SPECIFICATIONS OF DIESEL

Specification BS-I BS-II Euro-III

Sulfur, ppmw max

Cetane number, min Polyaromatics % max Density, kg/m3 Distillation T 85 max T 95 max
1

2500
48 No spec 820 - 860

500
48 No spec 820 - 860

350
51 11 820 845

350 370

350 370

No spec 360

DHDS Block Diagram

Purge Gas Naphtha PDS H2 Sour Diesel DHDS FDS Reformer Hydrogen H2S rich H2 Amine Section Rich Amine to D-SRU Sweet Diesel to Tanks Sour Water to D-SRU PSA Lean Amine from D-SRU

Hydrogen Production
Hydrogen Plant is designed to produce 2296 Kg/hr (25000 NM3/hr) of pure hydrogen (99.98%) using Steam Reforming of Naphtha with further enrichment in shift converter & purification in PSA. Process Steps Feed (Naphtha) Pre-desulphurisation Final desulphurisation Steam Naphtha Reforming (Reforming +Steam Generation) CO HT shift conversion H2 purification (PSA)

Pre - Desulphurization Section

To remove Sulphur from Naphtha which is poison to reformer catalyst (Sulphur reduction from 1000PPM to 10PPM). Naphtha and recycle H2 are heated and sent to Reactor where Sulphur compounds are converted to H2S over Cobalt-Molybdenum based catalyst RSH + H2 RH + H2S (Exothermic Reaction) T=3400C & P =24.5 Kg/cm2g Other Side Reactions O2+H2 2H2O ( Exothermic Reaction) CnH2n+H2 CO+H2O (Exothermic Reaction) CO2+H2 CO+H2O (Endothermic Reaction)

Process Description(PDS)
To Flare
PC003A/B To E02

60-F-01
FC002
61D01

FC003

E01

P01A/B

P13A/B

Recycle H2

LC001 Fuel Naphtha to Reformer Sour Naphtha FC327

R01

Process Description(PDS)
BFW SWS E02 D02 FC059

Naphtha from E01 SWR

Sour Water to D-SRU

FC058 LC062

E06 SWR SWS

E03A/B

D04

LC079A/B Naphtha to D11 Naphtha to C01 Sweet Naphtha to storage

K01A/B Recycle Gas to E01 Naphtha from C01 Bottom PC058

Process Description(PDS)
Flare Flare

Naphtha from D02 E05 SWR SWS

PC080A/B

PC084

FC075

E04

FC076 D03

D07 P02A/B Steam Sweet Naphtha

Sour Water Purge Gas from D02

Final Desulphurisation

To reduce the Sulphur content of Naphtha from 10 ppm to < 0.5 ppm. Naphtha and H2 are heated and processed in reactor(R11) to convert S compounds to H2S over Cobalt-Molybdenum based catalyst. R - SH + H2 R - H + H2S C2H5Cl + H2 C2H6 + HCl T=390oC & P= 30.8 Kg/cm2g Chloride Removal in R12A/B by sodium aluminate 2HCl+2NaAlO2 Al2O3 + 2NaCl +H2O The H2S generated in R11 is absorbed in ZnO reactor(R12A/B) ZnO + H2S ZnS + H2O

Process Description (FDS)

PC111A PC111B Hydrogen From MGC

FFC101 61D11 XV102 61E11

PC117A LC101 Sweet Naphtha from Tk186 61P11A/B

To 61E13A/B

Feed+H2 to 61CE15

Process Gas from 61R13

DHDS Refresher,2011

Process Description (FDS)

61AM12

SWR

61R11
SWS

PC116A/B

R12A R12B LC116 Feed + H2 from 61CE15 61PC117B Naphtha to 61D11

DHDS Refresher,2011

Steam Reforming

Desulfurised Naphtha is mixed with steam and passed through a Nickel catalyst packed in vertical narrow 104 tubes (34 Ni - 25 Cr) mounted in the reformer at high temperature Top Catalyst :Ni +dispersed Potash to suppress coke formation CnHm + nH2O nCO + (n+m/2)H2 (endothermic) CH4 + H2O CO + 3H2 (endothermic) C + H2O CO + H2 (endothermic)

Outlet T= 860oC & P=24.6 kg/cm2g

Process is endothermic and heat is supplied by fuel firing with 40 top fired burners.

Process Description (Reformer)

Reformer Feed from 61CE12

CE15 CE14 CE13 CE12 CE11 TC134

61CE16A 61CE17 61CE16B

STACK

Process Gas to 61E12 E16

Water from D15 Water /Steam to 61D15 61FC212 61KM12A/B

Blow down from 61D15

Process Description (Reformer)

XV152 FC152 FC151

Water/Steam

Feed+H2 from 61E11

Water from D15

TC153

Feed +H2 to R11

Desulphurised Short Loop Feed from Nitrogen 61R12A/B

Ammonia
Water from D15

PC152A

Water/Steam Steam from D15 Feed to F11 Export Steam

Process Description (Reformer)

CE-13 To F11

TC153 61D15 LC171 PC152B

Water/ Steam from CE17

Blow down to E16

Steam to Silencer BFW from 61E13 61E12 Water to CE14

Export Steam

Water/ Steam from CE11

Water/Steam from CE14

TC181

Process Gas from F11 Water to CE17

Process Gas to HT Shift Reactor

Water to CE11

Steam Reforming

Parameters influencing design and operation Pressure - favored by low pressure. Steam carbon ratio: Defined as moles of steam per atom of carbon in the HC feed. CARBON FORMATION

2CO C + CO2
Sufficient steam is required to avoid carbon lay down in the catalyst

Temperature : Conversion favored by high temperature.

Process Description (Reformer)

Syn Gas from Reformer AM11A/B PC191 Naphtha + H2 BFW to steam drum R13 DM Water to Degassifier 61E15

Naphtha+H2 to CE15

FC181

FC182

LC181

LC191

BFW from Degassifier

DM Water from Header Condensate to Degassifier

CO Shift Conversion
Process:

HT shift reaction converts the carbon monoxide present in the reformer gas to Carbon dioxide producing additional H2. CO + H2 CO2 +H2 (exothermic)

Iron oxide catalyst is used. Improve PSA performance by reducing CO load. The Catalyst should be operated at the minimum practical inlet temperature giving the desired conversion of CO. As the Catalyst ages it is necessary to increase the converter inlet temperature in order to maintain a satisfactory exit CO level.

Importance of Recycle Hydrogen

Recycle H2 of FDS section keeps this portion of catalyst in reduced state. Predominantly Reforming Reactions thus generation of H2

H2 molecules
Predominantly Catalytic Cracking Reactions & Olefin Saturation

Generated Hydrogen Keeps the catalyst of this portion in reduced state.

Process Description (Reformer)

Flare

Flare Process Gas from D13 H2 to B.L H2 to PDS

Purge Gas to Burners

PSA(Pressure Swing Adsorption)

Adsorption is the preferential partitioning of substances from the gaseous or liquid phase onto the surface of a solid.
Adsorbent : solid substrate Adsorbate : adsorbing phase PSA unit works on the principle that the adsorbent attracts and retains the impurities at higher pressure and releases them at lower pressure. 4 Basic steps carried out by automatic PLC controlled control valves

1. 2. 3. 4.

Adsorption Depressurization Purging Re-Pressurisation

Adsorption

Process Description (PSA)

SubCycle Time : 165 Second ( 2.75 Minute)
25

Cycle Time : 825 Second ( 13.75 Minute)

20

Adsorption,165

15

Repressurization, 130 P-Equalisation,70

10

R-Equalisation,30 Isolation-I, 30
5

Providing Purge,95
0 0 100 200 300

Dump,75
400 500

Isolation-II,95

600

700

800

900

Purge,95

DHDS Unit
DHDS Unit designed to supply High Speed Diesel with 0.25 % wt. sulfur content with a capacity of 5400 TPD. After revamp its capacity increased to 7290 TPD, and it can achieve 0.002 % wt. sulfur (Max).

DHDS Major Section

DHDS Reaction Section ( High Pressure Section ) Amine Absorption Section (High and Low pressure Section) Stripping Section (Low Pressure Section) Naphtha Stabilization Section (Low Pressure Section)

DHDS Process Description

Wash Water R02 Recycle H2 F01 R01 H2S rich Gas to HP amine absorber

Cold Separator Sour Diesel E01/02/34 HP Separator

E03 Stabilizer

E06 Sweet Diesel

Steam Stripper Stab. Naphtha

Compressor Section
E05A/B FC1801

E12A/B 60K01A/B/C

60K02

H2 from PSA Recycle Gas from HP Amine absorber 60FC1902 Recycle Gas to E01

To Quenches

DHDS Relatives
H2 to VRCFP

Sour Water to
D-SRU/Merox/VRCFP

Fuel Gas

H2 from VRCFP

Cold Feed from Tanks CDUs LD/HD/VD/VBN FCCUs LCO/HCO

DHDS

Sweet Diesel to Tanks

AAG to D-SRU

Stabilizer Naphtha to MS Tank / CDU-III Run down

Diesel Composition
Diesel composition : ( 9-23 Carbon atoms )

Paraffin ( straight chain Hydrocarbons) -- Olefins

Naphthenes (Cyclic Hydrocarbons)

Aromatic Compounds ( benzene Rings like structures)

DHDS Reactions

Desirable Reactions

Elimination of Sulphur Elimination of Nitrogen and oxygen Elimination of metals Saturation of olefins/ di-olefin & Aromatics

Undesirable Reactions

Hydro cracking coking

DHDS Reactions
Desulphurisation

Mercaptans , sulfides and disulfides react easily leading to saturated and aromatic compounds. Sulphur combined into cycles of aromatic structure is difficult to eliminate. Desulphurization reaction is exothermic, consume hydrogen and produce H2S. 2 to 3 molecules of hydrogen are consumed for every atom of sulphur removal. + 6H2 S H 2S + + Heat

DHDS Reactions
Elimination of Nitrogen C C C + 5H2 C C N

C5H12 + NH3 + Heat

Nitrogen removal is desired to improve feed stock color & color stability. De-nitrification rate is lower than the desulphurization rate.

Reactions are exothermic.

On average 4 molecules of H2 are consumed per atom of nitrogen

DHDS Reactions
Hydrogenation

Hydrogenations occur of olefinic and aromatic compounds. The reactions are highly exothermic and decreases the molecules. C-C=C-C-C-C + H2 C-C-C-C-C-C number of reacting

Demetalization:
The organo metal compounds ( As, Pb, Cu, Ni, V) are cracked and the metals are trapped on the catalyst.

Undesirable Reactions : Hydro cracking

Cracking of Hydrocarbon in presence of hydrogen * Consumes hydrogen * Reduces product yield * Hydrogen purity of recycle gas.

DHDS Reactions
Undesirable Reactions :Coking Heavy molecules are adsorbed on the active sites of the catalyst, it may get condensed and polymerize on the catalyst and form coke.

Catalyst Active Sites

Catalyst Pores

Effect of Temperature

Hydrodesulphurization

De-nitrification

Rate of Reaction

Aromatic/Olefin Saturation

Coking

Temperature

Effect of Pressure
Hydrodesulphurization
Aromatic/Olefin Saturation

Rate of Reaction

Coking

Pressure

Amine Section
Fuel Gas or Flare Header Flare or Fuel Gas Header Recycle Gas to RGC suction

LP Amine absorber Lean Amine from D-SRU

HPAA bypass
HC 1701

H2S rich gas from Reflux Drum

HP Amine absorber
H2S rich recycle gas from 60D02 Rich Amine to LP Amine absorber

Rich Amine to D-SRU

Chemistry of Amine Section

H2S is a weak acid & ionizes in water to form hydrogen ion & sulfide ion. H2S + H2O H3O+ + HSDi ethanolamine is a weak base and ionizes in water to form amine ion and hydroxyl ion

(HOCH2CH2)2NH + H2O (HOCH2CH2)2NH2+ + OHWhen H2S dissolves into the solution containing the amine ion, it reacts to form a weakly bonded salt of the acid & the base (HOCH2CH2)2NH2+ + HS- (HOCH2CH2)2NH2SH The sulphide ion is thus absorbed by the amine solution. (HOCH2CH2)2NH + H2S (HOCH2CH2)2NH2SH

Absorption independent variables

Temperature Lower Temperature favors the absorption. However lean amine temperature should be maintained 7 to 13oC higher than the gas temperature to avoid the condensation. Acid gas loading Absorption depends on restricting the H2S loading in the rich amine to favour the forward direction of the reaction given in equation. The H2S loading of the amine solution is controlled by adjustment of the amine circulation rate. Amine concentration Practical and economical considerations, confirmed by field experience, have generally shown that the optimum amine concentration for this unit is 25% wt DEA. This is based on the lowest heat requirement for the desired H2S removal, the lowest chemical losses, and the fewest operational problems.