EFFECTIVENESS OF COMO AND NIMO CATALYST

ON CO-HYDROPROCESSING OF HEAVY
ATMOSPHERIC GAS-OIL/WASTE COOKING OIL
S.Bezergianni
A.Dimitriadis
LaboratoryofEnvironmentalFuels&Hydrocarbons
ChemicalProcesses&EnergyResourcesInstitute
CentreforResearch&TechnologyHellas

S.J.Kiartzis
M.C.Magiliotou
A.N.Skandilas
V.S.Dimitropoulos
HellenicPetroleumS.A.
Thessaloniki,Greece

CERTH

Waste Cooking Oil Diesel-2G

9
+ 2
Biofuel
2G

WCO

Bettercombustion(increased
cetane)
Moreeconomic(highHHV)
Morestable(noTAN,highIP)
Sustainable

catalyst

?
Potential to cover 9,5% of
Greek diesel demand

Largescaleunitsrequirelarge
investments

www.biofuels2g.gr
Bezergianni et al. Diesel Sustainability Improvement Perspectives
WCO Incorporation in Existing Refinery Thessaloniki

Light hydrocarbons C1-C4

Isomerization product

Isomerization

CERTH

Reformate

Catalytic
reforming

Hydrotreating

Polymerization

Gasoline polymerization
Alkylate

Alkylation

Alkylation gasoiline
Straight-run kerozene

Hydrotreating

Straight-run diesel
Catalytic pyrolysis gasoline

Heavy Gasoil

Atm.
Distillation

Hydrotreating

Catalytic
pyrolysis

Catalytic pyrolysis
diesel

Light Vacuum Gasoil

Hydrocracking gasoline

Hydrocracking

Hydrocracking mid-distillate

Liquid gas

Final processing and blending

Naphtha

Fuel gas

Aviation
Fuels

Diesel

Unleaded
Gasoline

Heating
oil

Heavy Vacuum Gasoil

Thermal processing

Vacuum
Distillation

Fuel gas and gasoline

Heavy
fractions
upgrading

Lubricants
process

Lubricants

Coke

Thermal
process

Asphalt

Bezergianni et al. Diesel Sustainability Improvement Perspectives

WCO Incorporation in Existing Refinery Thessaloniki

CERTH

z
z
z

SustainDiesel Project

Aim:Improvementofdieselsustainabilityby
incorporatingWCOandRESinexistingrefinery
Projectduration:23.3.2011 22.3.2014
Partners:
Coordinator: CentreforResearch&TechnologyHellas(CERTH)
Academicpartners: AristotleUniversityofThessaloniki&

NationalTechnicalUniversityofAthens
Industrialpartners: HellenicPetroleum&SunlightS.A.
z

Financing:ProgramCompetitiveness(ESPA)withfunds
fromEUandGreekGovernment

Bezergianni et al. Diesel Sustainability Improvement Perspectives

WCO Incorporation in Existing Refinery Thessaloniki

SustainDiesel Technology
Overview

CERTH

Emissions
Emissions

Crude
oil

Other
products

Refinery
Diesel

WCO

FAME
H2 from
RES

A. Evaluatetechnical
feasibilityof
incorporatingWCOas
alternativefeedstock
fordieselproduction
Sameinfrastructure&
operation

B. Assesscarbonfootprint
andGHGemissions
improvementversus
currentmarketdiesel

Energy

Bezergianni et al. Diesel Sustainability Improvement Perspectives

WCO Incorporation in Existing Refinery Thessaloniki

CERTH

Technical Feasibility Study

nEvaluationof

hydrotreatingcatalyst
oDetermineoptimal
operatingconditions

Gas
Product

Oil
H2
HPLT
RX

Liquid
Product

T,P,2/oil,LHSV

pDeterminemaxWCO
mixingratio
qEvaluateemissions&
engineperformance
Bezergianni et al. Diesel Sustainability Improvement Perspectives
WCO Incorporation in Existing Refinery Thessaloniki

CERTH

Experimental Methodology (1/3)

Overview

Twocommercialcatalyst

NiMo

CoMo

CommercialNiMo
CommercialCoMo
z

Threefeedstocks
HeavyAtmosphericGasOil100%(HAGO)
HAGOwith10%wastecookingoil(WCO)
HAGOwith30%wastecookingoil(WCO)

z
z

Smallscalehydroprocessingpilotplant
8experimentalruns
Bezergianni et al. Diesel Sustainability Improvement Perspectives
WCO Incorporation in Existing Refinery Thessaloniki

CERTH

Experimental Methodology (2/3)

Catalysts & Operating Parameters
NiMo Catalyst

Temperatures
Feedstock
(HAGO/WCO)

330C

350C

370C

100/0

100/0

100/0

90/10

90/10

90/10

70/30

70/30

70/30

CoMo Catalyst

Temperatures
Feedstock
(HAGO/WCO)

330C

350C

370C

100/0

100/0

100/0

90/10

90/10

90/10

70/30

70/30

70/30

Pressure(psig)

812

LHSV(hr1)

H2/Oil(scfb)

3000

Bezergianni et al. Diesel Sustainability Improvement Perspectives

WCO Incorporation in Existing Refinery Thessaloniki

Comparison

CERTH

Experimental Methodology (3/3)

Infrastructure & Experiments

Hydrotreatingeffectivenessparameters

Heteroatomremoval(S,N)
Saturationofdoublebonds(Br,H/C)
Dieselyields(180C 360C)
Conversion
Catalystdecayratio

Bezergianni et al. Diesel Sustainability Improvement Perspectives

WCO Incorporation in Existing Refinery Thessaloniki

Heteroatom removal

NiMo catalystshowedaperformance
increaseforthefeedstockwiththe
largestWCOcontent
NiMo catalystexhibitedincreasedHDN
performancewithincreasingWCO
content
Nitrogen

Nitrogenvariation%

105
NiMo

100

CoMo

Sulphur
Sulfurvariation%

CERTH

100
99
98
97
96
95
94
93
92
91
90

NiMo
CoMo

100/0

90/10

70/30

FeedGasOil/WCO

95
90
85
80
100/0

90/10

70/30

WCOadditiondoesnot
decreaseproductqualitywhen
NiMo catalystisused

FeedGasOil/WCO
Bezergianni et al. Diesel Sustainability Improvement Perspectives
WCO Incorporation in Existing Refinery Thessaloniki

10

Saturation

CERTH

Br.Index
z

Bothcatalystsprovidegood
saturationofdoublebondsforall
typeoffeedstocks
H/C

WCOadditiondoesnot
limitsaturation

Bezergianni et al. Diesel Sustainability Improvement Perspectives

WCO Incorporation in Existing Refinery Thessaloniki

11

Diesel Yields-Conversion

CERTH

Diesel yields

CoMo offershigherconversionand
dieselyieldsforpureHAGOandlow
WCOcontent
TriglyceridescontainedinWCOcanbe
moreeasilyconvertedintodieselrange
hydrocarbons
Conversion

60
50

NiMo

Conversion%

CoMo

40
30
20
10
0
100/0

90/10

70/30

WCOadditionincreases
conversionandimproves
dieselyields

Temperature
Bezergianni et al. Diesel Sustainability Improvement Perspectives
WCO Incorporation in Existing Refinery Thessaloniki

12

Catalyst Deactivation

CERTH

2500

Sulphur(wppm)

2000
1500
S=24.264DOS+1405.5
NiMo

1000

CoMo

S=8.6838DOS+918.58
500
0
0

10

15

20

25

30

Daysonstream

NiMo deactivationrateis3timessmallerthanCoMo

Bezergianni et al. Diesel Sustainability Improvement Perspectives

WCO Incorporation in Existing Refinery Thessaloniki

13

CERTH

z
z

Conclusions & Future Steps

WCOadditioninHAGOhydrotreatmentdoesnotlimit
targetedreactions(heteroatomremovaland
saturation)
WCOadditionincreasesconversionanddieselyield
NiMocatalystmoresuitableforWCOcontaining
feedstocks
Futuresteps
EvaluationofmaximumWCOratiothatcanbe
incorporatedinexistingrefinery
AssessmentofmaximumpotentialGHGemissionbenefits
byincoporatingWCOandH2 fromRES
Economicfeasibilityanalysis
Bezergianni et al. Diesel Sustainability Improvement Perspectives
WCO Incorporation in Existing Refinery Thessaloniki

14

CERTH

Thank you
for your attention