PDVSA HDHPLUS® Process

Integrated Scheme with

Sequential Hydroprocessing

Elvis Castillo
14/11/2006
1
 HDHPLUS® Process

• HDHPLUS® is a slurry technology for deep

hydrocracking of heavy vacuum residues
(PDVSA ownership)
• Very high VR conversion level - up to or
more than 85% of the vacuum residue
• Intevep, Axens and IFP alliance for
• continuous improvements
• integration with Sequential Hydroprocessing
• worldwide marketing of integrated scheme
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 HDHPLUS® Main Features

• HDHPLUS® process can process heavy

refractory VR feeds regardless of sulfur,
metals, asphaltene and CCR contents (better
performance for high sulfur feeds)
• The HDHPLUS® process use a catalyst-
additive system at moderate pressure and
temperature

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 HDHPLUS® Main Features

• Catalyst: conventional catalytic metals

dispersed in the VR feed by the preparation of
catalytic emulsions
• Additive: solid material of different nature
prepared by simple grinding and/or thermal
treatment
• Particle size adjusted to reactor fluidynamic
• Controls foam formation promoting liquid phase
• Improves radial gas distribution

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 HDHPLUS® Main Features

• Thermal cracking of the heavy molecules into free

radicals
Rn-R1-R2 Rn-R1. + R2 . Endothermic

• Catalytic hydrogenation of the free radicals on the liquid

phase with the presence of dispersed catalyst
H2 H. + H .
Rn-R1. + H. Rn-R1 Exothermic

• Polymerization reactions can occur if H2 availability in

liquid phase is deficient, leading to coke production and
fouling:
Rn-R1. + Rn-R1. Rn--Rn Not desirable
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 HDHPLUS® Main Features

• HDHPLUS® Typical performance:

• VR Conversion: 85 – 92%
• Asphaltene conversion: 80 - 85%
• Low gas yields: 8 - 9 wt%
• Distillate yields over 100 vol% with HDHPLUS®
• Distillate yields over 110 vol% with integrated
hydrotreating/hydrocracking scheme
• Unconverted residue are solid flakes produced in
low quantities (< 10 wt% of VR feed).

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 HDHPLUS® Main Features

• HDHPLUS® Typical Operating Conditions:

• Total pressure, bar 180 – 200
• H2 partial pressure, bar 125 – 150
• Reaction temperature, °C 440 – 470
• Space velocity, hr-1 0.4 – 0.7
• H2 treat-gas ratio, Nm3/m3 600 - 700

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 HDHPLUS® Integrated Scheme

• Integration of HDHPLUS® with Sequential

HydroProcessing of primary hydrocracked
products
• SHP = MHC or high severity hydrocracking
• Production of on-specification products

VR HDHPLUS® SEP Euro V

SHP Product
H2 Quality
SR VGO
Catalyst Flakes
+ Additive
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 Integrated Scheme (HDHPLUS® + SHP)
Slurry Separation Sequential Fractionation
Hydroconversion Section Hydroprocessing Section

SR VGO
Recycle H2

FG
R1 R2 & LPG
HPS HDT HyK

Naphtha

Jet fuel
Vac VGO reused Diesel
in HDHPLUS®
Fresh H2 Additive Catalyst
+ Recycle H2 Emulsion VGO
Flakes
VR Feed
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 Integrated Scheme HDHPLUS® + SHP
Product Destinations

• LPG to sales
• Gasoline fraction  to Cat reformer
• Kerosene product  jet fuel pool
• Diesel product  diesel pool
• VGO product  FCC feed or lube base
• Residue product are solid flakes conveyed to
storage  solid fuel

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 Integrated Scheme HDHPLUS® + SHP
Product Destinations

• Solid Flakes produced by a conventional flaker

or equivalent solidification system
• Flakes: better properties than conventional pet
coke and can be marketable as pet coke, alone
or blended with pet coke (power generation and
cement industry are the preferable markets)
• Higher heating value (+10%)
• Lower sulfur
• Higher ash content

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 HDHPLUS® Development Stages

1983-1988 Development of HDH™ by Intevep in cooperation

with Veba Oel who developed VCC (Veba Combi
Cracking). Pilot plant 150 bpsd at Sholven-Germany

1988-1996 Engineering studies for commercial application

of HDH™ technology in Cardón Refinery

1998-2003 HDH™ improvement including the SHP Concept

(10 bpsd Pilot Plant) to generate HDHPLUS®
2004-2006 Integration with Axens for Puerto La Cruz and
El Palito deep conversion projects.
2006 Agreement Axens, Intevep, IFP and PDVSA for
improvement and marketing of integrated
scheme
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 HDHPLUS® Development Stages

Pilot Plant Objectives

HDH® PILOT PLANT 150 BPD Pilot plant:
[150BPD]  Fluid dynamics and
thermodynamic evaluation under
IN RUHR OEL REFINERY process conditions
 Heater evaluation (hi, fouling),
Heat of reaction evaluation
 Equipment evaluation (valve,
pumps, emergency systems etc)
 Integrated plant performance
(HDH®-SHP)
 Adiabatic reactors with
quenching system. Reactor
temperature control
 Information for commercial
design
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 HDHPLUS® Development Stages

Commercial Cold Model Pilot Plant Objectives

(Simón Bolívar University)
Diameter 2.5 m Commercial-size cold model
(Simón Bolívar University):
 Phase distribution study
 Liquid mixing evaluation
 Gas mass transfer evaluation
 Confirmation of fluid dynamic
scale-up

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 HDHPLUS® Development Stages

10 BPD Pilot Plant Pilot Plant Objectives

(PDVSA Intevep) 10 BPD Pilot plant (PDVSA
Intevep):
 Feedstock reactivity
 Yields and product quality
 H2 consumption
 Process stability
 Catalyst optimization
 SHP integration

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 HDHPLUS® Design Features

• Equipment design
• Pilot Plant experience incorporated in design
• Reactor Modeling from 0.3 m up to 2.5 m
diameter cold mock-ups experiments
• Standard equipment and metallurgy for the
entire HP section
• Cold Wall Reactors
• Hot Separator proven design (not entrainment)

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 HDHPLUS® Operability

• Operating procedures derived from Pilot

Plant experience
• Start-up, shut-down, emergency handling,
• Very stable operation controlled through the
gas velocity.
• Sedimentation and plugging control solved in
Pilot Plant and incorporated in design
• Strong reaction system that handles upsets
quickly without affecting the system stability
and the run length.

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 HDHPLUS® Case Study (1/4)
Feed Properties

• Heavy crude Vacuum Residue

• Specific Gravity 1.065
• Viscosity @150°C,cSt 2781
• Sulfur, wt% 4.47
• Nitrogen, wt% 1.013
• C7 Asphaltenes, wt% 16.0
• Conradson Carbon, wt% 25.1
• Nickel + Vanadium, ppm 894

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 Yields of HDHPLUS® Case Study (2/4)
Compared with Coker Yields

HDHPLUS® Coker
• Yield vs. VR Feed, vol%
• Naphtha 21.3 14.4
• Middle Distillates 51.2 38.0
• VGO 29.5 17.0
• Total liquid 102.0 69.4

• Yield vs. VR Feed, wt%

• H2S+NH3 4.0 1.4
• C1-C4 8.9 7.6
• Flakes (Coke) 7.5 32.9
• H2 consumption 2.3 0.0

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 HDHPLUS® Case Study (3/4)
Integrated Scheme HDHPLUS® + SHP Yields

• SHP Feed = HDHPLUS® effluent + SR VGO

• SHP in high severity hydrocracking mode

• Yields vs. SHP feed:

• Naphtha 31.2 vol%
• Middle Distillates 62.5 vol%
• VGO 17.1 vol%
• Total liquid 110.8 vol%
• H2 consumption 2.9 wt%
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 HDHPLUS® Case Study (4/4)
HDHPLUS® + SHP Product Properties (Euro V)

Heavy Naphtha Diesel

•Sp. Gr. 0.755 •Sp. Gr. 0.845
•Sulfur < 5 ppm •Sulfur < 10 ppm
•Nitrogen < 2 ppm •Cetane 55
 To cat reformer •Pour point < -25 °C
 To diesel pool

Kerosene Unconverted Oil

•Sp. Gr. 0.815 •Sp. Gr. 0.862
•Sulfur < 5 ppm •Sulfur < 50 ppm
•Smoke pt 23 mm •Nitrogen < 10 ppm
•Naphthalene < 1% vol •Hydrogen 13.5 wt%
 To Jet Fuel pool  FCC feed or base lube
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 PDVSA Puerto La Cruz Project
Integrated Scheme HDHPLUS® + SHP

• HDHPLUS® Unit
• 50 000 bpd of Merey VR
• VR Conversion: 85 - 92%
• Sequential Hydroprocessing Unit
• On-line high pressure HyK of a blend
• 51 000 bpd of HDHPLUS effluent
• + 47 000 bpd of SR VGO
• Conversion: 85 %
• Maximization of ULSD (S< 10 ppm, cetane> 51)
• Production of high quality Jet fuel
• Basic engineering in execution
• Start-up in 2011
• Investment $ 1.7 billion
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 PDVSA El Palito project
Integrated Scheme HDHPLUS® + SHP

• HDHPLUS® Unit:
• 46 000 bpsd of Merey-Mesa VR
• VR Conversion: 85 - 90%

• Sequential Hydroprocessing:
• On-line Mild Hydrocracking of a blend of:
• 44 000 bpsd of HDHPLUS
• + 44 000 bpsd of SR VGO
• Conversion 55%
• Production ULSD (S< 10 ppm, cetane> 45)
• Production of low Sulfur FCC feed

• Conceptual Engineering achieved

• Start-up in 2011
• Investment $ 1.8 billion
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 Conclusion

• HDHPLUS® is a slurry technology for deep

hydrocracking of heavy Vacuum Residues
• HDHPLUS® / SHP integrated scheme
technology enables:
• High conversion > 85% of heavy VR feeds
• Production of Euro V quality products
• Full research and development stages can
assure a successful commercial operation.
• Two commercial projects in progress in
Venezuela
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