Challenges and Opportunities in Refining Catalyst Development: IndianOil’s Efforts Global Refining & Petrochemicals Congress , New Delhi, 17-18 th July, 2019 Dr. K.O. Xavier IndianOil R&D Centre
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Challenges and Opportunities in Refining Catalyst
Development: IndianOil’s Efforts
Global Refining & Petrochemicals Congress , New Delhi, 17-18th July, 2019
Dr. K.O. Xavier
IndianOil R&D Centre
2
Agenda
Refining Catalyst Market
Catalyst design challenges
IndianOil Efforts & Catalyst portfolio
Summary
Refining catalysts3
➢ Catalyst is indispensable and strategic to refinery
➢ Right catalyst can promote the technology with a better performance
➢ Knowledge intensive, only select players in market
Ref: The Catalyst Review , June 2016
FCC
HDT+ HYC
REF + ISOM
ALKYLATION
Others
40 %
25 %
15 %
15 %
5 %
Refining Catalyst Market
Environment
Refining
Chemicals
27%
33 %
40 %
2020 INR 1000 Crores (18.4% of Asia-Pacific-US$ 782 million)
2030 INR 2000 Crores (100000 MTPA capacity)
Projected market in India
4
Development of Refining Catalysts
Heavier Feeds
Clean Fuels
Yields
Product flexibility
Low Cost
Selectivity
Activity
Stability
Metal functionality
Acidity
Surface characteristics
Pore Geometry and Architecture
Drivers Features Levers
Challenge for catalyst innovation to meet refining needs
Discovery stageInnovative catalyst science, basic
understanding & Scientific tools
Development stageCatalyst formulation, Cost effectiveness,
& Scalability
Deployment stageManufacture, Quality assurance,
Demonstrate & Use
Concept to Commercial
Catalysis is an
inter-disciplinary science
5
➢ Increased understanding of catalyst activesites and reaction mechanism
➢ Investigations now possible for realcommercial catalyst under operandoconditions
➢ Spatial resolution of evaluating singleparticle of FCC catalyst now feasible
➢ Active sites of DHDT/Hydrocrackingcatalyst now well understood, aiding newcatalyst designs
Characterization of a single FCC particle
Design of new DHDT catalyst with better
understanding of active site and reaction
mechanisms
Advancements in refining catalysis
Molecular level understanding key to new catalyst design
6
Conversion Process Catalysis
❑ FCC Catalyst additives
Fuel Quality Improvement Technologies
❑ Diesel Hydrotreating (DHDS/DHDT)
❑ Gasoline quality improvement
❑ Reactive Adsorbents
IndianOil’s efforts in refining catalysis
7
IOCL’s Catalysts Portfolio
Catalyst Portfolio
DHDT catalyst for BS VI Diesel
Proven capabilities in successful scale-up & commercialization
Proprietary INDMAX Catalyst
Enhancing yields of LPG & C3 -C4 olefins
Residue upgradation
CO Combustion Promoter
Proprietary Adsorbent for sulfur reduction in Gasoline
Selective DiolefinSaturation
Hydrotreating of Jet/Kero/Naphtha
Cumulative sales volume
8
0
500
1000
1500
2000
2500
3000
3500
4000
Ad
dit
ive
s &
Cat
alys
t So
ld, M
T
9
FCC Catalysis
IndianOil’s efforts in FCC catalysis
Residue upgradation
Production of light olefins
INDMAX:Olefin Production Technology
Breakthrough technology for
conversion of heavy hydrocarbon to
high yields of LPG/light olefins & high
octane gasoline
Innovative catalyst with improved coke selectivity, bottom
accessibility & superior metal tolerance
Product yields, wt% FCC IndMAX
DG, wt% 1-3 8-10
LPG, wt% 25-33 35-42
Propylene, wt% 7-13 17-22
INDMAX FCC Commercialization Snapshot
2000 BPSD grass-root unit at Guwahati
(Commissioned in June, 2003)
85000 BSPD grass-root unit at Paradip
(Commissioned in December, 2015)
15000 BPSD grass-root unit at Bongaigaon(Under installation)
94000 BPSD grass-root unit at a Asian Refinery(Detailed Engg completed )
54000 BPSD grass-root unit at Gujarat(BDEP preparation in progress)
49000 BPSD grass-root unit at CBR(BDEP preparation in progress)
34000 BPSD revamp at Barauni(Feasibility study in progress)
In collaboration with ‘Lummus
Technology’-a MCDERMOTT
company
Revamped to 3000
BPSD in 2016
12
❖ Enhance propylene/LPG yield and produce high octane gasoline
i-Max Series ZSM-5 Additives
Ind. Eng. chem. Res., 38 (10)1999,3849
❖Protection of ZSM-5 during steaming is key to additive performance
❖IOCL’s proprietary zeolite stabilization technology retains activity
0
1
2
3
4
5
6
7
8
9
10
1 2 3
LPG
Propylene
Supreme Premium Ultra
Widely used in Indian refineries for LPG/Propylene maximization
Schematic representation of the effect of phosphate on thestability of ZSM-5. (Chem. Soc. Rev., 2015, 44, 7342--7370 | 7353)
OCTAZOOM –Octane Boosting Additive
13
❑ OCTAZOOM- Octane boosting additive
❖ Enhanced octane number/gain
❖ Minimal loss in gasoline yield
❖ Proprietary zeolite system with
selectivity for octane enhancing
molecules
2 4 6 8
Yie
ld (
WT%
)
Carbon Number
Base Catalyst
Base Catalyst + commercialAdditive
Base Catalyst +OCTAZOOM
Shifting of reaction chemistry to
increase gasoline yield with high
octane
Attribute Comm.
catalyst
OCTAZOOM Delta
LPG, wt.% 18.64 16.9 -1.74
TCO, wt.% 26.85 27.56 +0.71
LCN, MT/h 38.80 42.50 +3.7
CLO, wt.% 7.93 5.1 -2.83
Octane-ton gain,
MT/day +355
GVA/day, ₹ in Lacs 12.10
14
➢Optimal pore architecture
➢Adequate acidic function
RUA: Reside Upgradation Additive
❑ Enhanced yields of value added products like gasoline/LPG
❑ Reduction of heavier fractions/coke
Product Base Base+RUA Delta
Dry gas 4.19 4.69 +0.50
LPG 23.48 23.76 +0.28
Gasoline 39.12 40.37 +1.25
TCO 19.51 18.00 -1.51
CLO 6.85 6.45 -0.40
Coke 6.85 6.73 -0.12
Conversion 190oC 73.64 75.55
Catalyst design challenges
15
Promotes combustion of CO to CO2 in regenerator
Heat supply to
endothermic cracking reaction
Minimize flue gas CO emission
➢ Cracking in FCC Unit lead to coke deposition on
catalyst
➢ Combustion of coke in regenerator to CO and
CO2
Eco-MAX: CO Combustion Promoter
C + O2 CO2 ∆H = - 94 Kcal/Mole
C + ½O2 CO ∆H = - 26.4 Kcal/Mole
CO + ½ O2 CO2 ∆H = - 67.6 Kcal/Mole
Efficient CO conversion and heat utilization
Catalysts/
Co-Promoter
Base +
Reference
Base +
Eco-MAX
Pt content (ppm) 400-600 400-600
Flue gas analysis results vol. %
H2 0.29 0.383
N2 84.08 83.27
CO2 15.03 15.78
CO 0.506 0.516
O2 0.096 0.052
CO2/CO ratio 29.708 30.57
% CO conversion 90% 90%
16
Hydroprocessing Catalysts
IndianOil’s efforts in Refining catalysis
17
Transition to BS(VI) in India
DHDS
DHDT
De
su
lf.
Ca
taly
st
ac
tivity
Fe
ed
Hea
vin
es
s
Op
. Pr
H2
Co
ns
um
p.
Ar
Hyd
BS IV: S=50 ppm
BSVI: S=10 ppm
TEM image of DHDT catalyst
18
IOCL’s INDICATPrime DHDT Catalyst
Indian oil’s new generation DHDT catalyst technology INDICATPrime is
capable to meet the BS(VI) regulations
Relative activity
Design
High performance INDICATPrime catalyst is
under commercial demonstration in a
refinery unit
19
Gasoline Desulfurization
indSelectG catalysts
▪ Balanced hydrogenation function for
retention of olefins
▪ Precise window of composition/properties
required
▪Optimum hydrogenation with feed
variance
0.00
0.20
0.40
0.60
0.80
1.00
1.20
1.40
0 100 200 300 400
Days on stream
% D
iole
fin
sSustained performance of catalyst,
scouted for commercial demo
INDAdept Technology
H2
O2
Adsorption Regeneration
H2
AirN2
Feed
1 2
Two stage swing operation, good regenerability of adsorbent
0
50
100
150
200
1 2 3 4 5 6 7 8 9 10 11 12Nap
hth
a/ A
dso
rbe
nt (m
l/g)
Process concept
INDAdeptG: Demo Unit
Demonstration Unit –Capacity 35000
MTPA
Feed Indmax Heavy Gasoline
Product 50ppm S & 10ppm S Gasoline
(RON Loss ~ 5 Unit)
Parameter
Design Commercial Unit
Feed Product BS
IV/ VIFeed Product
Sulfur (ppm) 1000 <50 <10 600- 750 ~ 5
RON 89 86 84 85-89 81-84
Feed Product
Guwahati Refinery
➢ Catalysts are integral element to refinery sustainability and profitability
➢ Research driven innovations towards development of tailor-made catalysts key to success
➢ Fundamental understanding of reaction pathways and process will further lead to utilization of right catalyst systems or combinations to maximize effectiveness.
➢ Case studies and applications from Indian Oil show efficacy of this approach
Summary
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