Diesel Hydrotreating and VGO Hydrocracking M PRAMANIK General Manager, Indian Oil Corporation Ltd.

Paradip Refinery

Agenda 1. Introduction 2. Chemistry 3. Chemical reactions 3. Feed Specification 4. Process description 5. Product Characteristics 6. Catalyst 7. Special Feature/Internals

Diesel Hydrotreating and VGO Hydrocracking

In today's scenario, hydro processing involves a major role for meeting. The quality specification of refinery products Increasing refinery margin.

Diesel Hydrotreating and VGO Hydrocracking

Hydro processing operation involves reaction of petroleum fraction with Hydrogen mainly for two applications : A. Hydrotreating Process :Removal of impurities like Sulphur/Nitrogen/Metals /saturation of olefins and aromatics from feed and products. B.Hydrocracking Process :Cracking of heavier molecule in presence of hydrogen to obtain valuable high quality lighter distillates for increasing refinery margin.

Diesel Hydrotreating and VGO Hydrocracking

Type of Hydrotreating process : Naphtha hydrotreating : For removal of sulphur/nitrogen /oxygen/traces of metals . Hydrotreated naphtha produced as feed to catalytic conversion process like CCR/Isomerisation unit/Hydrogen unit etc. Kerosene Hydrotreating : For ATF production. Diesel Hydrotreating : For production of Euro-III and Euro-IV diesel production. VGO hydrotreating : For producing good quality feed to FCCU for maximising Propylene production. Lube oil hydrotreating : Hydrofinishing of Lube oil stocks for improving quality and eliminate dewaxing process.

Diesel Product Specification

Sl. No. 1 Characteristics Unit Euro-II/ BS-II 48 370 35 1.6 820-870 500 0.05 % Vol -Euro-III Euro-IV

Cetane Number (CN), min. Distillation:95% volume recovery at C, max. Flash Point (Abel), min.

51

51

360

360

35

35

Sediment, max.

% mass kg/m3

0.05

0.05

Density @ 15 C

820 - 845

820 - 845

Total Sulphur, max.

ppm(wt)

350

50

Water content, max. Poly-cyclic Aromatic Hydrocarbon (PAH), max. Lubricity, corrected wear scar diameter (wsd 1,4) @ 60 C, max.

mg/kg

200

200

% mass

11

11

m (microns)

460

460

460

DHDT-Feed quality
DESIGN CASES (FEED COMPOSITION) CASE 1 LGO (HS) + Hvy. Kerosene HGO (HS) LVGO (HS) AGO (LS) FCC TCO VB Heavy Naphtha ATF (HS) HSD from DHDS Total 33.72 15.83 4.83 8.39 23.56 0.94 12.73 100 CASE 2 30.4 14.3 4.4 26.5 0.8 23.6 100

DESIGN CASES (FEED PROPERTIES) CASE 1 Specific Gravity @15C Sulfur, wt.% Nitrogen, ppmw Bromine No., gBr2/100g Aromatics, wt.% (total) mono di tri Cetane Number (D613) Flash point, C Metals, ppm wt. ASTM D86, C, Vol% IBP 5 10 30 50 70 90 95 FBP 0.847 1.02 236 9 31 19.7 10 1.3 45 41 0.5 104 160 196 262 279 320 361 380 419 CASE 2 0.856 1.26 298 10 32.1 20 11 1.1 44 42 0.5 104 175 215 280 293 326 363 380 419

DHDT-Process Flow Diagram

H2 MAKE-UP H2 HP AMINE ABSORBER

301-K-01 A/B
FEED

HP COLD SEPARATOR V -04

F-01
301-V-01

E- 01 H2

301-V-07

R-01

R-02
TO LP. AMINE ABSORBER 301-C-03

MP COLD SEPARATOR

LEAN AMINE

RECYCLE COMPRESSOR

DIESEL STRIPPER

DIESEL PRODUCT 301-V-08 C-01 C-04 NAPHTHA STABILIZER 301-V-09

E-07

NAPHTHA PRODUCT

Chemistry

DHDT-REACTIONS
HYDRO-DESULFURIZATION C C Thiophene + H2 C4H4S C C S HYDRO-DENITROGENATION
+ 5H2 CCCCC + NH3 n-Pentane

CCCC + H2S n-Butane C4H10

N
Pyridine C5H5N

OLEFIN SATURATION CCCCCC C + H2 CCCCCC C

1-Heptene C7 - H14 n-Heptane C7H16

Chemistry

Chemical Reactions

Chemical Reactions

Chemical Reactions

Chemical Reactions

Chemical Reactions

Chemical Reactions

Chemical Reactions

Chemical Reactions

Chemical Reactions

Chemical Reactions

Chemical Reactions

Chemical Reactions

Chemical Reactions

Chemical Reactions

Chemical Reactions

Chemical Reactions

Chemical Reactions

Chemical Reactions

Catalyst Loading Typical

ACT069, 150 mm, 3.564 mm, 3.564 m3, 3136 kg m3, 3136 kg ACT077, 600 mm, 14.25 m3, 7840 kg HMC868, 19800 kg

HF858, 113750 HF858, 113750 kg

kg

Balls, 150 mm, 3.564 m3, 4989 kg Balls, 150 mm, 3.564 m3, 4989 kg HR448, 3790 mm, 94.32 m3, 76399 kg Balls, 150 mm, 3.564 m3, 4989 kg Balls, 150 mm, 3.564 m3, 4989 kg

HR448, 7660 mm, 180.03 m3, 145824 kg

Balls, 150 mm, 2.761 m3, 3865 kg Balls, 1215 mm, 12.905 m3, 17422 kg

30

Reactor & Reactor Internals DHDT Unit

Reactor Internals (General Arrangement)
Catalyst & Ceramic Balls Bed Thermocouples (K1 to K10) Skin Thermocouples (TST & BST) Quench Inlet Nozzles Catalyst Unloading Nozzles

Reactor & Reactor Internals DHDT Unit

Reactor Internals (General Arrangement)
BED - 1 Inlet Device Lifting Lugs Test Blocks Filter Tray HD Tray Catalyst Bed Ceramic Balls Catalyst Support Grid (CSG)

Reactor & Reactor Internals DHDT Unit

Reactor Internals (General Arrangement)
BED 2, 3 & 4 (each) Liquid Quench Sparger HD Tray Catalyst Bed Ceramic Balls Catalyst Support Grid (CSG)

Reactor & Reactor Internals DHDT Unit

Reactor Internals (General Arrangement)
BED 5 Quench Ring Swirl & Jet Pipes Quench Tray Inter Bed PD Tray HD Tray Catalyst Bed Test Blocks Ceramic Balls Bottom Basket

UFQ

ISSUES DURING COMMISSIONING & TROUBLE SHOOTING

High Sulphur content in diesel run down(Contd.)

Channel head was tightened to 190kg torque

DHDT-Design Parameters
Parameters
The design capacity of feed for all the cases The catalyst life for the guard bed The cycle length The total catalyst life ASTM D-613 Cetane number for Case 1 The diesel product ASTM D-86 maximum temperatures for the 95 vol% recovery The diesel product recoveries for the design cases 1 The diesel product sulfur content The flash point of diesel product Design water content (D1796) in diesel product The stabilized naphtha product total sulfur content The stabilized naphtha product total nitrogen content The stabilized naphtha product RVP (ASTM D 323) The H2S content for the sweetened off gas product Pure H2 consumption as H2 consumed vs fresh charge processed

DESIGN
1.8 MMTPA 24 months 24 months min. 72 months min. 56 370C 98.0/ 96.5 <30 ppm. 35C.
200 wt max

5 ppm wt 5 ppm wt 0.4 kg/cm2g max 50 ppm vol (max.) <1.55 % wt of FF.

DHDT Typical Operating conditions

Unit Corrected Feed Rate TCO Feed Rate Hydrogen consumed H2 partial Pr. Overall WABT Diesel Yield Reactor 1 LHSV WABT Gas/Oil Ratio at R-01inlet Reactor Inlet temp Reactor Outlet temp Reactor 1 Total DP Reactor 2 LHSV WABT Reactor Inlet Temp Reactor Outlet temp Reactor 2 Total DP TPH Wt. % of FF Wt. % of FF Kg/cm2a C % hr-1 C C C Kg/cm2 hr-1 C C C Kg/cm2

Design SOR/EOR 225.00 27 % 1.28/1.55 97.20 360/390 98/97.6 1.36 360/390 410 333/373 368/398 3.0/7.0 1.13 360/390 352/382 368/398 5.0/8.0

Typical Parameters 225 10 % 1.33 99.23 348.51 99.7% 1.35 344.60 463.08 322.11 358.77 2.02 1.12 351.60 345.63 359.14 3.17

DHDT Typical Operating conditions Reactor DP vs Thruput

DHDT Typical Operating conditions Reactor WABT vs CETANE No.

DHDT Typical Operating conditions Feed Cetane vs Product Cetane

Hydrocracking
To Transform heavy, high boiling, low value and wide variety of feed stocks to premium quality lower boiling high value products By Carbon- carbon bond scission accompanied with simultaneous or sequential hydrogenation at high hydrogen pressure and high temperature

A Key Catalytic Conversion Process

Direct Conversion Technologies

Catalytic & Thermal Processes FCC Visbreaking Delayed Coking Deasphalting

C- Rejection

7 7 7 7

C- rejectionProducts of lower quality large amount of coke selectivity poor

Hydrogen addition Catalytic Process Hydrocracking 7 Fixed Bed 7Ebullated Bed 7Slurry Bed
H2-additionProducts of higher quality very high selectivity

Hydrocracking
It is a process of great industrial significance Products are eco friendly containing mostly saturated hydrocarbons & low to ultra low sulfur. So the technology is gaining greater and greater importance. Very high flexibility in terms of feed and products generated & very high selectivity for products. Wide spectrum of process technology& catalysts suiting refiners need

HYC a flexible versatile process using various feeds to give desired products with right catalyst under suitable conditions Naphtha LCGO/LCO/VBGO AGO/HCGO/HCO VGO/DAO

LPG Naphtha Naphtha/Middle Dist.

Naphtha/Middle Dist/FCC feed /LOBS/Ethylene feed Residue give dist.,FCC/Coker feed or low S fuel oil

Hydrocracker feedstocks
Heavy Gas Oils in North America for the production of naphtha. Vacuum Gas Oils in India & the Middle East. Specific Gravity: Distillation, ASTM D 1160, Deg C IBP / 5% 95% / FBP Asphaltenes, ppm Metals, ppm PNA, vol% Sulphur, ppm Nitrogen, ppm 0.89 0.91

340 / 390 550 / 575 < 100 ppm <1 40 / 25 / 35 (Typical) 3000 5000 400 - 1200

Typical Hydrocracker product pattern, wt%

Feed Streams VGO Hydrogen 100.0 2.25

Product Streams FG LPG Light Naphtha Hy. Naphtha ATF / Kero Diesel Bottoms 1.5 4.5 12.5 3.0 39.45 39.3 2.0 102.25

Total

102.25

Total

Postulated Hydrocracking Mechanism of a Paraffin

(A) Formation of Olefin R-CH2-CH2-CH-CH3
CH3
Metal

R-CH=CH-CH-CH3 CH3

Postulated Hydrocracking Mechanism of a Paraffin

(B) Formation of tertiary Carbenium ion R-CH=CH-CH-CH3 CH3 R-CH2-CH2-C-CH3 CH3

Acid

Postulated Hydrocracking Mechanism of a Paraffin

R-CH2-CH2-C-CH3 CH3 R-CH2 + CH2=C-CH3 CH3

Acid

Postulated Hydrocracking Mechanism of a Paraffin

CH2=C-CH3 CH3 CH3-CH-CH3 CH3
Metal H2

N-Paraffins Hydrocracking
Adsorption on metal sites Dehydrogenation (olefin forms) Desorption from metal sites and diffusion to acid sites Skeletal isomerisation and/or cracking of olefins on acid sites through carbenium ion intermediates Desorption of olefins from acids sites and diffusion to metal sites Hydrogenation of these olefins on metal sites Desorption of resulting olefins

Heavy PNA Formation and Coking

Raw feedstocks Contain Precursors Large PNAs formed on Catalyst Surface HPNAs in Reactor Effluent Coke Formation
Condensati on Reactions

Hydrocracker Process flow Diagram

Makeup H2 MUC Ex MPU Ex PSA F-1 V-1 Feed Filter V-2 E-1 MPU To MUC Diese l V-3 CR Wash Water HP Amine R-1 R-2 Amine Scrubber Heavy Naphth a ATF/Kero RGC

Gas & LN to recovery sec.

Unconverted Oil

PRT AM HVGO Feed Preheat Ex BH HVGO V-8

V-9

F-2

Hydrocracking configurations
Single Stage Once Through (SSOT):
In this configuration, there is one Hydrocracking reactor. This reactor is preceded by a Pre Treat reactor for HDS / HDN / HDM of the feed. This configuration runs on partial conversion mode (65-70 lv%). The unconverted bottoms is routed as feed to the FCCU.

H2 Feed

Once Through Hydrocracker Flow Scheme: Single Reactor

Recycle Gas

Gas + LPG

Interbed Quench 1 Reactor Quench 2 Fractionator

Naphtha

Kerosene Diesel

HP Separator

HT Bottoms

Hydrocracker Configurations
Single Stage Complete Conversion
Single Pre Treat Stage; followed by, One Hydrocracking Reactor

Unconverted bottoms from the 1st Pass is recycled back to the Hydrocracking reactor. Lower Cost Lower flexibility Single Stage Hydrocracker operates at higher temperature levels.

Once through Hydrocracker with Pre Treat Reactor: Part Gas & Full recycle
M/up H2 Feed Recycle Gas Naphtha

Pre Treat Reactor

Fractionator

Kerosene

HC Reactor

HP Separator

Diesel

Recycle Feed

Bottoms

Hydrocracking configurations
Two Stage Units with complete conversion
Two Hydrocracking Reactors Pre Treat function carried out in the 1st bed of the 1st Stage Reactor.

More expensive in terms of capital cost. Offers extra operating flexibility. 2nd Stage operates at much lower temperatures in a N free environment. Gives an opportunity to fine tune yields.

Two Stage Hydrocracker: Chevron Scheme

M/up H2 RG 1 RG 2

Feed Q1 Frac Q1

Q2 HPS 1 1st Stage 2nd Stage

Q2 HPS 2

Bleed

Hydrocracking Unit Reactions

Desired reactions
Treating to remove contaminants Adding hydrogen to unsaturated hydrocarbons Cracking to obtain desired boiling range products

Undesired reactions
Coking Contaminant poisoning

Why Pretreat Feedstock

Improve cracking catalyst effectiveness
By reducing organic nitrogen in cracking reactor feed

Reduce temperature rise in cracking beds

Treating reactions can be very exothermic

Treating Catalyst is expensive

Treating Reactions
Metals removal Olefins saturation Sulfur removal Nitrogen removal Oxygen removal Aromatic saturation
Easiest

Hardest

Treating By-products
Organic Sulfur Organic Nitrogen Oxygen Compounds H2S NH3 H2O

Features of HDS and HDN Reactions

Hydrodesulfurization (HDS)
Sulfur removed first then the olefin is saturated

Hydrodenitrogenation (HDN)
Aromatic saturated first then nitrogen is removed

Implications of HDN Chemistry

Complexity makes HDN more difficult than HDS Saturation of aromatic rings requires more H2 for HDN than HDS (on a molar basis) Higher H2 consumption releases more heat Aromatic Saturation is equilibrium controlled at high temperature (>400 oC ) Desired aromatic saturation requires a narrow range of temperature applicability

Metals Removal
Organo Metallic Compounds
Adsorption Reaction

(Metal +Catalyst) + Hydrocarbons

Hydrocracking Reactions
Adding of Hydrogen to Aromatic centres Addition of hydrogen to olefinic double bonds Acid Catalyzed cracking of paraffins and side chains on aromatics Acid-catalyzed isomerisation of paraffins Formation of coke on the surface of catalyst Removal of coke by addition of H2

Hydrocracking Reactions
Bi-functional mechanism Requires two distinct types of catalytic sites to catalyze separate steps in the reaction sequence

Bi-Functional Mechanism
Metal Function:
Generates olefin or cyclo-olefin

Acid Function:
Generates Carbenium ion from olefin by proton transfer Carbenium ion cracks Converts carbenium ion to olefin by proton transfer

Metal Function:
Saturates olefins

Hydrocracking Kinetics
Rate of hydrocracking typically follows first-order kinetics Relative reaction rates depend on strength of adsorption of reactants

Hydrocracking Reactions
Paraffins Mono-naphthene Multi-ring naphthene Mono-aromatic Reaction Difficulty Multi-ring Aromatic Hetero-aromatic

Heat Release Kcal/m3 H2 (BTU/SCF H2)

Reaction Desulfurisation Denitrogenation Deoxygenation Olefin Saturation Aromatic Saturation Hydrocracking Heat Release 2.1-3.4(50-80) 3.0-3.4(70-80) 3.0-3.4(70-80) 5.4-6.3(130-150) 3.0-3.4(70-80) 2.1-4.2(50-100)

Major Classes of Reactions in Hydrocracking

Hydrotreatment Bed - HDM - HDO - HDS - HDN - HDA Hydrocracking Beds - Isomerization - Hydrodealkylation - Naphthene ring opening - Paraffin hydrocracking

Coking is side reaction deactivating the catalyst

Typical Hydrocracking Reactions

1-Hydrogenolysis
+ 6 H2 S H2S +

Benzothiophene

+ 7 H2

NH3

Quinoline

Polyaromatics Hydrogenation
+ 2 H2 + 3 H2

Naphthalene

Tetralin

Decalin

Monoaromatics Hydrogenation
R + 3 H2 R

Hydrodealkylation
R + H2 + RH

R + H2 + RH

Hydrodecyclization
R + H2 R1H + R2H

+ H2

C2H6

Decalin

Hydrocracking
CnH2n+2 CmH2m+2 + CpH2p+2 [m+p= n]

Hydroisomerization
R R1-CH2-CH2-R2 CH-CH2-R2 R

Comparison of Cracking Mechanisms

Mechanism Activation Catalyst Reaction Intermediate s Radicals Carbenium Ion Carbenium Ion

Thermal Catalytic Hydrocracking

Thermal Acidic Bi-functional

None SiO2/Al2O3/ Zeolite NiMo, NiW, noble metal on amorphous or zeolite

Selectivity of Cracking Mechanism

Mechanis IsoC1+C2 Olefin m paraffin Thermal Catalytic Hydrocracking Low Some High High Some Low High High High Aromat iC4 ics and / nC4 Coke Some Low High Some High High

Hydroprocessing Catalysts
Hydrotreating
Nitrogen and sulfur removal Non-noble metal on alumina base

Hydrocracking
Hydrogenation Function
Noble Metal Base Metal

Cracking Function
Amorphous (SiO2/Al2O3 ) Zeolites

Typical Catalyst Components

Hydrogen (metal)
Nickel Molybdenum Tungsten Noble Metals (Platinum, Palladium)

Cracking (acidic, base)

Silica alumina Zeolites

Unicracking Catalyst
Acid function (provided by support)
Amorphous Zeolite

Metal function
Active metal
Group VIA (Mo, W)

Promoter metal
Group VIIIA (Co, Ni, Pd, Pt)

Catalyst Support
Amorphous
Large pores Moderate acidity Lower surface area

Zeolite
Smaller pores Variety of structures High acidity

Acidic Support Materials

Materials Mixed Metal oxides Zeolite NonZeolitic molecular sieves Example SiO2-Al2O3 Y Zeolite SAPO-5

Cracking Function
Provided by an acidic support Solid oxide support materials
Amorphous (Al2O3, Al2O3 SiO2) Zeolite ( Modified Y-zeolite )

Cracking activity determined by :

Acid site strength Acid site concentration

Catalyst Metals
Base metal
Metal sulfide is the active form
Mo and W sulfides considered Active Ni and Co sulfides considered Promoters

Combination Active + Promoter metals used

Pd, Pt
Strong hydrogenation function Sulfur intolerant

Pre Treating Catalyst

Typical Composition
NiO 3 - 10 wt% MoO3 10-25 wt% P2O5 1-4 wt% Al2O3 Remainder

Active Component is MoS2 promoted with NiS HDN catalysts are also good HDS catalysts; but consume more H2

Hydrocracking Catalyst is Bifunctional

Acid support provide Cracking function Amorphous SiO2-Al2O3 Low Zeolite Amorphous SiO2 Al2O3 High Zeolite & binder Metals provide Hydrogenation function Non Noble Metals Ni- W/ Ni-Mo/ Co-Mo Noble Metals Like Pt, Pd

Hydrogenation Function / Activity

Cracking Function / Activity

Pt(Pd) Ni-W Ni-Mo Co-Mo

Zeolite

Silica- Alumina

Metal Component
Metal type Non noble transition metals from group IA ( Mo &W) and group III A (Co, Ni). Noble metals Pt, Pd in sulfur free environment Ratio & amount of metals Base metal atomic ratio is about 0.25 and is equal to metal grIII / (metal gr III + metal grI) Noble metal content is < 1 wt %. Ni or Co oxides = about 3 to 8 wt. % Mo or W oxides = about 10 to 30 wt. %

 Metals : Ni-W / Ni-Mo / Pt or Pd Acidic Support : Amorphous / Zeolite / Amorphous + Zeolite Surface Area, m2/g : 260 to 380 Pore Volume, ml/g : 0.35 to 0.5 Shape : Cylindrical or lobed shapes Diameter,mm : 1.4 to 2.5 Bulk Density,kg/m3 : 700 to 900 Crush Strength, N/mm : 30 to 45

Typical Characteristics of Hydrocracking Catalysts

Catalyst shape and size

Catalysts or catalyst support commonly formed into extrudates, spheres or pellets. P in fixed bed reactor affected by catalyst shape and size. Extrudate length 2 - 4 times its dia (typically F about 1.2 mm). Simplest form of extrudate is cylinder. Forms like tri lobes / twisted tri lobes / tetra lobes also found. Multi lobe cross sections have higher surface to volume ratio than cylinders. Shaped catalyst particles reduce diffusional resistance, create more open bed and reduce P

Source Axens

Tri lobe

Source- Haldor Topsoe

Refiners need better and better catalysts to have following typical benefits
Rugged to upsets. Higher tolerance to poisons. Higher technoeconomic returns

Higher 1-Activity 2-Selectivity 3-Stability 4-egenerable

Better product quality. Capable to process difficult and heavy feed

Catalyst selection
The selected catalyst system in Hydrocracker consists of a series of pretreat catalysts for hydrodemetallation (HDM), hydrodenitrogenation (HDN) and hydrodesulfurization (HDS), followed by hydrocracking catalysts with both activity and selectivity tailored to meet specific conversion objectives.

Pretreatment- A key step in Hydrocracking

Nitrogen content in the feedstock is controlled to avoid poisoning of the hydrocracking catalyst. Aromatic rings need to be hydrogenated to facilitate the cracking reactions. Improvement in hydrotreating catalyst activity will effect the total catalyst requirements to carry out given conversion requirement.

S.N.

Cat. Shape Designati on TK 10 TK 711 RF 200 HC-H DHC-32 DHC-8 7hole tablets Ring

Size

Primary Function Inert Ni-Mo, HDM HDM Ni-Mo,HDS / HDN

1 2 3 4 5 6

30 20 20 13 16 11

Void Bul Fracti De on % lb/ft3 55 41

3-lobe

Shaped Ex. Shaped Ex. Cylinder 1.6 mm Sphere

Zeolite, Ni-W, Hydrocracking 1.6 mm Amorphous, Ni-W, Hydrocracking,

Source S Frazer et al, ARTC,, April 99, Singapore

52.2 44

Typical loading of catalyst in Hydrocracker

Reactor 1 Top Bed of graded cat + HDM + HDT Quench Next Bed of HDT cat Quench Bottom Bed of HDT cat Reactor 2 Top bed HC Cat Quench Bottom bed HC Cat Reactor 3 HC cat Quench Next bed- HC cat Bottom - HDT cat

Typical Hydrocracking Catalysts

Catalyst Metal Function ICR106 ICR120 ICR126 Ni-W Ni-W Ni-W Acid function Amorphous (A) A A+ Zeolite(Z) A+Z Z Z SA, m2/g 272285 285 285 375 300 380 PV ml/g 0.36 0.38 0.38 0.39 0.36 0.62 CBD Kg/m3 881 to 950 881912 926 690 720 545

ICR 139 Ni-Mo ICR160 Ni-W ICR220 Noble

Catalyst deactivation caused by physical & chemical processes

Coking / Fouling Poisoning

Major Deactivation Mechanism

Sintering

Typical Additional Reasons for Deactivation

Blocking of catalyst pore by metals or coke Forming inactive compounds by reaction of active metals with support. Destruction / loss of active sites.

Coke composition and formation

Empirical formula for coke Cn Hn to CnH0.5n Formed during hydrocarbon conversion reactions. It becomes significant over a long period of time on fixed bed hydroprocessing catalysts and may block active sites or plug pores. In upsets, non catalytic thermal reactions may form carbon deposits in the interstices of the catalyst particles or inert material. Such deposits increase the reactor pressure drop. Catalytic coke usually do not affect P. The coke affects activity and selectivity.

Mechanism of Coke Formation

It occurs via complex reactions. Aromatics alkylation, olefins oligomerization & dehydrocyclzation, aromatization through hydrogen transfer & condensation lead to coke. Polyaromatics may be formed from monoaromatics through a chain of addition reactions via carbenium ion mechanism

 In bifunctional catalysts, metal and support both contribute to coking. The intermediate olefins formed on the metal sites may polymerize on the acidic support. Polyaromatics formed on the catalyst get dehydrogenated leading to coke. With uniform distribution of coke through the catalyst, the reactions occur throughout the catalyst A given amount of coke concentrated at the pore is more toxic or deactivating than the amount distributed uniformly.

Catalyst Regeneration
With the progress of cycle, catalyst deactivates approaching EOR conditions.The product may not meet the specifications, the reactor P may be high affecting the recycle gas flow rate. The catalyst activity may be recovered by in situ or ex situ regeneration. The coke on the catalyst is burnt under controlled conditions of temperature and air- nitrogen flow. Oxygen concentration in the reactor I/L nitrogen is monitored & air supply is strictly regulated to control reactor T. Caustic scrubbing downstream of air cooler and NH3 injection in effluent exchanger is carried out to protect against sulfur oxides. Some of the latest super active catalysts may not regain the high activity during in-situ regeneration. They are to be properly regenerated ex- situ.

Unicracking Process Variables

Reactor Temperature Feed Quality Feed Rate Product End Point Hydrogen Pressure Liquid Recycle Rate Recycle Gas Rate

Makeup Hydrogen

Effect of Operating Variables

Increasing the temperature favors conversion. Decrease in temperature favors heavier product formation. Aging affects activity and selectivity. Effect of aging on selectivity is lower for amorphous catalyst compared to zeolite catalyst. The aromatic content of middle distillates increases with catalyst age due to enhancement of temperature. Increase in temperature increases coking rate Higher temperature can process difficult feeds. Increase in temperature reduces cycle length. H2 partial pressure affects the degree of hydrogenation and the hydrocracking rate. It also affects HDN Effect on HDS is also there but to lower extent.

Fresh Feed Properties

Gravity Boiling Range Sulfur Nitrogen UOP K Bromine Number Hydrogen Content Con Carbon Heptane insolubles Color Metals Content

Fresh Feed Quality

Metals Content
Naturally Occuring: Ni, V, As
High levels may indicate residue entrainment

Upstream processing: Pb, Na, Si, P Soluble iron naphthenates

Permanent Catalyst poisons

Solid corrosion products (iron sulfide) do not poison catalyst, but plug the bed

Feed Stock Consideration

High nitrogen feedstock to be processed at higher pressure and lower SV. Ni + V content should be < 2ppm. CCR < 1% and asphaltenes <0.05%. Increase in pH2 reduces coking tendency.

Feed Stock Effect on Hydrocracking

Typical Composition of VGO from different crude sources Bombay High 26 28 46 23 31 0.5 410 Minas Arabian Heavy 24 22 17 25 58 3.0 150 Crude Source Maya California

LV% Yield of 340 540C API Gravity LV%, P N A Sulfur Wt. % Nitrogen ppm

37 34 44 34 21 0.1 610

23 21 11 29 58 3.1 1880

24 14 1 42 57 1.0 6470

Source : R. L> Howell et.al., Pet. Ref. Conf. Tokyo

Feed Stock Consideration

Highly paraffinic feed require higher temperature. They have low coke forming tendency. Produce more paraffinic higher quality products. They consume less hydrogen relative to aromatic feed. Longer paraffin chains can be cracked at lower severity compared to smaller ones. Aromatic feed should have hydrogenation activity for pretreatment as well as conversion catalyst. Acidity should be moderate. Polyaromatics have diffusional problems. Moderate to high acidity required for heavier feedstocks. High nitrogen feedstock to be processed at higher pressure and lower SV. Ni + V content should be < 2ppm. CCR < 1% and asphaltenes <0.05%. Increase in pH2 reduces coking tendency.

Weighted Average Bed Temperature Attribute a weight fraction of the Catalyst bed to each TI A=25% catalyst TI1. B=35% catalyst A TI2 C=40% catalyst eight B
C TI3

WABT = 0.25*TI1+0.35*TI2+0.4*TI3

Effect of Feedstock Properties

Property Endpoint Sulfur Nitrogen Aromatics Con Carbon C7 Insoluble Metals Effect Reduced Cycle Length Minimal Effect (Cracking) Reduced activity Reduced Cycle Length Reduced Cycle Length Reduced Cycle Length Reduced Catalyst Life Limit

<0.5 wt% <0.05 wt% <2 wt ppm

Comparison of Feedstock Bulk Properties

Property API Gravity SG@15.5 oC D1160 Dist,oC IBP 10% 50% 90% EP Feed A 22.5 0.9188 Feed B 20.1 0.9334 Feed C 25.7 .9001

252 351 449 532 572

345 401 470 541 579

285 357 418 483 511

Feedstock Processability
Prediction from Bulk Properties Compared to Pilot Plant Data Feed B Property SOR Temp, oC Predicted Pilot Plant Feed A Feed C

Base Base

+10 +11

-2 +3

Deactivation Rate Predicted Base Pilot Plant Base

*1.8 *3.0

*0.4 *0.7

Recycle Gas Rate

Ensures H2 availability at catalytic sites Provides a heat sink Helps to maintain good flow distribution Gas/Oil or Hydrogen to Hydrocarbon ratio Typical Gas/Oil ratios
Treating Inlet > 3000 SCFB (500 Nm3/m3) Cracking Inlet >7000 SCFB (1200 Nm3/m3)

H2/HC=Gas/Oil * Recycle Gas H2 Purity

H2 to Oil Ratio

It affects bed Dt Improves distribution of materials. Reduces over cracking Suppresses coke formation.

Increase in LHSV Poorer product properties at same average temperature. Higher temperature to meet product properties reducing cycle length.

Pressure
Hydrogen Pressure is key Required Pressure is determined by:
Feedstock Desired product quality Desired Cycle life

Higher pressure or higher purity Inhibits coke formation H2 Partial Pressure = Recycle Gas H2 purity * Pressure

Dependence of catalyst fouling on hydrogen partial pressure

Increase in hydrogen pressure favors cycle length reducing fouling rate. First stage cracking : Fouling rate =

1 (pH2)4

First Stage HDN

Fouling rate =

f f

(pH2)6 1 (pH2)4
Second Stage cracking Fouling rate =

HPNAs What Are They ?

PNAs = Polymeric Aromatics Hydrocarbons containing > 2 aromatic rings HPNAs PNAs with 7+ rings

HPNA
HPNA basic in nature. Adhere strongly to the acid site. The deposition leads to premature deactivation causing temperature to be increased to get the activity, again enhancing HPNA formation. Vicious cycle takes place. HPNA have low solubility in reactor effluent with precipitation at lower temperature in F/E exchanger Foulant red brown in color. The consequences are D P increase and fall in HTC causing the operation to drop thruput, gas to oil ratio and higher furnace duty.

Polynuclear Aromatics (PNAs)

Aromatic Ring Benzene PCA-9 Rings Coronene

Heavy PNA

Wash Water
Removes Ammonia from recycle gas
Maintains catalyst activity Prevents exchanger fouling due to ammonia salt formation

Required for operation

Catalyst loading methods

Sock Loading
Easiest and Fastest Must use proper technique

Dense loading
More catalyst in given volume May be slower than sock loading Closely monitor to ensure optimum loading Lower void fraction

Choosing Catalyst Loading Method

Available reactor volume Pressure drop higher for dense loading
Review pressure drop history, particularly for top bed Consider recycle compressor head availability and catalyst support beam system

Flow distribution

Good Flow Distribution

Charecteristics
Good radial temperature profiles No hot spots Not sensitive to minor upsets

Results
Minimized risk of temperature excursion Longer cycle length Improved selectivity

Reactor Unloading Methods

Gravity Dumping
6-7 m3/hr typical May not flow readily

Vacuuming
3-5 m3/hr typical Higher losses (10-30 %)

Combination

Unicracking Metallurgy
Process Factors
High pressure up to 200 kg/cm2 (2850 psi) Moderately high temperature: 400-455 oC (750-850 oF) Hydrogen, H2S and NH4HS are present Strength Toughness Corrosion resistance Fabrication compatibility

Materials Properties

Reactor Metallurgy General MPT Guidelines

2 Cr -1 Mo 93 oC (200 oF) 2 Cr -1 Mo 150 oC (300 oF) 2 Cr 1 Mo 1/4 V or 3 Cr 1 Mo V Pre 1990 Metallurgy Newer Metallurgy 66 oC (150 oF)

Reactor Startup Procedure

For heavy wall reactors heat to MPT before pressurizing above 20% shop test pressure For older reactors, may need to reduce pressure and increase temperature if cracks exist For newer units, lower temperatures may be used

Reactor-Shutdown Procedure
Normal shutdown cooling rates are fine 28oC/hr (50 oF/hr) No special degassing procedures required Excessive cooling rates of heavy wall equipment could lead to:
Potential H2 stress cracking Increased overlay disbonding

Typical Examples of Poor Performance and Trouble shooting of Hydrocrackers

Hydro cracker plant problems may sometimes cause huge economic loss due to Non utilization of full capacity and consequences on other units/ ullege problems. Catalyst activity problem Selectivity problem Corrosion, fouling, plugging Safety aspects.

Reactor Top Bed Pressure Drop

Pleated filters have five times surface area than the normal cartridge. Screening Baskets at the top bed may some time help in controlling pressure drop. Efficient graded beds have been found to be effective. Typical loaded scheme found effective in the present case.

Ammonium Bi-sulfide Corrosion

May be common in conventional hydrocrackers particularly using demetallized oil. Main source of potential under deposit corrosion and tube pitting occur by NH4HS.

The Important parameters are : The NH4 HS concentration is wash water

The fluid velocity in tubes of condenser. The hydraulic symmetry of the circuit. The water injection point, water quality and quantity Condenser outlet temperature

Operational Parameter Kp Factor NH4HS wt.% in water Wash Water rate, Vol. % of feed O2 in wash water, ppm Condenser tube velocity, ppm

Typical Optimum Values 0.15 4.8 5.2 0.05 15

Source Al-Naim et al, ARTC,99

Severity of Ammonium Bisulfide Fouling Depends on Kp factor (mol. % NH3 X mol. % H2S) Severe Moderate Low Kp > 0.5 Kp < 0.15 Kp < 0.07

Water Injection Point

Upstream of effluent condenser with even

distribution of wash water. Restriction orifices may be used for good distribution. 20% of injected water to remain in aqueous phase to avoid acidic dew point corrosion.

Water Injection Rate

About 5 8 LV% of fresh feed. Concentration of NH4HS not to exceed 5 wt.%. Water Injection Quality Clean stream condensate is good. chloride will be harmful as it Traces of will form

ammonium chloride. Water from open tank has 1-10ppm of O2. So water tank be blanketed with inert. Only deareated water be used.

 Pipings should be symmetrical to ensure equal distribution of oil, water and vapor phases. Effluent condenser tubes and piping to have velocity of 10-20 fps for CS. Severe corrosion by NH4HS in Riyadh

Hydrocracker resulting in loss of production, high maintenance cost and potential hazard became acute after revamp performed for overcoming HPNA problem in condenser tubes.

Hydrocracker Runaway
The overall reaction rate is significantly exothermic. Under some situations the exothermicity may increase the bed temperature to high level, the heat generated leading to higher rate and more heat. This can spiral running out of control and potential loss to vessel or pipings by excessive temperature. In normal operation quench sweep the heat. In emergent situation the depressurization can reduce and stop reaction. De-pressuring can be fast or slow based on the use of either of the system deemed necessary.
Source : E. M. Marszal, Exida

 Operator may first try slow system. If response is not satisfactory he may opt for fast system. Safety Integrated Function (SIF) may also initiate depressuring on detecting high temperature..

Sorce : E. M. Marszal, Exida

The initiating events that may cause runaway are

Recycle Compressor Failure The hydrogen flow decreases. gas flow stops. The quench So heat removal from the

reactor stops. Due to ample hydrogen pressure the reactions may continue to result in starting of runaway phenomenon so the SIF may start slow depressurisation or manual activation of slow depressurisation.
Source : E. M. Marszal, Exida

2 Reactor Internals Failure

Failure of Cat. Support screens, distribution boxes help. can initiate the temperature runaway. may Sometimes quench management

If the damage is severe, it may be

difficult. So depressuring for safe state.

3. Quench Failure Low or no quench flow due to controller failure or CV failure. hand jacking the CV. 4. Plugging/ contamination controlled. 5. Improper channeling. catalyst loading leading to Channeling/ leading to Coking hot spots and be Sometimes manual operations of valve from control room/field by

6. Bed temperature measurement failure Failure of bed temperature can lead to runaway if the failure action decreases/ stop the quench. Manual operation of CV can prevent the initiation of runaway. 7. Failure of recycle gas flow controller. 8. Change in feed flow and gas to oil ratio. 9. Failure of fired heater O/L temperature control leading to high heater O/L temperature.

Special features - Reactor Internals

Feed Diffuser

LIQUID DISTRIBUTOR TRAY TRAY LIQUID DISTRIBUTOR TRAY

CATALYST SUPPORT GRID

QUENCH TRAY

H2 QUENCH PIPE

OUTLET COLLECTOR

CATALYST UNLOADING NOZZLE Thermocouple nozzle

Reactor Thermocouples

Thank you