TECHNOLOGIES FOR CLEAN AND

RENEWABLE ENERGY PRODUCTION

RESIDUE UPGRADATION 1
DR. PRASENJIT MONDAL
CHEMICAL ENGINEERING DEPARTMENT

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 Contents

 Petroleum Residue and its upgradation

 Residue upgradation routes
• Solvent deasphalting
• Visbreaking
• Delayed coking
• Gasification

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 Petroleum Residue and its upgradation
Petroleum residue: Atmospheric residue (AR) and Vacuum residue(VR) (Bottom of the barrel)
Properties Viscosity, cSt S, % N, % Asphaltenes % H/C ratio , (a/a) CCR, % oAPI

Crude oil 3.5@55 oC 1-3 0.1 2.8 2 2.8 33

AR 480 @ 50 oC 2.5 0.16 4.4 1.8 6.4 12.3
VR 1030 @ 100 oC 3.8 0.2 10-30 1.3 20.5 5.8

Thus the residual oils differ from the average crude oil in respect of
Higher viscosity
High sulfur, metals and asphaltene contents
Higher average boiling point
Low H/C ratio
High CCR
Essential requirement for upgradation - Improve properties e.g. increasing H/C ratio
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 Residue oil
A residual oil can be described as a colloidal system in which the dispersed phase is composed
of asphaltenes and resins etc., whereas the continuous phase is composed of maltenes (oil).
Both the phases are in equilibrium
During thermal cracking, the oil phase cracks and after certain limit of cracking the colloidal
equilibrium is disturbed, which results in flocculation of asphaltenes.
At this stage cracked fuel oil becomes unstable in nature. Some physicochemical properties of
residue are:
- Higher viscosity, higher salt content
- Higher heavy metals content
- Higher Sulphur and nitrogen content
- High naphthenic acid content

Asphaltene structure (Hus 1981)

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 Routes for upgradation
 Extraction based process (Solvent deasphalting)
 Thermal conversion based process (Cracking, gasification)
 Hydroprocessing based process (Hydrocracking)

 Thermal and hydrocracking may be catalytic or non catalytic type

• Some thermal cracking routes are
– Visbreaking
– Delayed coking
– Fluid coking
– Flexi coking
– Hydrovisbreaking
– Donor solvent cracking
– Hydropyrolysis
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 Routes for upgradation

Hydrogen
addition

Carbon
rejection

Other
technologies

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Worldwide distribution of commercial residue processing capacity
(Castaneda et al. 2014)(Web3)

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Residue Upgradation: Process selection

https://pubs.acs.org/doi/pdf/10.1021/ie0710871
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 Solvent deasphalting
FCC
De-asphalted oil (DAO) Hydro-cracker
Thermal cracking
Vacuum Lubes
residue SDA

Bitumen
Pitch
Power
CFBC Steam

Power
Steam
Gasification
H2
Petrochemicals
Applications of solvent deasphalting Fuels
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 Mixer

DAO
Solvent separator

Mi Extractor
Feed
xer Mixer
Pitch DAO
stripp stripp Condenser
er er
Modified from
Solvent Deasphalting process (Lee et
al. 2014) https://doi.org/10.1016/j.fuproc.2013.11.014
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 Deasphalting solvents
 Commercially used solvents are :
Light paraffin hydrocarbons, e.g., Propane, Butane(s) & Pentane(s) etc.
• Lighter solvents : propane & isobutane
– Higher selectivity
 General properties
– Reject all resins and asphaltenes – Solubility of oil decreases with
– Suitable for production of lubes oils increase in temperature
• Heavier solvents : n-butane, pentane (n& i) – More selective at higher
and light naphtha temperatures
-- Less selective than the lighter solvents – Exhibit lower critical solution
– Produce higher yields of DAO/DMO temperature.
(suitable as conversion feedstocks)

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 Deasphalting - Process variables
• Solvent Composition
– Blends of light hydrocarbon solvents
– Increased operating flexibility
• Solvent-to-feed Ratio (S/F)
– Selectivity improves by increasing S/F at constant DAO yield
– Economically optimum S/F is used
• Temperature / Temperature Gradient
Oil solubility in solvent
– Decreases with increase in temp. (optimum temps)
– Temp. gradient improves separation between DAO-asphalt phases
• Pressure
– Maintained above V.P. of solvent at operating temperatures.

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 Comparison of solvent (c3 – c5)
Solvent Feed Propane (C3) Propane – butane Butane (C4) Pentane (C5)
(SR) (C3/C4)

DAO
Yield, wt% 100 29 46.8 67.3 82.8
API gravity 6.6 21 16 12.1 10.3
Viscosity, cSt @ 100°C 1900 35 110 340 800
CCR, wt% 22.1 1.5 5.0 10.6 14.0
Sulphur, wt% 4.29 2.60 3.0 3.6 3.9
Asphaltenes, wt% -- -- -- -- --
“V” ppm 70 1.1 2.5 7 23
“Ni”, ppm 21 0.3 0.7 2.1 7
ASPHALT
Sp. Gravity -- 1.047 1.089 1.116 1.175
Sof. Pt. (R&B), °C -- 160 225 270 390
PEN. (25°C, 100g, 5 sec.) 1/10 mm -- 5 0 0 0
(Feed : Arabian medium V.R)
https://www.slideserve.com/edan-knight/mohan-konde- 13
hpcl-mumbai-refinery
 General operating conditions of SDA
units vs. Type of solvent
Operating Propane Butane Pentane
conditions

Extraction range 50 – 80 100 – 130 170 – 210

(°c)
Pressure range 3.5 – 4.0 ~ 4.0 ~ 4.0
(MPa)
Solvent ratio 6–9 4–7 3-5
(vol.)

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 Solvent recovery

Recovery of solvent from DAO & Asphalt phases made by

• Evaporative mode
– Multiple effect evaporation (up to 3 stages)
– Series of progressively lower pressure flashes followed by stripping
• Supercritical mode (for DAO/DMO phase)
– Phase separation at / above critical temperature of solvent
– 85 to 93% solvent recovered as lighter phase for heat exchange and recycle
in the process
– Recovered solvent has very low DAO content
– Remaining solvent from DAO recovered by flashing / stripping

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Advantages of supercritical solvent recovery

• More energy efficient approach Solvent recovery technique Relative energy

cost
• Utilities savings up to 40% Supercritical unit 100
(with heavier solvents) Triple effect evaporator 150
Double effect evaporator 170
• More compact unit Single effect evaporator 280

• Savings in capital investment for grass root plants (15 to 25%)

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 DEASPHALTING TOWER / EXTRACTOR
Column internals • Structured packing
• Baffle trays / Louvre trays Currently used in all ROSE units
Advantages claimed
• Rotating disc contractor
– Better quality of DAO
(RDC)
– Higher circulating solvent purity
• Packing (random / – Higher capacity for existing SDA units
structured) – Lower operating cost
• Parallel interceptor plate
• PIP assemblies
(PIP) assemblies
Used in UOP/FW SDA pilot units
Baffles Advantages claimed
Being used in all PDA plants in
the country – Increased separation efficiency (lower S/F ratio)
UOP/ FW offers choice of PIP – Reduced size of extractor vessel
or RDC – Reduction in capital and operating costs
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 Processing of DAO and asphalt
DAO
LUBE : Lube production increased by approx 20%
CRACKING : 1/3rd of cat. cracking feed in a refinery can be DAO
HYDROTREATING : Economical, consumes less hydrogen, less investment

Asphalt
BLENDING : Tailor made asphalt (bitumen) or fuel oil
VISBREAKING : Minimizes need for cutter stock
GASIFICATION : Hydrogen, steam and power production

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 SDA – technology licensors & units
Operating units
Licensor
Conventional Supercritical
(Technology)
Kellogg brown & root -- 33
(ROSE)* combine cap. > 600,000 bpd
UOP/FW (SDA)*
50
(Tech. merger in 1996)
IFP, FRANCE (SOLVAHL)
7
EIL/IIP (PDA) 2 --
RIPP, China (SDA) -- 5
* source: H.P. Nov. 2002 Exxon Mobil also offers PDA technology

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 PROPANE DEASPHALTING (PDA)
PDA PRODUCES DAO FOR:
– Heavy lube oil base stock / bright stock
– Cylinder oils
OPERATING CONDITIONS:
– Temperatures : 50 to 80C
– S/F (vol /vol) : 6 to 10
– Pressure more than vap. pr. of the solvent

QUALITY OF DAO FROM REFINERIES:

HALDIA CPCL HPCL
KIN. VISC. cSt @98.9°C 36-42 35-38 28-32
CCR, wt% 1.7 – 2.0 1-1.2 1.5-2.2

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 PROPANE DEASPHALTING - STATUS
Plant Capacity, MMT/A Technology
HPCL, Mumbai 548,000 IIP / EIL
CPCL, Chennai 574,000 IIP / EIL
IOC Haldia 650,000 Romanian/ expansion by EIL
/ ROSE

- All plants produce LOBS(BS)

- Solvent recovery : evaporation mode / supercritical mode
- Development of know-how for supercritical mode is done by IIP,EIL
&HPCL

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Thanks…

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