Heavy_residue_upgrading

Heavy Residue Upgrading
1
The Major Problem With Residue Complexity of Feed Stock & Analysis
of Its Components
What’s the Reason?
Asphaltene is thought to be the most complex, high
molecular weight, polar and highly aromatic in nature
molecule present in petroleum.
Residue Specifications
Low H/C Ratio (1.2-1.4)
High Metals, Asphaltene, Nitrogen & Sulfur
Contents
Strategy Increasing H/C Ratio
Goal To Make Lighter Products
The process economy of residue conversion is strongly affected by the amount of
low value by-products and the amount of hydrogen in-put requirements.

2
Routs for Residue Upgrading Based on H/C Ratio
Carbon Rejection Hydrogen Addition
Visbreacking
Gasification
Coking
Deasphalting
Catalytic Cracking
Hydrotreating
HYCAR
Catalytic Cracking
HDM
Fixed Bed
HDS
HDN
Moving Bed
Ebullating Bed
Slurry Phase
RFCC

3
Technologies for Residue Upgrading Based on Catalyst Application
Non-Catalytic Catalytic
Solvent
Deasphalting
Thermal
Gasification
Delayed Coking
Fluid Coking
RFCC Hydroprocessing
Flexi Coking
Visbreaking
Fixed Bed HDT
Fixed Bed HDC
Slurry HDC
Ebullated Bed HDT
Ebullated Bed HDC

4
Road Diesel Deficit

5
This process uses a heavy solvent (typically C4, C5) to separate vacuum residue into a
deasphalted oil (DAO) and a pitch stream which contains most of the contaminants
in the vacuum residue feed (e.g. Ni+V, Conradson Carbon). DAO is normally used as
FCC or hydrocracker feed.
Solvent deasphalting is a technology which could be used to develop a phased
approach to investment .
Bottom-of-the-barrel upgrading at low cost
SDA is a separation process base on molecular weight (density), not a conversion process
Yields and deasphalted oils product properties controllable
Flexibility to meet a wide range of Deasphalted Oil (DAO) qualities
Lower operating expenditure with supercritical solvent recovery
Asphalt pitch can be used as a fuel component, or gasified to make power, steam and hydrogen

6
Residue Separation

7
Thermal Processes:
Residue Gaseous productsGasification
Integrated gasification combined cycle (IGCC) is an
emerging technology for efficient power generation or
electricity sector with minimum effect on the
environment (low SOx and Nox)
The capital cost of residue upgrading schemes based
on gasification continues to fall steadily. The capital
cost of gasification for power production (Integrated
Gasification Combined Cycle, IGCC), for example, is
now reported to be in the 850 / 950 $/kw range
compared to 1,500/2,500 $/kw just 5-10 years ago
un-controlled selective coal conversion
High Temperature (>1000)
Syngas
Carbon Black
Ash
The conversion by partial oxidation of a carbon containing gas, liquid or solid into a
synthesis gas, in which the major components are hydrogen and carbon monoxide.

8
Thermal Processes:

9
Thermal Processes:
Residue Coke & Liquid productsDelayed Coking
The process inherent flexibility to handle any type of Residue
The process provides essentially complete rejection of metals and carbon while providing partial conversion to liquid
products (naphtha and diesel).
This process is more expensive than SDA, although still less expensive than other thermal processes
Development of automated coke drum unheading devices, allowing the operator to carry out the decoking
procedure safely from a remote location.
Understanding of process parameters affecting yields, coker product qualities and coke qualities (e.g. shot coke).
Design and operation of major equipment items, in particular coke drums (allowing shorter coking cycles) and the
delayed coker heater (on line spalling / decoking and minimization of coking in furnace tubes).
The foremost disadvantage of this process is high coke
formation and low yield of liquid products.
The product selectivity of the process is based on the
operating conditions mainly pressure and temperature.
delayed coking is the most frequently preferred process
for refiners to residue processing.

10
The coke from the delayed coker could be used in many ways
Thermal Processes:
As an export product. The European countries are ideally located to export coke to
local and more distant markets.
Fuel in cement kilns or as a blend in coal fired power stations. Petroleum coke typically
has a heat value some 20% higher than coal and around 20% petroleum coke can be
blended into coal without the need for significant modification to the power plant.
In addition, some or all of the petroleum coke could be used in a future project based
on gasification, raising power and/or producing more transportation fuels,
petrochemicals, hydrogen and steam.

11
Thermal Processes:
Fluid coking can have liquid yield credits over delayed
coking because of shorter residence time.
higher quantities of liquids and less coke in comparison
with Delayed Coking
Lower Utilities cost and fuel consumption in comparison
with Delayed Coking
lower quality of products
The temperature (1000 C) used is insufficient to burn
all the coke.
Fluid coking and flexi-coking are fluid bed processes developed from fluid catalytic
cracking (FCC) technology. Fluid as well as flexi-coking technologies are
comparatively front runner technologies in residue processing. In these processes,
circulating coke carries heat from the burner back to the reactor, where the coke
serves as reaction sites for the cracking of the Residue into lighter products.
Fluid Catalytic Cracking Developing Fluid coking Extension Flexi-coking
Flexi-coking is an extended form of fluid coking and uses a coke gasifier to convert
excess coke to Syngas.

12
Thermal Processes:
Increase refinery net distillate yield. Increased conversion during visbreaking will turn to more
sediment deposition.
Visbreaking is a mature process that may be applied to both AR, VR and even Solvent
Deasphalter Pitch, which means a mild thermal decomposition or improvement in
viscosity.

13
Carbon Rejection & Hydrogen Addition
Thermal Processes incur low investment and operating costs than Hydroprocessing.
The yield of light products during Thermal Processes tends to be lower than Hydroprocessing.
liquid products obtained from thermal processes contain S, N and metals (V, Ni, etc.) that indeed need further
purification by HDT process like HDS, HDN and HDM respectively.
Thermal process or coking based technologies suffer from the disadvantage of producing a large amount of low value
by-products and require extensive further processing of its liquid products.
The importance of thermal processes remains lower than catalytic processes, but due to their lower investment these
processes continue to be the most common for residue upgrading.
Carbon rejection method has flexibility for feedstock specification like atmospheric residue with up to 20% Conradson
carbon and 10,000 ppm metal content (Ni+V),. whereas Hydrogen addition can accept feeds (Atmospheric Residue)
with up to 38% Conradson carbon and about 4000 ppm metal content (Ni+V).

14
Catalytic Residue Processes:
FCC RFCCExtension
RFCC offers better selectivity to high gasoline and
lower gas yield than other Hydroprocessing and
thermal processes.
RFCC avoids perverse high coke yield, high catalyst
consumption and unit operability. So this character
makes that process less likely than hydroprocessing.
Catalyst design to accommodate higher metals feed
and to minimize catalyst coke .
Riser design and catalyst / oil product separation to
minimize over cracking.
Regenerator design improvements to handle high coke
makes and avoid damage to catalyst structure.
The major limitation of RFCC process is the need of good
quality feedstock (high H/C ratio and low metal content).
The catalyst pore limitation with respect to residue
diffusion.
this process can only treat atmospheric residue, which
predominantly contains relatively low amounts of metals,
sulfur and carbon.
The limitation for RFCC process is metal deposition, since
Ni and V deposition increases olefin yields through
dehydrogenation resulting in more coke formation, while
gradual deposition of impurities in a catalyst eventually
plugs the pores and deactivates catalytic sites
FCC is a well established approach for converting a significant portion of the heavier
fractions of the crude barrel into a high-octane gasoline blending component. RFCC is
an extension of conventional FCC technology that was developed during the early 1980.

15
Catalytic Residue Processes:
Residue Light productsHydroprocessing
High product selectivity of light products
Better selectivity of liquid yield (85% and higher) than
any other process
To obtain cleaner fuel specifications
The diversity stems from the hydroprocessing is not
only the catalyst development, but also process
technology, which can be selectively chosen on the
basis of desired product yield.
these processes have enough scope to modify the
process parameters and so the product selectivity and
shifted the commercial importance of the technology.
Hydroprocessing is relatively high in investment and
operating costs compared with thermal processes.
The race to high activity per volume unit for a long run is
still matter of catalyst formulation and some process
parameters optimization.
processes involve relatively high pressure operation (150
bars +).
hydrogen addition technologies make up only one-fifth of
global residue upgrading capacity .
Hydrogen
HDT
HDSHDMHDNMHCCCR
HCR
Hydroprocessing is the combination of HDT and HCR processes in which residue
feedstock is treated at low temperature but at high hydrogen pressure with or
without catalyst.

16
Hydroprocessing Tech.s classification based
on the position of the Catalysts
Fixed Bed Reactor Moving Bed Reactor Ebullated Reactor

17
Hydroprocessing:
Hydro-Visbreaking
Hydro-Visbreaking Process (HYCAR) is one kind of non-catalytic processes, which is
based on Visbreaking and involves treatment with hydrogen at mild conditions.
Visbreaking Dematallization Hydro-cracking
Another extension of Visbreaking process is Aqua-conversion (Hydro-Visbreaking), which
is a catalytic process using catalyst in slurry mode. This process was developed in 1996.
Hydro-Visbreacking Aqua-ConversionExtension
A shocker visbreaker is modified by the introduction of catalytic additives in feedstock and
water steam. The presence of the oil soluble catalyst and water prevents the coke
formation and deposition of sediment that often occurs during visbreaking.

18
Hydroprocessing:
Catalytic Hydro-processing
Fixed bed Moving/Ebullated bed
Fixed bed residuum or
vacuum residuum
desulfurization RDS/VRDS).
Hyvahl process
Residue hydrocracking
Moving Ebullating
HYCON H-Oil
LC-Fining

19
Hydroprocessing:
There is a wide variety of sulfided catalysts used for
hydroprocessing
a combination of RDS/VRDS and RFCC has gained wide
acceptance due to the selective conversion of residue
and smaller amount of by-products.
poisoning of catalyst over the time
requires development of new catalysts including support
and active metal, either by up-dating of former ones or
developing new formulations.
The limitation for RFCC process is metal deposition which
includes product yield and quality reduction.
During subsequent exposures to steam-stripping the
vanadate becomes very mobile, presumably as vanadic
acid, which is proficient to displace alumina from the
zeolite structure
designed for vacuum residue processing now run on
lighter feed or atmospheric residue for FCC feed.
fixed-bed designs have suffered from short catalyst lives (6
months or less) even though large catalyst volumes are
used (LHSV typically in the 0,5-1,5 range).
Fixed bed residuum or
vacuum residuum
desulfurization RDS/VRDS).

20
Hydroprocessing:
fixed bed using swing mode reactor
high temperature
High hydrogen pressure
low contact time
Hyvahl process

21
Hydroprocessing:
The growing demand for middle distillates has increased
the need for HCR in terms of process flexibility as well as
configuration and product Composition.
The catalysts used for HCR should have dual functionality,
i.e. cracking and hydrogenation (HYD) functions.
Residue
hydrocracking
most of residue hydroprocessing reactors are fixed
bed reactors.
selection of appropriate HDM and HDT catalysts, which
contribute to increase the performance of new processes
for residues refining.
must be shut down to remove (regenerate) the spent
catalyst.
fixed bed reactors may not likely use effectively for further
processing of heavy oil and its residue.
There are several other hydrocracking processes used by refiners on the basis of their
product selectivity such as: mild hydrocracking, Iso-cracking, uni-cracking HDS, IFP
hydrocracking process, MRH process etc.

22
Hydroprocessing:
Ebullating bed reactors are capable of converting
the most problematic feeds, such as AR, VR and all
other heavy oil feedstocks, which have high content
of asphaltenes, metals and sulfur.
They can perform both HDT as well as HCR
functions thus; these reactors are referred as dual
purpose.
moving bed catalysts are chemically quite similar to
the fixed bed catalyst, except that catalyst particle
and their mechanical strength and shape should
meet the more demanding situation.
utilizes a three-phase system that is gas, liquid, and
solid (catalyst).
By using of Ebullated technology the hydro-
processing upper limit of metal contaminants
increased from 200ppm to 460ppm. The
asphaltene upper limit increased from 12-19 % to
28 %, as well.
In Ebullated bed hydroprocessing, the catalyst within the reactor is not fixed.
In such a process, the hydrocarbon feed stream enters at the bottom and flows
upward through the catalyst; the catalyst is kept in suspension by the pressure of
the fluid feed
There are two most important
Ebullated bed processes, which are
similar in concept but different in
mechanical details.
H-Oil Process LC-Fining Process

23
Hydroprocessing:
catalyst and residue operates in co-current flow, the
fresh catalyst enters at the top of the reactor.
deactivated catalyst is removed from the bottom.
The catalyst is replaced at a rate to insure a total
plant run time of at least a year, which depends on
the metal contaminants in the feed.
HYCON
The HYCON process is typically operated in fixed bed mode but with increasing the
metal content in feedstock, one or more moving bed ‘‘bunker’’ reactors are added
as the leading reactors for HDM.

24
Hydroprocessing:
H-Oil Process
can operate over a wide range of conversion levels .
It has adapted to heavy vacuum Residue with high
metals and Conradson carbon
To maintain constant product properties during the
cycle length.
it has the ability to handle exothermic reactions, solid
containing feedstock and a flexible operation while
changing feedstocks or operating objectives such as
the use of single-stage or two-stage processes.
Extension T-Star Process
T-Star units can maintain global conversions in the
range of 20–60% and specifically HDS in the 93–99%
range.
The unit can act as either an FCCU pretreater or VGO
hydrocracker.
In mild hydrocracking mode is that the T star catalyst is
not sensitive to sulfur and nitrogen levels in the feed
and will provide constant conversion, product yields,
and product quality
the Ebullation results in a back mixed reactor so
desulphurization and hydroconversion are less than
obtainable in a fixed-bed unit.
H-Oil catalyst can be used in the T-Star process. A T-Star reactor can also be placed in-
line with an H-Oil reactor to improve the quality of H-Oil distillate products such as
virgin distillates, FCCU light or heavy cycle gas oil, and coker gas oils.
hydrogen and feed enter at the bottom of the reactor, thereby expanding the catalyst bed.

25
Hydroprocessing:
Schematic H-Oil Process

26
Hydroprocessing:
LC-Fining Process
can be operated for HDS, HDM, and HCR of
atmospheric and vacuum residues.
is well suited for extra-heavy residue, bitumen
and vacuum residue HDT feedstocks
Has demonstrated long cycle lengths
The LC-Fining process can achieve conversion
for HDS of 60–90%, HDM of 50–98%, and CCR
reduction of 35–80%.
low investment
more light-ends recovery
lower operating costs
yields a full range of high quality distillates
heavy residue can be used as fuel oil, synthetic
crude, or feedstock for a Resid FCC, coker,
visbreaker or solvent Deasphalter.

27
Ebullated bed processes can use extra-heavy feeds residues with elevated sulfur, nitrogen, and
metals content (i.e. compared with other crude oil distillation cuts) and do not require
pretreatment prior to the Ebullated bed process. These processes have high liquid yield, however
the conversion is not 100%. For any type of feedstock, high sulfur reduction is seen in all products
with significant nitrogen reduction, but to a lesser degree than the sulfur.

28
Slurry hydrocracking has an unusual history; it was first used in Germany as early as 1929
for hydrogenation of coal and two units were successfully working during the World War
II, which were switched to VR feed and operated until 1964.
Different commercial slurry units gain importance such as Veba combi-cracking, CanMet,
Microcat, CASH process etc.
recently both units have operated again for very poor quality feedstocks. Eni slurry
technology (EST) process is moving towards the commercial proof at one of the Agip’s
refinery in Italy.
in slurry hydroprocessing a selected catalyst is dispersed in the feed to inhibit coke
formation.
the effectiveness of the slurry hydroprocessing technology is highly dependent upon catalyst
selection.
so-called micro-metallic-coke or micro-cat catalysts efficiently convert low value heavy feeds
to a single-phase product with increased API gravity, lower viscosity and reduced
contaminants.

29
On the basis of Low value products
thermal process produce large amount of coke and undesirable products, while
RDS/RFCC strongly favor the residue processing but due to unavailability of good
quality feedstock this process is not likely by refiners.

30
Choices of process for residue hydroconversion as a function of 343 C residue properties
[ Carbon Residue; Sulfur; API gravity].

31Source: SFA Pacific

32
Residue Upgrading
Goal
the costs associated with the deep HDS
should be re-examined and compared with
the cost of fuel products produced by
conventional methods.
when fine catalyst particles were
slurried/dispersed in a residue feed. With
respect to catalysts, this may be a
‘‘oncethrough’’ option. Thus, it may not be
possible to recover catalyst for reuse. Low
cost, throw-away materials possessing
catalytic activity may be identified. In this
case, the once-through option may be more
attractive.
The properties of AR and VR feedstocks,
particularly content of metals and
asphaltenes, should be clearly established
above which hydroprocessing becomes less
attractive than carbon rejection methods.
coking of high metals and asphaltenes
heavy feeds may have more merit,
particularly if it is integrated with an
efficient utilization of petroleum coke.Concern
about
the solvent deasphalted could be an
important process. Therefore, separation of
asphaltene before hydroprocessing could
be an option to modify the process and one
step advance towards the deeper and
stricter environmental legislation as well as
catalyst stability.

33
hybrid schemes of fixed bed or Ebullated bed technologies with thermal processes,
may deserve more analysis from technical and economic point of view.
The integrated process indicates that once the asphaltene separated from the residue, the
deasphalted oil (DAO) is easier to process in hydroprocessing units. While the heavy asphalt
or pitch can be processed through thermal process using gasification to complete conversion,
which will produce synthesis gas (CH4, H2, CO) as a major products. Further depending on
the need of fuel oil, the synthesis gas may be converted into kerosene or gas oil pool by using
Fischer Tropsch synthesis and Isomerization processes.

34
Performance of Ebullated bed and slurry hydrocracking processes
Product slate of slurry hydrocracking (wt. %)

35
Conversion
Installation cost Re-used equipment Incremental cost Pay back period
Conversion Grass root
60% 112 MM$ 7 months
68 MM$ 84 MM$

36
1998 - 1999
Delayed Coking Low
Ranges from 10% /year to 24% / year Ranges from 30% /year to 38% / year
RFCC Middle
Residue
Hydrocracking
High
U.S. Gulf coast location
Stanford Research Institute (SRI)2000.

37
220,000 Barrels per day
crude oil price is between 16 to 24 $ / barrel
The coke price is taken conservatively as Zero $/ton (by using the current trade price of 20 $/ton, the Delayed coking option IRR is
improved by 3%).
The analysis includes the primary residue upgrading plant, plus the plant required to refine its products (for example additional
FCCU capacity).
The power price is taken as 5 cents/ KW.
IGCC has the largest capital cost, $ 800 Million of which is due to the power generation train. The annual operating cost is also the
highest ($ 150 Million).
IRR values are pre-tax ones and do not include the owner’s costs
(IRR) between 7 to 20%(AR HDS has the higher IRR, then IGCC and delayed coking).
For cheaper , heavier crude slates , the delayed coking and IGCC become more economically attractive , and also more
operationally flexible from the crude selection point of view.
The IRR is very sensitive to the atmospheric residue price, and each 1$ / barrel change of its price can change IRR by 2% to 8%(for
delayed coking).
Foster Wheeler Energy Limited, European Refining Technology Conference , Paris ,2002.

38Snamprogetti & Eni Technologie, 3rd. Bottom of the Barrel Technology Conference & Exhibition, Antwerp,(2004).
Comparison of four residue upgrading schemes

39
• 100,000 barrels per day grass roots crude oil processing (Arabian Heavy) in each of the plants studied.
• 3.50 $ / M Btu gas price
• product slate to liquid intermediate products and solids / pitch
• capital recovery at 15 % ROI
• US Gulf Coast location
• primary conversion unit about 20 % of total capital
• operating cost not including crude oil feedstock costs
Exxon Mobil Research & Engineering Co., AVS Resid Conversion, 2004.

40Axens North America Inc.& IFP-Lyon , 3rd. Bottom of the Barrel Technology Conference & Exhibition ,Antwerp,2004.
The projected global demand of refined products shows an appropriate situation for
the residue conversion processes construction, especially for hydro-processing ones.
There is a promising future for middle distillates and gasoline producing upgrading
processes.

41
there is a stability limit for the high conversion region of the Ebullated bed hydrocracking process.
due to the increasing natural gas prices , hydrogen production from residue , via gasification can be economical.
there is a balance point between the hydrogen consumption and production, which limits the residue conversion level (to e.g. 83 %).
Promoting of the slurry hydrocracking processes
Axens North America Inc.& IFP-Lyon , 3rd. Bottom of the Barrel Technology Conference & Exhibition ,Antwerp,2004.

42
Delayed Coker
heaviest,
contaminated
crude oils
Total conversion to Gasoil
– distillates – Lighter
Hydrocarbon -coke
the lowest capital
cost among high
conversion processes
Suitable flexibility
and for refineries
with coke export
can be an
interesting route
one-third of installed
residue upgrading
plants all over the
world
some of the liquid fuels
produced by delayed coking
should be intensely
hydrotreated.
Solvent de-
Asphalting
vacuum residue
feed and a
paraffinic solvent
(C3 , C4 , C5 or a
mixture of them)
De- Asphalted Oil (DAO)
(usually 35-75
vol.%) and a De-Oiled
Asphalt (DOA)
DAO is used as
hydrocracker, FCCU
feed or lube oil
blending agent.
Essential
pretreatment unit
The integrated
processing of delayed
coking and solvent de-
asphalting specially
developed supercritical
one has considerable
energy conservation.
DOA is a low value rich pitch
stream.
RFCC
heavy residue
especially AR
gasoline/diesel,
propylene or
petrochemicals
High value products High operating cost
Around 24% of the
global residue
upgrading capacity
it is driven by sweet crude
oil availability.
High olefin cons. of
products.
Visbreaking heavy residue
partially converted into
lighter hydrocarbons and
coke
by Hydro-visbreaking,
lower coke formation
and more stable
products, higher
conversions than
straight visbreaking
can be achieved.
Cost effective
conversion of
visbreaking into
delay coking unit.
About 26 % of the
global residue
upgrading capacity
low conversion of this
process and limited future
market for fuel oil and the
possibility of profitable
converting of visbreaking
into delayed coking process.
Gasification
Range of natural
gas to heaviest
high metals and
sulfur petroleum
or coal derived
pitches
Syngases for production
of power and steam,
petrochemicals,
Transportation fuels and
even hydrogen
Removing sulfur
easily by converting it
into H2S.
there is no need to
expensive refining
of heavy fuels.
it has been widely used
in petroleum refineries
and integrated
combined cycle power
generation plants
(IGCC).
Rarely, a feed with a price
higher than 10 $/barrel is
used for gasification.
Residue
Hydrocracking
Heavy residue high quality lighter fuels
Good quality
products make this
family of processes,
one of the best
options for residue
upgrading
Feedstock
flexibility, and
almost complete
conversion(slurry
mode)
about 17.5 % of the
residue upgrading
global capacity for
fixed bed category.
Deactivation of catalyst by
poisoning and coking
processes

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