Mathura Refinery

2010

January 20,

Report on Suitability of metallurgy for

high Sulfur & Nitrogen VGO feed in
DHDS.
Ref: MR/IPN/67
Revision - 1

By:
MATHURA REFINERY
Inspection Section

Report on suitability of metallurgy for high sulfur and nitrogen feed in

DHDS

MATHURA REFINERY
Inspection Section
Ref: MR/IPN/67
October 06, Date: 05.10.2008
Sub: Suitability of metallurgy for high Sulfur &
Nitrogen feed in DHDS.
Executive Summary
1. The Design ParametersPaymasters of the unit
below::
Sl.
Feed
rate
and Original
No
impurities level
Design
.
Diesel Case
1
Feed rate (m3/hr)
161.2
2
Sulphur (Wt% max)
1.45
3
Nitrogen (ppm)
120
4
Stripper Inlet Temp.
270
5
Hydrogen
in C-02 24701.61ppm
feed
vol.

for original and VGO case as

VGO Case

78.4
2.8
800
290
32423.13 ppm vol.

2. The revamp of the unit was carried out in Jul2007 to process VGO as feed on
need basis. However, VGO process may be required on sustainable basis after
FCCU revamp.
3. Unit operation with VGO as a feed has been carried out nine times so far.
After revamp in Nov2007 trail run for 05 days was conducted successfully.
4. Significant corrosion product in the form of Sulphide scale was found in
Stripper Bottom Pump during 2nd time VGO processing.
5. Need was felt to find out the probable source of corrosion product and
suitability of the existing metallurgy for the proposed case to process VGO
onas a sustainable basis with minimal corrosion product/ Problem to avoid any
unwanted failure.
6. The main areas affected due to high Sulphur and Nitrogen are as
follows.
a.
Reactor feed upstream of H2 injection (02-V-01,P-01 and connected
Piping)
b.
Reactor
feed
downstream
of
H2
injection
(02-E-01AE,E02,F01,R01,R02 and connected Piping)

Report on suitability of metallurgy for high sulfur and nitrogen feed in

DHDS

c.

Reactor
effluent
circuit
and
REAC.
(02E-02,E01EA,V32,AC01,E05,V03 and connected Piping)
d.
Stripper
Feed,
Bottom
and
stripper
column
(02-E-04AC,E03,C02,AC03 and connected Piping)
e.
Stripper over head system (02-AC-02,E08 and connected Piping)
7.

The requirement of metallurgy up gradation based on the study is

as follows
- 02-C-02: Part shell with SS410 lining, 02-E-04C: T/B up gradation to
A.S., 02-E-08: T/B up gradation to Duplex SS.
- Piping: Stripper feed & Bottom ckt. from E03 to C02 with SS321 &
C02 to P05A/B to E4C with A.S.
- Up-gradation of 02-C02 column top 10 trays with SS316L material.
Detail report is enclosed which may be suitably converted into action plan
after wetting by process Licenser of the Unit M/s Axens. Proposed
modifications are also shown in PFD enclosed as an Annexure-I.

Detail report is put up for kind perusal

INTRODUCTION
Diesel Hydrodesulphurization unit (DHDS) at Mathura Refinery was
commissioned in Aug1999 with design capacity of 1.1 MMTPA (137.5 T/hr)
with single reactor configuration, licensed by M/s Axens, France. The unit
was originally designed to produce diesel with sulfur content of 2000 ppm.
However, in Nov 2000, the second reactor was added for producing diesel
with S content of 200 ppm. Originally unit was designed to process
161.2m3/hr Diesel. The material selection of the equipment / piping was
based on the designdesigned impurity level in the feedstock originally
specified as 1.45 wt% Sulphur and 120 ppm wt. Nitrogen.
With the commissioning of DHDT in May05, a part of DHDS capacity was
underutilizedunder utilization. Accordingly, for effective utilization of
available surplus DHDS facility towards Refinery margin improvement by
processing more of cheaper high sulfur crude, a low cost retrofit for
sequential processing of Vacuum Gas Oil was carried out in Jul2007 under
the license of M/s Axens, France. The new unit designed feed stock
parameters are 78.4m3/hr of VGO feed rate with impurity level 2.8 wt%
Sulphur and 800 ppm wt. Nitrogen.
Report on suitability of metallurgy for high sulfur and nitrogen feed in
DHDS

The detail in-house Engineering for the new equipment and piping
was carried out with reference to the technical specification of
M/s Axens.
The first trial run in VGO mode was taken from 14 th Nov to 18th Nov2007
satisfactorily. Thereafter VGO processing was carried out on following
period as given below
2nd VGO run: 06.09.2008 to 10.09.2008.
3rd VGO run: 20.12.2008 to 23.12.2008.
4th VGO run: 07.08.2009 to 10.08.2009.
5th VGO run: 19.08.2009 to 10.09.2009.
6th VGO run: 15.09.2009 to 21.09.2009
7th VGO run: 16.11.2009 to 19.11.2009
8th VGO run: 13.12.2009 to 15.12.2009
9th VGO run: 07.01.2010 to 09.01.2010
After the second run of VGO operation and after overchangeover to Diesel
operation, corrosive material in the form of iron flakes were observed in
the stripper column bottom pump, 02-P-05A/B suction strainer. Frequency
of choking was 4 to 6 hrs. and took about one week to clear the corrosion
product.

An exercise was carried out to identify the cause of corrosion product in

stripper bottom pump and to check the suitability of the existing
equipment / piping metallurgy in the unit and identify the areas needing
metallurgy / hardware upgrades. This report addresses the respective
problems and suitable suggestions considering the change in the
feedstock specifications as above.
1. TECHNICAL DISCUSSION:
Following technical articles and standard were referred with respect to the
corrosion due to high Sulphur and nitrogen.
API 571: Sulfidation - Corrosion of carbon steel and other alloys
resulting from their reaction with sulfur compounds in high
temperature environments. The presence of hydrogen accelerates
corrosion. Sulfidation of iron-based alloys usually begins at metal
temperatures above 500oF (260oC).
Report on suitability of metallurgy for high sulfur and nitrogen feed in
DHDS

Modified McConomy curves showing typical effect of temperature

on high temperature
Sulfidation of steels and stainless steels.

API 571: High Temp H2/H2S Corrosion The presence of hydrogen in

H2S streams increases the severity of high temperature sulfide
corrosion at temperatures above about 500oF (260oC). This form of
sulfidation usually results in a uniform loss in thickness associated with
hot circuits in hydro processing units.

Critical Factor:
a) The major factors affecting high temperature sulfidation are the
temperature, the presence of hydrogen, the concentration of H2S
and the alloy composition.
b) When hydrogen is present in significant quantities, corrosion rates
are higher than those associated with high temperature sulfidation
in the absence of hydrogen.
c) Sulfidation rates increase with increasing H2S content and especially
increasing temperature as illustrated in Figure below.
d) Higher corrosion rates are found more in gas oil
desulfurizers and hydrocrackers than naphtha desulfurizers
by a factor of almost 2.
Report on suitability of metallurgy for high sulfur and nitrogen feed in
DHDS

f) Increasing chromium content of the alloy improves resistance.

However, there is little improvement with increasing chromium
content until about 7-9Cr.

Corrosion rate of carbon steel in H2/H2S service in a naphtha desulfurizer

from the Modified Couper-Gorman curves.
API 581 High Temperature Sulfidation Module by API Spring
Conference - 2005
1H2S/H2
a) Consideration for general thinning in Gas Oil or Naphtha service
b) Based on Couper and Gorman curves
c) Key operating temperature range from 400 1,000 OF
d) Currently does not consider velocity or localized elevated
temperatures (maximum temperature) that might locally increase
corrosion rates
Influence of Sulphur On High Temperature Degradation Of Steel
Structures in theihe Refinery Industry - BY Joanna Huciska,
Gdask University, Poland
The main forms of damage caused by Sulphur to the steel structures
include weight loss corrosion and sulphide stress cracking in low
Report on suitability of metallurgy for high sulfur and nitrogen feed in
DHDS

temperature aqueous environments, and high temperature sulphide

corrosion in non aqueous environments at 200 500C
Sulphide corrosion without hydrogen present:
The modified McConomy curves suitable for hydrocarbon fractions
containing 0.6 wt % of Sulphur and correction factors for the fractions
with various total Sulphur content are presented. Beneficial effects of
alloying steels with chromium may be seen. Corrosion rates are roughly
tenfold reduced when ferritic 9Cr steel instead of carbon steel is
applied. Lowest corrosion rates are noted for austenitic steel.
In certain circumstances these modified McConomy curves have been
proven unreliable, particularly in hot distillation section of
hydrocracker units. In some conditions they under predict the
observed corrosion rates, and very low Sulphur levels (< 30 wppm
total Sulphur) are beyond the parameters of the curves. Further data
are needed to be collected in order to review and assess the existing
Sulphide corrosion prediction curves used by the refinery industry
Sulphide
corrosion
hydrogen present

with

The presence of hydrogen in

some refinery operations, for
example
hydrotreating,
hydrocracking
and
catalytic
reforming,
increases
the
severity of sulphide corrosion. In
this case the corrosion is
detrimental not only because of
metal loss but also because of
volume of sulphide scale formed
Figure showing the effect of
temperature
and
hydrogen
sulphide
concentration
on
corrosion
rates
in
H2-H2S
environment in carbon steel
(gas oil),

Report on suitability of metallurgy for high sulfur and nitrogen feed in

DHDS

1.5 REFINING OF KUWAIT'S HEAVY

CHALLENAGES
by H.M. Shalaby

CRUDE

OIL:

MATERIALS

Sulfur at a level of 0.2% and above is known to be corrosive to carbon

and low alloy steels at temperature 232 oC to 455oC. At high
temperature conditions, the presence of Naphthenic acids was found to
increase the severity of sulfidic corrosion.
Presumably, the presence of these organic acids disrupt the sulfide film
thereby promoting sulfidic corrosion on alloys that would normally be
expected to resist this form of attack (i.e., 12% Cr and higher alloys).
When sulfur is the only contaminant, McConomy curves, with other
factors, are used to predict the relative corrosivity of crude oils and
their various fractions. Important elements include:
1.
The increased severity of corrosion with sulfur
concentration and service temperature between 250 oC and 400oC,
and
b.
2. The benefit of increased Cr content in steels to reduce the
corrosion rates.
c.
3. The McConomy curves are useful in estimating the
corrosion rate that will be expected based solely on sulfur content.
a.

Report on suitability of metallurgy for high sulfur and nitrogen feed in

DHDS

1.6
ENGINEERING
STANDARD
CONSIDERATION IN DESIGN by IMP

FOR

CORROSION

Report on suitability of metallurgy for high sulfur and nitrogen VGO feed in
DHDS

Effect of temperature and hydrogen sulfide content on hightemperature H2S/H2h2s/h2 corrosion of carbon steel (gas oil
desulfurizers) 1 mil/yr = 0.025 mm/yr
2.0
OPERATIONAL HISTORY
The following are the important parameter before and after change
over to VGO feed from material and corrosion point of view.
Sl
No.

Feed
rate
and Original
impurities level
Design
Diesel

VGO

1
2
3
4

Feed rate (m3/hr)

Sulphur (Wt% max)
Nitrogen (ppm)
Stripper
Inlet
Temperature
Hydrogen in stripper
feed

78.4
2.8
800
290

Chemical analysis
corrosion scale:

results

161.2
1.45
120
270

24701.61 ppm 32423.13

vol.%
ppm vol.%
of

the

stripper

S.NO. TEST

RESULTS

UNIT

1. Moisture content
@ 100C
2.
Loss on ignition
3. Fe as Fe2O3
4. Silica as SiO2
5. Sulphide

4.37

%
12.42
68.82
12.24

2.67

bottom

pump

%
%
%
%

3.0 CORROSION BEHAVIOUR AND MATERIAL SELECTION

The composition of Reactor Feed, Reactor effluent streams and Amine
column feed will change due to increase in S & N2 content of the
feedstock. As a result, this is expected to affect the corrosion behavior
as discussed below,
3.1 Reactor Feed System
3.1.1 Up-stream of the Hydrogen Injection Point:
Report on suitability of metallurgy for high sulfur and nitrogen VGO feed in
DHDS

The feed circuit upstream of the Hydrogen injection point is

susceptible to corrosion due to presence of Sulfur (>2.8 wt %) /
dissolved H2S in the feed. The corrosion phenomena normally occur
above 240 deg C in case of high temperature Sulfur corrosion &
Naphthenic Acid corrosion. High temperature Sulfidation begins at
metal temperature above 260 deg C (Ref. API 571, 4.4.2.3) to
Carbon Steel metallurgy necessitating up gradation. The corrosion rate
largely depends on the amount of these impurities present in the feed,
temperature and turbulence.
Equipment and piping of the Circuit:
SL.
No.
1.

Equipment

2.

Piping:
P01.

02-V-01
02V01

Temperature
45(In
VGO
800C)
to 45(In
VGO
800C)

Material

Remarks

case of CS
Temp is

Satisfactory

case of CS
Temp is

Satisfactory

3.1.2 Down-stream of the Hydrogen Injection Point (Up to

Reactor):
After the Hydrogen injection point, susceptibility to Hydrogen attack
and high temperature H2-H2S corrosion also becomes prevalent as the
temperature of the feed is increased. The threshold temperature for
H2-H2S corrosion in Carbon Steel depends on the amount of H2S
introduced with the recycle gas, but mostly it is 246 deg C. Hydrogen
attack becomes a material consideration in the Reactor feed system
above 232 deg C (H2 partial pressure > 50 psia : Ref API 941).
However, As per API 571 H2&H2S corrosion in CS material is very
much prominent at 260 deg C. as shown in the Modified CouperGorman curve above under Ref. of API 571.
The curve indicates higher corrosion rates are found more in
gas oil desulfurizers and hydrocrackers than naphtha
desulfurizers by a factor of almost 2.
Based on above considerations, the existing metallurgy of
equipment / piping, Increase in Sulphur content to a level of
2.8 wt % in the feedstock would not result into any significant
corrosion attack in the Reactor feed circuit up to the I-stage
Reactor.
Equipment and piping of the Circuit:
SL.
No.

Equipment

Temperature

Material

Remarks

Report on suitability of metallurgy for high sulfur and nitrogen VGO feed in
DHDS

1.
2.

02-E-01A
(Shell)
02-E-01B
02-E-01C
02-E-01D
02-E-01E

80-100

CS, NACE

Satisfactory

CS, NACE
CS
AS(P11)
AS (P11)

02-E-02

106 - 130
150-200
200-236
236-270.6
(289 at EOR)
270.6-316

02-F-01
02-R-01
02-R-02

305- 357
374
374

AS+SS321
CLAD
SS321H
AS+SS347
AS+SS347

Satisfactory
Satisfactory
Satisfactory
Minor corrosion in high
Sulphur service
Satisfactory

Piping:
E01A to E1B
E1B to E1C
E1C to E1D
E1D to E1E
E1E to E02
E02 to F01
F01 to R01
R01 to R02

106
150
200
236
316
SS
SS
SS

CS
CS
CS
CS
AS (P11)
SS321
SS321
SS321

Satisfactory
Satisfactory
Satisfactory

Satisfactory

3.2 REACTOR EFFLUENT SYSTEM

The material selection for Reactor Effluent System from 1 ST Reactor to
2nd and 2ND Reactor bottom to Reactor effluent exchanger 02-E-02 &
02-E-03 is based on the high temperature (> 246 Deg C) H2-H2S
corrosion and High temperature (232 deg C) H2 attack. However, the
corrosion rate largely depends upon the temperature and the partial
pressures of H2S / H2. In case of increase in S content in the feed VGO
from the designed value, the H2S partial pressure in the Reactor
effluent would increase. The following are the material and
temperature configuration.
Acceptable limit for corrosion rate in CS metallurgy is 10 mpy (0.25
mm/yr) as per M/s Chevrons and metallurgy upgradation required as
per the following limiting criteria mentioned below
1.1

1.1 Due to high temperature H2-H2S corrosion.

a) 246 deg C for H2S partial pressure of 100 psia (7 Kg/cm2)

b) 252 deg C for H2S partial pressure of 10 psia (0.7 Kg/cm2)
c) 274 deg C for H2S partial pressure of 0.1 psia (0.07 Kg/cm2)
d) 382 deg C for H2S partial pressure of 0.01 psia (0.007 Kg/cm2)

1.2

1.2 Due to high temperature H2S corrosion.

Report on suitability of metallurgy for high sulfur and nitrogen VGO feed in
DHDS

a) 288 deg C for H2S concentration greater than 2500 ppmw

b) 299 deg C for H2S concentration of 2500 ppmw
c) 311 deg C for H2S concentration of 800 ppmw
d) 318 deg C for H2S concentration of 150-200 ppmw
e) 321 deg C for H2S concentration of 30-100 ppmw
Criteria 1.1 b) is applicable at reactor outlet circuits and 02-E-02 & E03 heat exchanger.
Equipment and piping of the unit:
SL. Equipment Temperatur
No.
e
02-E-02
371-300
(T/S)
02-E371-272
03(T/S)
02-E299-275
01E(T/S)
02-E275-245
01D(T/S)
02-E245-211
01C(T/S)
02-E211-168
01B(T/S)
02-E168-135
01A(T/S)
02-V-32
141
02-AC-01
96-65
02-E65-50
05(S/S)
02-V-03
50
Piping:
R01 to R02 357
R02 to E02
371
E02 to E03
371
E03 to E1E
299
E1E to E1D 275
E1D to E1C 245
E1C
to 211
E01B
168
E01B
to 141
E01A
96
E01A
to 65
V32
50

Material

Remarks

Tube: SS321

Satisfactory

Tube: SS321

Satisfactory

Tube: SS321

Satisfactory

Tube: SS321

Satisfactory

AS (T11)

Satisfactory

CS

Satisfactory

CS

Satisfactory

CS
CS
Shell: CS
T/B: SS316L
CS, NACE

Satisfactory
Satisfactory
Satisfactory

SS
SS
SS
SS
AS
AS
CS
CS
CS
CS
CS
CS

Satisfactory
Satisfactory
Satisfactory
Satisfactory
Satisfactory
Satisfactory
Satisfactory
Satisfactory
Satisfactory
Satisfactory
Satisfactory
Satisfactory

Satisfactory

Report on suitability of metallurgy for high sulfur and nitrogen VGO feed in
DHDS

V32
to
AC01
AC01
to
E05
E05 to V03.
This temperature is lesser of the threshold temperatures of H2-H2S
corrosion (246 deg C) and H2 attack (232 deg C) in CS material.
Hence metallurgy is adequate for handling Reactor Effluent stream up
to the inlet of Reactor Effluent Air Cooler.
Naphthenic acid-resistant materials are not needed beyond
the I-stage Reactor, because the acids are destroyed quickly
upon contact with the catalyst.

3.3 Reactor Effluent Air Coolers (REAC) and Outlet piping

The Reactor Effluent stream entering the REAC contains both Ammonia
and Hydrogen Sulfide, which react to form Ammonium Bisulfide. At a
temperatures less than 100 deg C, the Ammonium Bisulfide
crystallizes out of the vapour phase. This may quickly plug up the
REAC tubes and cause severe erosion-corrosion. To prevent plugging of
the REAC tubes, continuous wash water injection is given at the inlet of
REAC. The resultant Ammonium Bisulfide solution is highly corrosive to
Carbon Steel. The presence of small quantities of cyanides and
Ammonium Chloride in the process fluid tends to further accelerate
corrosion.
Detailed study of REAC corrosion by specialists has led to a general
understanding of the following important factors;
a) a) Corrosion rate increases with increase in concentrations of

Ammonia and Hydrogen Sulfide in the process stream.

b) b) Severe corrosion-erosion of the tube / tube ends, particularly
Carbon Steel metallurgy is likely at process fluid velocities in excess
of 20 ft/sec.
c) c) Increased rates of water injection ahead of the REAC tend to
reduce corrosion. Conversely, water injection at less-thanrecommended rates can lead to accelerated corrosion. The
presence of Oxygen and high level of dissolved iron in wash water
leads to rapid corrosion and fouling. Hence, the injection water
must be free of Oxygen (< 15 ppb).
Report on suitability of metallurgy for high sulfur and nitrogen VGO feed in
DHDS

d) d) Good flow distribution of vapour, liquid hydrocarbon and water

phases is essential to prevent corrosion. This is accomplished by

using a balanced inlet as well as outlet piping for REAC and by
keeping fluid velocities high enough to minimize phase separation.
The phase separation problem places a lower limit on the velocities
(>10 fps) in the REAC, while 20 fps corrosion-erosion limit places a
maximum on the permissible velocity range.
e) e) Injection of Sod Polysulfide ahead of REAC helps to reduce
corrosion. The Polysulfide is typically added to the injection water.

To sum up the above, the major factors that affect REAC corrosion are
given below:

Report on suitability of metallurgy for high sulfur and nitrogen VGO feed in
DHDS

The Kp factor for the Diesel and VGO cases are as follows:
Diesel EOR: H2S: 2.459836 & NH3: 0.027305
Kp Factor for Diesel Case: (mol% H2S X mol% NH3) = 0.067165
(Limit <0.2, condition satisfactory)
VGO EOR: H2S: 2.455405 & NH3: 0.106990
Kp Factor for VGO Case: (mol% H2S X mol% NH3) = 0.262705
(Limit <0.2)
Based on above considerations, the following conclusion can
be drawn;
The ammonium bisulphate concentration needs to be checked
in the sour water of cold separator vessel, 02-V-03, and and if
it is more than 8%,.%,.%. Metallurgy up gradation or increase
in wash water injection rate to be done after consultation with
process Licenser.
a) Kp value and NH4HS concentration increases as N2 increases in
the feedstock. Thus, a higher S content can be tolerated in the
feedstock if the N2 content is kept low.
For Kp factor above > 0.2, metallurgy upgradation to Duplex
2205 of the REAC tube bundles and the outlet piping shall be
required. This will allow for higher concentration of NH4HS up
to 12 wt% in separator sour water thereby giving much
greater flexibility for processing feeds even much higher in
Nitrogen and Sulfur.
3.4

Separator Vessels

The Separator vessels normally have very low corrosion rates. The only
major concern is that the incoming process fluid may impinge on one
of the vessel part, causing localized corrosion at that point. The
internal condition of the vessel is to be inspected and if required
impingement baffle of adequate size is to be installed.

Report on suitability of metallurgy for high sulfur and nitrogen VGO feed in
DHDS

3.5

Recycle Gas System

This system is generally found free from significant corrosion. The only
potentially serious materials problem is Sulfide cracking of the Recycle
Gas Compressor piping. However, protection like keeping the
compressor dry with the provision of a good condition mist eliminator
in the Knock Out Drum (KOD) and steam tracing of the suction line
from KOD would prevent the Sulfide cracking.

3.6

Distillation Section

Stripper Inlet
Corrosion in the distillation equipment depends upon temperature, H2
and H2S concentration. H2S corrosion, in absence of H2, begins to
occur at significant rate above 288 deg C, if H2S concentration is
greater than 2500 ppmw. When the temperature exceeds 315 deg C,
corrosion may occur at H2S levels as low as 1 ppm.
Stripper VGO Feed contains:
H2: 32423.13 ppm vol., H2S: 11429.39 ppm vol. & Partial
pressure of H2S is 0.08 Kg/cm2
- AS per M/s Chevron, at 274 deg C temperature, H2 presence and H2S
partial pressure of 0.1 psia (0.07 Kg/cm2) Austenitic stainless steel
material is to be considered.
- As per API 571, H2 & H2S corrosion in CS material is very much
prominent at 260 deg C. as shown in the above in Sl. No. 3.1.2.
Corrosion also becomes double in case of VGO processing.

Details of the metallurgy up gradation required in distillation

section based on above consideration:
SL.
No.

Equipment
02-E-04A

Temperature
(deg. C)
134 -

Material

Remarks

CS,HIC

Satisfactory

Report on suitability of metallurgy for high sulfur and nitrogen VGO feed in
DHDS

(S/S)
02-E-04B
(S/S)
02-E-04C
(S/S))
02-E03(Shell
side)
02-C-02

Piping:
V03 to E4A
E4A to E4B
E4B to E4C
E4C to E03
E03 to C02

CS,HIC

Satisfactory

-243 (In CS,HIC

case of VGO
Temp is 2430C)
243-290
CS+SS321
(Increased to CLAD
290)

Satisfactory

52
134
- 243
- 290
(Increased to
290)

Satisfactory
Satisfactory
Satisfactory
Satisfactory
Increase
corrosion
anticipated.

VGO case temp.

Increased from 270
to 290 deg. C,
Material
satisfactory.
290-268
CS+SS410 Inlet
temp.
(Inlet
and Clad up to increased to 290
bottom)
tray
no. and bottom to 268
13.
deg. C. Corrosion
Tray:
anticipated at CS
SS410.
part
CS
CS
CS
CS
CS

in
rate

Stripper Bottom:
The streamsteam analysis of the stripper bottom does not show any
Sulphur connects. However, the final product indicates the 0.2%
Sulphur in the product. The stripper top shall contain the most of the
Sulphur in H2S form. The bottom portion shall also contain the Sulphur
in organic form and some portion in H2S form. Sulphur contents is also
anticipated incase of poor stripping. So corrosion is also anticipated in
the stripper column bottom portion of the shell, piping and 02-E-04C
stripper feed/ bottom exchanger tube side.
Based on the literature survey indicates the Sulfur at a level of 0.2%
and above is known to be corrosive to carbon and low alloy steels at
temperature 232oC to 455oC. At high temperature conditions, the
presence of Naphthenic acids was found to increase the severity of
sulfidic corrosion. Presumably, the presence of these organic acids
disrupt the sulfide film thereby promoting sulfidic corrosion on alloys
that would normally be expected to resist this form of attack (i.e., 12%
Report on suitability of metallurgy for high sulfur and nitrogen VGO feed in
DHDS

Cr and higher alloys) (Ref. Workshop on Corrosion and Protection of

Metals by H.M. Shalaby)

Equipment and piping of the unit:

SL
.
No
.

Equipment

Temperature

Material

Remarks

02-E-04C
(T/S)
02-E-04B (T/S)
02-E-04A
(T/S))
02-AC-03
Piping:
C02
(Bottom) to
E4C
E4C to E4B
E4B to E4A
E4C to AC03
AC03
to
E07A/B

268 -

CS
CS
CS

Corrosion
anticipated.
Satisfactory
Satisfactory

162-65

CS

Satisfactory

268

CS

Corrosion
anticipated.

-162

- 162
162
65

CS
CS
CS
CS

Satisfactory
Satisfactory
Satisfactory
Satisfactory

4.0 CONCLUSION
The composition of Feed as well as Reactor effluent streams and feed
to distillation section has been changed due to increase in S & N2
content of the feedstock. This would affect the corrosion behavior of
these streams.
Accordingly, an attempt waswere made in this study to check the
adequacy of the existing material and hardware for processing
feedstock of higher S & N2 content than specified in order to avoid
unacceptable corrosion rate resulting into failures.

Report on suitability of metallurgy for high sulfur and nitrogen VGO feed in
DHDS

Based on the above study, an increase in corrosion rate is anticipated

in some of the equipments and piping circuits. The reactor feed as
well as reactor effluent circuits are already protected by using
austenitic steels of stabilized grade.
The 02-E-03, stripper feed exchanger Shell and tube side is protected
with SS310 material with low Sulphur condition (Diesel Mode) at low
temperature i.e. 270 deg. C. However, the piping downstream of
the exchanger to column is of CS material having 3MM
corrosion allowance and NACE. In the present case of VGO the
stripper feed temperature has been increased to 290 deg.C
and column bottom temp. to 268 deg.C. Due to increase in
temperature and H2S concentration in the presence of hydrogen
accelerated corrosion is anticipated. Based on the above following
metallurgical up gradations are proposed to avoid frequent stripper
bottom chockage with corrosion scale.
It may also be noted that VGO stream contain higher %age of
Naphthenic Acid compared to the other stream from CDU/VDU.VDO.
The Naphthenic acid corrosion is not considered in the original design
of the unit and stream data is also not available. It may be noted
incase of increase in Naphthenic acid, the corrosion trend shall be
changed. In that case material changes shall be required according to
the Naphthenic acid corrosion in reactor feed circuits.
It may also be noted that in case of Naphthenic acid corrosion or
corrosion due to high Sulphur in the reactor feed circuit, the top
catalyst bed of the first reactor mayreactor may get chocked with
sulphide scale, resulting in higher pressure drop across that bed.

Report on suitability of metallurgy for high sulfur and nitrogen VGO feed in
DHDS

5.0 RECOMMENDATIONS
The following may be needed to avoid unacceptable corrosion rate
resulting into failures and pump chockage:

5.1 Metallurgy up gradation from CS to Austenitic steel shall be

required for the stripper feed piping from 02-E-03 to 02-C-02.
5.2 The stripper column shell below tray no. 13. The CS portion needs
to be upgraded to austenitic steel lining. Based on the SS410 lining
in other units (OHCU), as well as, in the top portion of the column.,
SS410 lining may be considered.
5.3 The stripper bottom circuit from column to Pump 02-P-5A/B to 02E-4C needs to be upgraded to Alloy steel.
5.4 The tube bundle of the Stripper feed/ bottom exchanger 02-E-04C
(1st) tube bundle up gradation to AS/SS.
5.5

REAC:

The

ammonium

bisulphate

concentration

has

been

increased Kp (mol %NH3 x mol % H2S at inlet to the REAC) > 0.2.
The Process licenser needs to be consulted for any requirement in
increase in wash water injection rate or metallurgy up gradation.
The sour water concentration in 02-V-03 and REAC inlet velocity
needs to be checked.

Metallurgy up gradation of the Reactor Effluent Air Cooler (REAC)

together with the outlet piping shall be required from carbon steel
Report on suitability of metallurgy for high sulfur and nitrogen VGO feed in
DHDS

to Duplex 2205 in case of any of the following process parameters

being exceeded:
a) a) Kp (mol %NH3 x mol % H2S at inlet to the REAC) > 0.2
b) b) % NH4HS in separator sour water > 8 wt% (measured at 02-V-

03)
c) c) Velocity at inlet and outlet piping exceeds 20 fps

5.6 Metallurgy upgradation of the Stripper O/H cooler tube bundles in

02-E-08 is required from Admiral Brass to Duplex 2205 in view of
higher H2S and NH3 concentration. The Diesel case does not
contains NH3. The VGO case contains: H2S 25413 ppm vol. & NH3
- 163.1654 ppm vol.
5.7 The diesel stripper column was inspected during the Jul2009
shutdown and severe corrosion of the top 10 trays of material
SS410 observed. The trays were found to be perforated and
removed in pieces. Considering the sever corrosion of the SS410
trays the top ten tray needs to be upgraded to SS316L material of
austenitic steel.
The above metallurgy adequacy check has been done based on data
provided from as built documents of the Equipment. The above
proposed recommendations need to be vetted by the Licensor (M/s
Axens) prior to initiating any action in this regard.
Submitted for kind perusal,

Sudarshan Kumar
Walekar
DMIP
SPSE

Dattatray

B.

Report on suitability of metallurgy for high sulfur and nitrogen VGO feed in
DHDS

IPM

DGM (TS)
Thru CIPM
GM (TS)

Report on suitability of metallurgy for high sulfur and nitrogen VGO feed in
DHDS

Annexure-I

Stripper O/H Cooler T/B Duplex

SS

Column Feed line from

E03 to C02 with
SS321.
Stripper Column Shell from Tray no. 13 to
bottom portion with SS410 Lining & Tray
no. 1 to 10 with SS316L

Column bottom up to &

including E4C (T/B)
with AS

Report on suitability of metallurgy for high sulfur and nitrogen VGO feed in DHDS

Annexure-I

Stripper O/H Cooler T/B Duplex

SS

Column Feed line from

E03 to C02 with
SS321.
Stripper Column Shell from Tray no. 13 to
bottom portion with SS410 Lining

Column bottom up to &

including E4C (T/B)
with AS

Report on suitability of metallurgy for high sulfur and nitrogen VGO feed in DHDS

Report on suitability of metallurgy for high sulfur and nitrogen VGO feed in DHDS

Report on suitability of metallurgy for high sulfur and nitrogen VGO feed
in DHDS