HYDROTREATING/ HYDROPROCESSING OF NEW GENERATION CATALYSTS Dr. G. VALAVARASU Deputy Manager (R&D) Chennai Petroleum Corp. Ltd.

SimplifiedFlowSchemeofanOilRefinerywithPossibleLocationsof Hydrotreating Units

Why Hydrotreating/ Hydroprocessing?

Refiners are faced with the need to convert heavy components of crude barrel into lighter, more valuable products. This situation is due to the following:

Increasingly heavier crudes with high impurity levels (sulfur, nitrogen, metals etc) Lower demand for heavy fuel oils Increasing market demand for gasoline, middle distillates (Jet fuel, kerosene and diesel) Environmental pressure to upgrade the quality of petroleum fractions (Especially diesel and gasoline) Improved engine designs requiring high quality fuels (high octane gasoline, high cetane diesel)

Hydrotreating/ Hydroprocessing plays a pivotal role to meet the multiple challenges faced by todays refining industry.

SPECIFICATIONS OF DIESEL

Characteristics Density at 15oC, kg/m3 Kinematic Viscosity at 40oC, cSt Flash Point, oC Pour Point, oC, max., Winter Summer Cetane Number, min Cetane Index, min RCR on 10% Residue, max. Total Sulfur, wt.%, max. Polycyclic Aromatic Hydrocarbon (PAH), wt.%, max. Distillation, 85 vol.% Recovery at oC, max. Distillation, 95 vol.% Recovery at oC, max.

Euro- III

Euro-IV

Bharat-II

BharatIII 820-845 2.0-4.5 35 3 15 51 46 0.3 0.035 11 360

Bharat IV 820-845 2.0-4.5 35 51 48 0.3 0.005 11 360

820-845 2.0-4.5 55 51 46 0.3 0.035 11 360

51 0.005 11 360

820-860 2.0-5.0 35 3 15 48 0.3 0.05 350 370

SPECIFICATIONS OF GASOLINE

Characteristics Density @ 15oC, gm/cc RON, Min MON, Min Sulfur, wt.%, max.

Bharat-II

Euro III/ Bharat- Euro IV/ Bharat III IV 0.720-0.775 91 81 0.015 0.720-0.775 91 81 0.005

0.710-0.770 88 0.05

Benzene content, vol.%, max. Olefin content, vol.%, max. Aromatics content, vol.%, max.

3.0 -

1 21 42

1.0 21 35

Diesel Specifications Need for Improvement

Compound Sulfur Harmful Effects Increases emissions of SOx and nonmethane HC Can lead to corrosion and wear of engine systems and thus decreases relative engine life Contributes to fine particulate emissions Affects efficiency of exhaust after-treatment systems by sulfur poisoning Affect combustion and the formation of particulates and PAH emissions Influences flame temperature and NOx emissions Increases engine deposits Increases tailpipe emissions Affects formation of particulates in the exhaust Increases PAH emissions

Aromatics

PAH

Diesel Specifications Need for Improvement

Compound Cetane No Harmful Effects Decreases engine crank time at a given engine speed Reduces NOx, HC and CO emissions Reduces fuel consumption Reduces combustion noise

Density and Reduces particulate emissions Viscosity Reduces particulate and NOx emissions from heavy duty engines Increases fuel consumption and reduces power output Reduces CO2 emissions T95 Reduces coking, tailpine emissions of soot/smoke/PM Reduces NOx emissions Reduces particulate matter

Gasoline Specifications Need for Improvement

Compound Sulfur Harmful Effects Increases emissions of SOx and HC Poisons the catalyst in catalytic converter and thus reduces its efficiency Affects ignition time and temperature and hence reductions its efficiency across full range of air/fuel ratios Lead to deposit formation and increased emissions of reactive (ozoneforming) hydrocarbons and toxic compounds Thermally unstable and lead to gum formation and deposits in the engines fuel intake system Increases engine deposits and tailpipe emissions including CO2 Affects deposit formation, particularly in combustion chamber Produces carcinogenic benzene in exhaust gas due to combustion A human carcinogen Specification on Benzene in gasoline is the most direct way to limit evaporative and exhaust emissions of benzene from automobiles

Olefins

Aromatics

Benzene

Gasoline Specifications Need for Improvement

Compound Octane Volatility Harmful Effects Affects fuel consumption, drivability and power Increases vapour locking Increases evaporative emissions Affects ease of starting and good warm-up performance Improves starting and warm-up performance Affects vapour lock index

T50

Salient Aspects of Hydrotreating/ Hydroprocessing

Hydroprocessing technology could upgrade the heavy components of crude oil apart from improving the quality of fuels Hydroprocessing includes a variety of technologies to fulfill the following objectives: - Removal of heteroatoms (S, N, metals etc.) - Saturation of unsaturated hydrocarbons - Cracking of heavy hydrocarbons Hydrotreating is a catalytic reaction takes place in the presence of hydrogen at elevated temperature and pressure

Classification of Hydroprocessing

Hydroprocessing

Hydrocracking

Mild Hydrocracking

Hydrotreatment

Hydrodesulfurisation Fuels Lube Hydrodemetalisation

Lube/Wax Hydrofinishing Hydrodenitrogenation

Distillate

Resid

Hydrogenation

Hydroisomerisation

Industrial Applications of Hydrotreating

Naphtha Hydrotreating
Pretreatment of reformer feed for removal of sulfur, metals Selective desulfurization from FCC gasoline

Hydrotreatment of Pyrolysis Gasoline - Desulfurization and selective hydrogenation

Kerosene/ Jet fuel Hydrotreating - Desulfurization and Denitrogenation - Aromatic & Olefin saturation

Diesel Hydrotreating
- Desulfurization and Denitrogenation - Aromatic & Olefin saturation - Hydrodewaxing

Industrial Applications of Hydrotreating

Lube Oil/ Wax Hydrotreating Vacuum Gas Oil Hydrotreating - Desulfurization - Denitrogenation - Demetallisation - Hydrogenation - Reduction of CCR

Residue Hydrotreating - Desulfurization - Denitrogenation - Demetallisation - Saturation - Reduction of CCR - Partial Cracking

Hydrotreating Reactions Desirable Reactions

Hydrodesulfurization (HDS) Hydrodenitrogenation (HDN) Hydrodeoxygenation (HDO) Hydrodearomatization (HDA) Saturation of olefins Hydrodemetallation (HDM)

Undesirable Reactions
Hydrocracking Coking

Hydrodesulfurization
Mercaptans, sulfides and disulfides are easiest to remove and converted to corresponding saturated or aromatic compounds and H2S Sulfur combined into cycles of aromatic structure such as thiophenes, benzothiophenes, dibenzothiophenes and substituted dibenzothiophenes are more difficult to desulfurize Exothermic reaction Consumes hydrogen

+ 6 H2

H2S

Benzothiophene

TypicalSulfurCompoundsPresentinFuels
Fuel Boiling Range in oC 25-225 Sulfur Compounds

Gasoline

Mercaptanes (RSH), Sulfides (R2S), Disulfides (RSSR), Thiophene and its alkylated derivatives, benzothiophene

Jet Fuel/ Kerosene Diesel Fuel

130-300

Mercaptanes, Benzothiophene, alkylated benzothiophenes Alkylated benzothiophenes , dibenzothiophenes, alkylated dibenzothiophenes

160-380

Hydrodenitrogenation
Nitrogen compounds are removed as ammonia Slower reaction than HDS Exothermic reaction Consumes hydrogen

+ 7 H2 N R Quinoline

NH3

Hydrodeoxygenation
Fatty acids, naphthenic acids, alcohols, aldehydes and phenols are some are the organic nitrogen compounds present in fractions Organic oxygen compounds are removed as water Water is later removed during stripping Exothermic reaction Consumes hydrogen
OH + H2 R R + H2O

Hydrodearomatization
Thermodynamic equilibrium limited Exothermic and the number of molecules decreases Favored by low temperature and high pressure

Polyaromatics Hydrogenation
+ 2 H2 + 3 H2

Naphthalene

Tetralin

Decalin

Monoaromatics Hydrogenation
R R + 3 H2

Saturation of Olefins
Olefins are not found in straight run fractions, but present in cracked stocks Very rapid reaction Highly exothermic Consumes hydrogen

Hydrodemetallation
Metals present as organo metallic compounds Nickel and Vanadium compounds in crude oil concentrated in residue Metals are adsorbed on the catalyst during hydrotreating Results in catalyst deactivation and shortening of catalyst life

M-porphyrin

H2 (H2S)

MxSy + H-porphyrin

Hydrocracking
Undesirable side reaction during hydrotreating Breaking of longer hydrocarbons into shorter molecules in presence of hydrogen Consumes hydrogen Reduces product yield High temperature favors higher hydrocracking reaction

CnH2n+2

CmH2m+2 +

CpH2p+2 [m+p= n]

Coking
Heavy molecules adsorbed on catalyst sites condense and polymerize to form carbonaceous deposit called coke Coke is more than 90% carbon Reduces the catalyst activity by depositing on active sites Regeneration of catalyst restores the original activity Low temperature and high hydrogen pressure reduces coking reactions

+ Olefins Polyaromatics Alkylation

- H2

Cyclization

- H2

Coke Precursors

Hydrotreating Process Schematic

Process Variables
Reactor Temperature Reactor temperature is an important operating variable to control HDT reactions Should be kept at optimum levels to limit undesirable reactions Hydrogen Partial Pressure - Results from operating pressure, hydrogen make-up and recycle rates and purity Higher pressure favors desirable reactions (HDS and hydrogenation) and decreases undesirable reactions (Hydrocracking and coking) Liquid Hourly Space Velocity Important process variable to control HDT reactions Ratio of liquid feed rate to catalyst volume Lower LHSV favors desirable reactions H2/Oil Ratio - Fixed considering the stability and life of catalyst

TypicalHydrotreatingConditionsofVariousStreams
Refinery Stream Temperature, deg C Pressure, kg/cm2 LHSV, h-1 H2/Oil Ratio, m3/m3

Naphtha Jet Fuel/ Kerosene Diesel Vacuum Gas Oil Residue/ Fuel Oil

290-370 315-360

14-40 20-40

2-6 1-3

50-150 100-250

315-400 370-425

30-100 50-150

0.5-2 0.5-2

150-300 200-500

380-450

80-200

0.5-1.5

200-800

Hydrotreating Catalysts
Catalysts play an important role in hydrotreating by means of enhancing the rate of specific reactions Group VI B metals (chromium, molybdenum and tungsten) are active for desulfurization, especially when promoted with metals from Group VIII (cobalt, nickel etc.) The catalysts are usually supported on high surface area alumina (100-300 m2/g)

Hydrotreating Catalysts CoO-MoO3/ Al2O3 and NiO-MoO3/ Al2O3 are the commonly used catalysts NiW / Al2O3 is used for special applications Molybdenum or tungsten is the active desulfurization component Nickel or cobalt act as a promoter to increase catalyst activity In certain applications such as aromatic saturation and cetane improvement, supported noble metals (Pt/ Pd) are employed in pure reaction environment

Activity Ranking of Sulfides and Sulfide Couples of Group VI-B and Group VIII metals
The various pairs of non-noble metal sulfides that are possible, do not have the same activity for various conversions. The ranking of sulfides and sulfide couples of metals by order of activity is illustrated in the following table:
Hydrogenation of aromatics and olefins Metals in zero valent state: Pt > Rh > Ni > Pd >Co (Aromatics) Rh > Pd >Pt >Ni > Co (Olefins) Pure sulfides: Mo > W >>Ni >Co Sulfur Pairs at optimum: Ni-W > Ni-Mo > Co-Mo > Co-W Pure sulfides: Mo > W >> Ni > Co Sulfide Pairs at optimum: Co-Mo > Ni-Mo > Ni-W > Co-W Pure sulfides: Mo > W > Ni > Co Sulfide Pairs at optimum: Ni-Mo = Ni-W > Co-Mo > Co-W

Hydrodesulfurization

Hydrodenitrogenation

Chemical Composition of the Active Components

Chemical composition plays a crucial role in determining the overall activity of the catalyst. For optimum conversions, the ratios of Group VI-B to Group VIII metals are always in the range of 0.25 0.40. Concentration by wt. of the metals is usually as follows: Co, Ni : 1 4 % Mo W : 8 25 % : 12 25 %

Catalyst Activation
Hydrotreating catalysts are supplied in oxide form and these catalysts have to be activated before the start of the process. The active state of these catalysts which are mostly Mo, W, Ni, Co or a combination of these metals on alumina support is in the form of sulfides. Sulfiding of the catalyst is done as the activation step in the start-up procedure (In-situ presulfiding) Sulfiding is performed in the presence of liquid agents such as DMDS or with hydrogen sulfide gas Sulfidation is an exothermic process and therefore the procedure employed has a significant influence on the type of active sites generated and thereby on the catalyst activity and stability.

TypicalShapesofHydrotreatingCatalystParticles

TypicalPropertiesofHydrotreatingCatalysts
Property Physical Properties Shape Diameter, mm Length, mm Surface area, m2/g Pore volume, ml/g Bulk density, kg/m3 Chemical Properties MoO3, wt% NiO, wt% P, wt% Na2O, wt% 20.5 2.35 1.35 0.05 22.8 4.5 0.9 Extrudate Trilobe 2.5 6.1 176 0.51 750 Extrudate Trilobe 2.2 5.8 245 0.39 850 CoMo NiMo

Diesel Quality Improvements Challenges

Deepdesulfurization Increase of Cetane number Reduction of T95 Reduction of PAH

ReactivityofVariousOrganicSulfurCompoundsversustheirring sizesandpositions ofalkylsubstitutionsonthering(SongC.,CatalysisToday)

The different types of S compounds in distillates

Typical S compounds Approximate content (ppm) in SR diesel Sulfides; disulfides Benzothiophenes (alkyl) (I) Non-beta-substituted dibenzothiophenes (II) Mono-beta substituted dibenzothiophenes (III) Di-beta-substituted dibenzothiophenes (IV) Other ring S-compounds 5500 2800 Moderate 600 900 Difficult 1500 2300 Moderate 5000 1700 1000 Cracked diesel 300 7300 1900 Reactivity over HDS catalysts. Moderate Very easy Easy

Typical structures of the benzothiophene compounds:

R R (I) S R S (II) R R R (III) S R R R (IV) S R R

Why is it difficult to desulfurize diesel to 50 ppm or less? Due to the presence of sterically hindered S-compounds that cannot adsorb easily on the CUS sites.
Relative reactivity of different S compounds over HDS catalysts

[Mobil, 1996]

Schematic representation of the steric effect of methyl groups on adsorption of 4,6-DMDBT at CUS sites

Slow Reaction Adsorption Difficult

S
CH 3 DM DBT CH 3
CH 3

S
CH 3

Fast Reaction Adsorption Easy

S
DBT

Experiments carried out with pure 4,6-DMDBT suggest that it undergoes transformation in three different ways over the complex catalysts:

S R Dealkylation R H2

S R -H2S Direct

S R

-H2S

-H2S

Diesel feed; 15,000 ppm

Me DBT Alkyl BT DBT D B T

4,6 DMDBT 4,6 DMDBT

DMDBT

Deep HDS
Alk. DMDBT

40 ppm S
Alk. DMDBT

2500 ppm S
4,Me DBT 4,6 DMDBT

HDS

DMDBT

PFPD analysis of S compounds in different diesel oils

TECHNOLOGICAL OPTIONS TO IMPROVE THE QUALITY OF DIESEL

Getting the most of existing units
Higher Reactor Temperature Reducing Throughputs Increasing Hydrogen Partial Pressure Reducing Hydrogen sulfide Partial Pressure Increasing H2/Oil ratio Improved Reactor Internals

Additional Reactor Volumes Catalyst Options New Technologies

TECHNOLOGICAL OPTIONS TO IMPROVE THE QUALITY OF DIESEL

Getting the most of existing units
Higher Reactor Temperature Reducing Throughputs Increasing Hydrogen Partial Pressure Reducing Hydrogen sulfide Partial Pressure Increasing H2/Oil ratio Improved Reactor Internals

Additional Reactor Volumes Catalyst Options New Technologies

TECHNOLOGICAL OPTIONS TO IMPROVE THE QUALITY OF DIESEL

Getting the most of existing units
Higher Reactor Temperature Reducing Throughputs Increasing Hydrogen Partial Pressure Reducing Hydrogen sulfide Partial Pressure Increasing H2/Oil ratio Improved Reactor Internals Development of new generation high activity HDS catalysts
Albermale STARS, NEBULA etc. Criterion CENTINEL Haldor Topsoe Trimetallic Nanoparticulate catalysts

Additional Reactor Volumes Catalyst Options New Technologies

ROLE OF R&D IN CLEAN FUELS PROGRAM

Pilot plant evaluation of various feedstocks - diesel, gasoline, kerosene and lube oil base stocks Catalyst selection for various applications from pilot plant data Optimization of operating parameters (Temperature, pressure, LHSV and H2/oil ratio etc) Data generation for kinetic modeling and simulation of DHDS, catalytic reformer and hydrocracker units

R&D HYDROPROCESSING FACILITIES Hydrotreating Pilot Plant High Pressure Reactor System Catalytic Reformer Micro Reactor Unit Parr Autoclave Reactor

HYDROTREATING PILOT PLANT

Procured from Xytel India pvt limited, Pune during 1998 Designed for temperatures upto 550oC and pressures upto 250 kg/cm2 Two reactors in series with 500 ml volume each 5 zone electric furnace to maintain isothermal temperature profile Liquid Flow Rate up to 6 lit/h H2 Rate 600 SLPH Hydrotreating/Hydrocracking/Isodewaxing studies can be carried out in the unit using different catalysts and feedstock

HYDROTREATING PILOT PLANT

HIGH PRESSURE REACTOR SYSTEM

Procured from Vinci Technologies, France during 1993 Designed for temperatures up to 600oC and pressures up to 300 kg/cm2 Single reactor with 500 ml volume 4 zone split type electric furnace to maintain isothermal temperature profile Liquid Flow Rate up to 600 ml/h H2 Rate 30 - 300 SLPH Hydrotreating/ Isodewaxing studies can be carried out in the unit using different catalysts and feedstock

HIGH PRESSURE REACTOR SYSTEM

R&D ACTIVITIES HDS OF DIESEL

Pilot plant evaluation of different new generation high activity catalysts for DHDS application to generate base data on their performance. These data will be useful during catalyst change over in DHDS unit Evaluation of indigenous DHDS catalyst samples Evaluation of different process technologies for the selection of suitable technology for DHDS or other applications Generation of kinetic data for various HDT reactions

New Generation Hydrotreating Catalysts A Case Study

CPCL has a DHDS unit with a capacity of 1.85 MMTPA to produce Bharat II and Bharat III diesel. The unit has two reactors in series For producing Euro IV diesel meeting 50 ppmw sulfur, it was decided to add additional high volume reactor in the existing unit with investment cost more than 100 crores Suggestion from CPCL R&D was sought from Dev./ PE

New Generation Hydrotreating Catalysts A Case Study

CPCL R&D suggested the use of high activity catalyst in the existing unit in place of additional reactor facility to meet Euro IV diesel sulfur spec. CPCL R&D generates data base on new high activity HDT catalysts as part of its pilot plant evaluations By utilization of this data base on different new generation catalysts along with the use of in-house developed process model, CPCL R&D suggested the possibility of producing 50 ppmw sulfur in diesel by catalyst change over instead of opting new reactor with high investment cost.

Differences between Pilot Plant and Industrial Trickle Bed Reactors

Industrial Reactor

Pilot Plant Reactor

Length Diameter Gas Velocity Liquid Velocity Wetting Flow Regime Axial Dispersion Catalyst Irrigation Mass Transfer Channeling and Wall Effects Mode of Operation

10 25 m 14m 14.8 2200 cm/s 0.8 2.5 cm/s Complete Trickle/Slug Flow Negligible Very Good Very Good Negligible Non-Isothermal

0.5 2.0 m 0.5 4.0 cm 1.48 220 cm/s 0.08 0.25 cm/s Partial Trickle Significant in some cases Poor Poor Significant Isothermal

Schematic Diagram of of Pilot Plant Reactor

Schematic Diagram of Trickle Bed Reactor Model

Gas Phase: (For Pilot Plant Reactor Simulation Where 0 mm z 900 mm)

dPH 2 dz

PH RT l l k H2 a p 2 CH2 HH uG 2 = PH S RT l l k H 2S a p 2 C H 2S HH S uG 2

(A 1.1)

dPH 2 S dz dP 3 NH dz

(A 1.2)

PNH RT l l k NH3 a p 3 CNH3 HNH uG 3

(A 1.3)

P dP RT l HC l = kHCa p HC CHC H dz uG HC

(A 1.4)

Liquid Phase: For reactive zones (For Pilot Plant Reactor Simulation Where 250 mm z 700 mm)

l dC H 2

dz
l dC H 2 S

PH 1 l l s l s k H2 a p 2 CH2 + k H2 as CH2 CH2 HH uL 2

)} )}

(A 1.9)

dz
l dC NH 3

PH S 1 l l s l s k H 2S a p 2 C H 2S + k H 2S as C H 2S C H 2S HH S uL 2

(A 1.10)

dz

PNH 3 1 l l s l s k NH 3 a p C NH 3 k NH 3 a s C NH 3 C NH 3 H NH uL 3

)}

(A 1.11)

l dC S 1 s l s = k S as CS CS dz uL l dC N 1 s l s = kN CN CN dz uL

(A 1.12)

) ) ) ) )

(A 1.13)

l dC O 1 s l s = k O a s CO CO dz uL

(A 1.14)

l dC GO 1 s l s = k GO C GO C GO dz uL l dCWN 1 s l s = kWN CWN CWN dz uL l dC HC 1 s l s = k HC C HC C HC dz uL

(A 1.15)

(A 1.16)

(A 1.17)

l dC Poly

dz

1 s l s k Poly C Poly C Poly uL

(A 1.18)

l dC Di 1 s l s = k Di (C Di C Di ) dz uL l dC Mono 1 s l s = k Mono (C Mono C Mono ) dz uL

l dC Naph

(A 1.19)

(A 1.20)

dz

1 s l s k Naph C Naph C Naph uL

) )
(A 1.21)

l dC Mono 1 s l s k Mono C Mono C Mono = = dz uL

Heat Balance Equation: (For Industrial Reactor Simulation Operated Under Non-Isothermal Conditions)

uL C p

dTR = rS ( H S ) + rN ( H N ) + rO ( H O ) + rGO ( H GO ) dz rPoly ( H Poly ) + rDi ( H Di ) + rMon ( H Mono )

(A 1.22)

Across Liquid-Solid Interface:

3 s l s k H 2 a s C H 2 C H 2 = B rS + rN + rPoly + 2rDi + 3rMono + rGO + rWN + rHC + rO 2

(A 1.23)
s l s k S a s C S C S = B rS

(A 1.24) (A 1.25) (A 1.26) (A 1.27)

(A 1.28) (A 1.29) (A 1.30) (A 1.31) (A 1.32)

s l s k H 2 S a s C H 2 S C H 2 S = B rS s l s k N a s C N C N = B rN

3 s l s k NH 3 a s C NH 3 C NH 3 = B rN 2
s l s k O a s C O C O = B rO s l s k H 2O a s C H 2O C H 2O = B rO s k GO s kWN s k HC l GO l WN l HC s C GO = B rGO s CWN s C HC

(
s

( a (C a (C a (C
s s

) ) = r ) = r
B B

WN

HC

s l s k Poly a s C Poly C Poly = B rPoly s l s k Di a s C Di C Di = B rDi s l s k Mono a s C Mono C Mono = B rMono s k Naph l Naph s C Naph

(A 1.33) (A 1.34) (A 1.35) (A 1.36)

( a (C
s

) )=

rNaph

Kinetic Equations Based on Surface Concentrations of Reactants:

rS = k app , S

(C ) (C ) (1 + k C )
s m1 S ad s N

m2 s H2 2 s H 2S

(A 1.37) (A 1.38) (A 1.39) (A 1.40) (A 1.41) (A 1.42) (A 1.43) (A 1.44) (A 1.45)

rN = k kapp , N C
s rO = k app ,O C O

s rGO = (k1 + k 2 )C GO s s rWN = k 2 C GO + k 3 CWN s s rHC = k1C GO k 3 CWN s s rPoly = k Poly C Poly k Poly C Di s s rDi = k Di C Di k Di C Mono s s rMono = k Mono C Mono k Mono C Naph

Initial Conditions for the Simulation of Pilot Plant and Industrial Trickle Bed Reactor
PH 2 = PH 2 , 0 PH 2 S = PH 2 S ,0 PNH 3 = PNH 3 ,0 PH 2O = PH 2O ,0 P = P HC , 0 HC l l C H 2 = C H 2 ,0 l l C H 2S = C H 2S ,0 l l C NH 3 = C NH 3 , 0 l l C H 2O = C H 2O , 0 l l C HC = C HC ,0 C l = C l S ,0 S l l C N = C N ,0 l l CO = CO ,0 l l C GO = C GO , 0 l l CWN = CWN ,0 C l = C l Poly , 0 Poly C l = C l Di , 0 Di l l C Mono = C Mono,0 l l C Naph = C Naph ,0 T = T R ,0 R

At Reactor Inlet: PH 2 = PH 2 , 0 PH 2 S = PH 2 S ,0 PNH 3 = PNH 3 ,0 PH 2O = PH 2O ,0 P = P HC , 0 HC l l C H 2 = C H 2 ,0 l l C H 2S = C H 2S ,0 l l C NH 3 = C NH 3 ,0 l l C H 2O = C H 2O , 0 l l C HC = C HC , 0 C l = C l S ,0 S l l C N = C N ,0 l l CO = CO,0 l l C GO = C GO ,0 l l CWN = CWN ,0 C l = C l Poly , 0 Poly C l = C l Di , 0 Di l l C Mono = C Mono,0 l l C Naph = C Naph , 0 T = T R ,0 R

At Reactor Outlet:
PH 2 = PH 2 , p PH 2 S = PH 2 S , p PNH 3 = PNH 3 , p PH 2 O = PH 2 O , p P = P HC , p HC l l CH = CH , p 2 2 l l CH 2 S = CH 2 S , p l l C NH 3 = C NH 3 , p l l CH 2 O = CH 2 O , p l l CHC = CHC , 0 Cl = Cl S, p S l l CN = CN , p l l CO = CO , p l l CGO = CGO , p l l CWN = CWN , p l l CPoly = CPoly , p Cl = Cl Di , p Di Cl = Cl Mono , p Mono l l C Naph = C Naph , p T = T R, p R

Properties of Diesel Feedstock

Property Density at 15 oC, gm/cc Viscosity at 40 oC, cSt Pour Point, oC Aniline Point, oC Flash Point, oC Rams Bottom Carbon Residue, wt.% Sulfur, wt.% Nitrogen, ppmw Olefins, wt.% Total Aromatics, wt.% Polyaromatics, wt.% Diaromatics, wt.% Monoaromatics, wt.% Total Saturates, wt.% Naphthenes, wt.% Paraffins, wt.% Value 0.8575 3.90 0 71 118 0.1221 1.11 120 6.1 37.40 3.50 10.10 23.80 62.60 19.25 43.35

ASTM D-86 Distillation IBP, oC 5 vol.%, oC 10 vol.%, oC 20 vol.%, oC 30 vol.%, oC 50 vol.%, oC 70 vol.%, oC 80 vol.%, oC 90 vol.%, oC FBP, oC 164 234 247 264 275 294 316 331 350 370

0.30 TR - 320 C 0.25 TR - 340 C TR - 360 C Sulphur, wt.% 0.20

o o o

Catalyst - A

0.15

0.10

0.05

0.00 0.5 1.0 1.5 LHSV, h1

2.0

2.5

3.0

Experimental Data on the Effect of Liquid Hourly Space Velocity on Product Sulphur - Catalyst-A

0.30 Catalyst - A 0.25 LHSV - 1.0 h

-1 -1 -1 -1

LHSV - 1.5 h LHSV - 2.0 h LHSV - 2.5 h

0.20 Sulphur, wt.%

0.15

0.10

0.05

0.00 310 320 330 340 350

o

360

370

Reactor Temperature, TR, C

Experimental Data on the Effect of Reactor Temperature on Product Sulphur - Catalyst-A

23 m3 17 m3 40 m3 135 m3

Schematic Diagram of Industrial Trickle Bed Reactors

Simulation of Industrial Reactors - Model Prediction vs. Operating Data

Parameter Reactor Pressure, kg/cm2 H2/oil Ratio Feed Rate, m3/h Reactor Temperature, oC Concetration in Reactor outlet: Sulfur, wt.% Nitrogen, ppmw Olefins, wt.% Polyaromatics, wt.% Diaromatics, wt.% Monoaromatics, wt.% Naphthenes, wt.% Wild Naphtha, wt.% Light Hydrocarbons, wt.%

Industrial Reactor Operating Point 44 160 270 340 0.0145 38 3.0 1.1 6.0 26.6 19.5 0.9 0.1

Model Prediction

% Deviation

44 160 270 340 0.0156 42 3.01 1.01 6.22 26.56 19.29 0.85 0.11

-7.58 -10.53 -0.33 8.18 -3.66 0.15 0.15 5.55 -10.00

Performance Prediction of Industrial Reactors with Catalyst-A and Catalyst-C: Effect of Reactor Temperature on Product Quality

Reactor Temperature, oC 290 Reactor Pressure, kg/cm2 H2/oil Ratio Feed Rate, m3/h Concetration in Reactor outlet: Sulfur, wt.% Nitrogen, ppmw Olefins, wt.% Polyaromatics, wt.% Diaromatics, wt.% Monoaromatics, wt.% Naphthenes, wt.% Wild Naphtha, wt.% Light Hydrocarbons, wt.% 44 160 270 0.0939 66 3.61 1.46 6.87 26.09 19.28 0.73 0.06 310 44 160 270 0.0383 55 3.33 0.84 5.37 27.02 19.30 0.79 0.08 330 44 160 270 0.0115 44 3.06 0.74 5.11 27.15 19.31 0.85 0.11 350 44 160 270 0.0035 34 2.79 1.50 7.99 25.49 19.29 0.89 0.14

Case 1: Catalyst-A in Reactor 1 and Catalyst-C in Reactor 2.

Performance Prediction of Industrial Reactors with Catalyst-A and Catalyst-D: Effect of Reactor Temperature on Product Quality
Reactor Temperature, oC 290 Reactor Pressure, kg/cm2 H2/oil Ratio Feed Rate, m3/h Concetration in Reactor outlet: Sulfur, wt.% Nitrogen, ppmw Olefins, wt.% Polyaromatics, wt.% Diaromatics, wt.% Monoaromatics, wt.% Naphthenes, wt.% Wild Naphtha, wt.% Light Hydrocarbons, wt.% 44 160 270 0.1935 68 3.58 1.35 6.52 26.26 19.28 0.72 0.06 310 44 160 270 0.0435 57 3.30 0.78 5.08 27.14 19.31 0.78 0.08 330 44 160 270 0.0158 46 3.03 0.71 4.95 27.23 19.32 0.84 0.10 350 44 160 270 0.0058 35 2.76 1.49 7.96 25.50 19.29 0.88 0.13

Case 1: Catalyst-A in Reactor 1 and Catalyst-C in Reactor 2.

0.06 TR - 330 C 0.05 0.04 0.03 0.02 0.01 0.00 200 220 240 260 280
3 o o o

TR - 340 C TR - 350 C Industrial Reactor Operating Point

Reactor 1 - Catalyst A Reactor 2 - Catalyst B

Sulphur, wt.%

300

320

340

Feed Rate, m /h Simulation of Industrial Trickle Bed Reactor Effect of Feed Rate on Product Sulphur

0.12 Feed Rate - 250 m /h Feed Rate - 270 m /h Industrial Reactor Operating Point 0.08 Sulphur, wt.%
3 3

0.10

0.06

0.04 Reactor 1 - Catalyst A Reactor 2 - Catalyst B

0.02

0.00 300 310 320 330 340 350 360 Reactor Temperature, TR, oC

Simulation of Industrial Trickle Bed Reactor - Effect of Reactor Temperature on Product Sulphur

360 358 356 354 352

Temperature, C

350 348 346 344 342 340 338 336 332 330 0 50 100 150 200

Reactor 1 Reactor 1 Reactor 1 334 Bed 3 Bed 1 Bed 2

Reactor 2 Bed 1

Temperature Profile of Industrial Trickle Bed Reactor System - Simulated

New Generation Hydrotreating Catalysts A Case Study

Simulations showed the possibility of producing diesel with < 50 ppmw sulfur in existing DHDS unit Based on R&D suggestion, it was decided to go for competitive bidding for selection of suitable high activity catalyst Three catalyst samples supplied by different vendors evaluated in pilot plant for their activity Based on catalyst activity, Grace Catalyst system was chosen for the unit The unit is running successfully for more than 3 years with production of < 50 ppmw sulfur

TECHNOLOGICAL OPTIONS TO IMPROVE THE QUALITY OF DIESEL

Getting the most of existing units
Higher Reactor Temperature Reducing Throughputs Increasing Hydrogen Partial Pressure Reducing Hydrogen sulfide Partial Pressure Increasing H2/Oil ratio Improved Reactor Internals

Additional Reactor Volumes Catalyst Options New Technologies

TECHNOLOGICAL OPTIONS TO IMPROVE THE QUALITY OF DIESEL

Recently Commercialized Processes
MAKFining Premium Distillates Technology
Mobil, Akzo Nobel, Kellog and Total Fina

Novel Processes/Technologies
Selective Adsorption
SARS by PSU

Reactive Adsorption
S-Zorb by Philips Petroleum

SYN Technologies
ABB Lummus, Criterion and Shell Global Solutions

Oxidative Desulfurization
ASR by Unipure

MQD Unionfining - UOP Prime-D Technology - Axens

Biodesulfurization
Energy Biosystems

SynSat/SynShift Process:
Uses catalysts developed by Criterion Counter current flows of gas and liquid streams Inter stage stripper to separate gas and liquid products SynHDS for ultra deep HDS SynSat/SynShift for Cetane Improvement, Aromatic saturation and T95 improvement

MQD Unionfining Process

Based on multifunctional catalysts optimized to achieve varied product qualities Latest HDS catalysts for ultra deep HDS AS-250 catalyst for aromatic saturation HC-80 and DW-10 catalysts for PP improvement

SARS-HDSCS Process
Being developed at PSU Couples selective adsorption of organic sulfur compounds with HDS More efficient for ULSD Consumes less H2

ASR-2 Process
Produces ultra low sulfur fuels ( < 10 pppm) from a feed sulfur of 1500 ppm (announced both for Gasoline and Diesel) Based on oxidation chemistry and reactions are carried out at lower temperature (100oC) and pressure (just enough to contain the vapour) Uses H2O2 (oxidizing agent) and organic acid catalyst to convert sulfur compounds to sulfones Does not require H2 and fired heaters

Thank you