m
(PH)
is the mass inside the pre-heater (kg);
_
m
ð Þ
is theliquid mass flow (kgs
À
1
);
_
m
V
ð Þ
is the gas and vapor mass flow(kgs
À
1
);
pPH
ð Þ
is the mass heat capacity (kJkg
À
1
°
C
À
1
) insidethe pre-heater;
(PH)
is mass temperature inside the pre-heater(
°
C);
p
ð Þ
is the liquid heat capacity (kJkg
À
1
°
C
À
1
);
(L)
is theliquidtemperature(
°
C);
pV
ð Þ
is the gas andvapor heat capacity(kJkg
À
1
°
C
À
1
);
(V)
is the vapor temperature (
°
C);
D
(V)
is thevaporization enthalpy (kJkg
À
1
);
_
q
0
ð Þ
is the energy loss rate inthe pre-heater (kJs
À
1
); and
_
q
S
0
ð Þ
is the energyconsumptionratein the pre-heater (kJs
À
1
).The mass and energy balances for the reactor section are pre-sented as follows:
Mass balance in the reactor section,
dd
m
ð Þ
 Ã
¼
_
m
V
ð Þ
À
_
m
P
ð Þ
ð
9
Þ
Energy balance in the reactor section,
dd
m
ð Þ
p
ð Þ
ð Þ
h i
¼
_
m
V
ð Þ
pV
ð Þ
V
ð Þ
h i
À
_
m
P
ð Þ
pP
ð Þ
ð Þ
h i
À
D
ð Þ
_
m
V
ð Þ
 Ã
À
_
q
1
À Á
þ
_
q
S
1
À Á
ð
10
Þ
where
m
(R)
is the mass inside the reactor (kg);
_
m
P
ð Þ
is the prod-uct mass flow (kgs
À
1
);
p
ð Þ
is the mass heat capacity (kJkg
À
1
°
C
À
1
)insidethereactor;
(R)
isthemasstemperatureinsidethereactor(
°
C);
pP
ð Þ
istheproductheatcapacity(kJkg
À
1
°
C
À
1
);
(R)
is the reaction temperature (
°
C);
D
(R)
is the reactionenthalpy (kJkg
À
1
);
_
q
1
ð Þ
is the energy loss rate in the reactor(kJs
À
1
); and
_
q
S
1
ð Þ
is the energy consumption rate in the reactor(kJs
À
1
).Consideringsteady-stateconditionsforthepre-heaterandreac-tor, the mass balance for these two sections can be rewritten as:
_
m
ð Þ
_
m
V
ð Þ
_
m
P
ð Þ
ð
11
Þ
Consequently, the heat balances can be written for steady-stateconditions to predict the vaporization and the reaction enthalpy,respectively:
D
V
ð Þ
¼
_
m
ð Þ
p
ð Þ
ð Þ
h i
À
_
m
V
ð Þ
pV
ð Þ
V
ð Þ
h i
À
_
q
0
À Á
þ
_
q
S
0
À Á
_
m
ð Þ
ð
12
Þ
D
ð Þ
¼
_
m
V
ð Þ
pV
ð Þ
V
ð Þ
h i
À
_
m
P
ð Þ
pP
ð Þ
ð Þ
h i
À
_
q
1
À Á
þ
_
q
S
1
À Á
_
m
V
ð Þ
ð
13
Þ
Fig. 1.
The schematic diagram of the pyrolysis pilot plant.
V.R. Wiggers et al./Fuel xxx (2009) xxx–xxx
3
ARTICLE IN PRESS
Please cite this article in press as: Wiggers VR et al. Biofuels from waste fish oil pyrolysis: Continuous production in a pilot plant. Fuel(2009), doi:10.1016/j.fuel.2009.02.006

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