7.0 Corrosion in Hydroprocessing Units

70
7.0
CORROSION IN HYDROPROCESSING UNITS
Combined M273 Advanced Refinery Corrosion & M183

Materials and Corrosion Engineering
Shell Projects & Technology,
Westhollow Technology Center
Copyright of Shell Brands International AG Shell Projects & Technology, Westhollow Technology Center November 2010 1
OUTLINE
Process Introduction & Overview
Materials of Construction – Generic Overview
Introduce Key Issues
Reaction Section
Effl
Effluent
t Separation
S ti Section
S ti
Fractionation Section
Corrosion Loops
Degradation Mechanisms
PROCESS OVERVIEW – HYDROPROCESSING
Hydrogenolysis of sulfur compounds
The sulfur is combined with hydrogen to form H2S.
Hydrogenolysis
H d l i off nitrogen
it compounds
d
The nitrogen compounds are partly converted into ammonia (NH3)
in the reactor under normal hydrodesulfurization conditions.
Hydrogenation of chlorides
Organic and inorganic chloride compounds are converted to
hydrogen chloride (HCl)
(HCl).
Hydrogenation of unsaturated compounds
Olefins and aromatics compounds are hydrogenated to paraffins.
Hydrogenolysis of oxygen compounds
Naphthenic acids and phenols are the best-known types of oxygen
compounds present in mineral oils and these are converted into
hydrocarbons and water
PROCESS OVERVIEW – HYDROPROCESSING
Hydrotreating/Hydrodesulfurization: may be characterized
as non-destructive hydrogenation:
Feedstock is reacted with hydrogen
h drogen at high temperat
temperatures,
res 300
300-425
425
°C (572-800°F), and elevated pressures, 50-200 bar (725-2900
psig) under presence of a catalyst
Improve product quality without appreciably altering the boiling
range
Metals are simultaneously removed and deposited on the catalyst
Hydrocracking: may be characterized as destructive
hydrogenation
y g
Higher pressures (100-200 bar) (1450-2900 psig)
Produces lower boiling range product (gasoline, kerosene, jet
f l) and
fuel) d thus
h enhances
h yields
i ld off these
h llower b
boiling
ili
components
PROCESS OVERVIEW & CORROSION LOOPS (NHT)
R ti
Reaction, FFeed,
d Effluent,
Effl t and
d Separation
S ti
Loop 3
Loop 7
Loop 4
Loop 2
Loop 1
Loop 5 L
Loop 6
G
Generic
i naphtha
hth hydrotreater
h d t t reactor
t section
ti
DOWN-FLOW FIXED-BED REACTOR
Feedstock enters at top

Catalyst fixed in place
Exothermic reaction
Quench between beds with
recycle gas
Temperatures controlled
ll d at inlet
l
to each bed to maintain catalyst
activity
PROCESS OVERVIEW AND Naphtha Fin Fan Trim Stabilisor
Stabilisor Condenser Cooler Accumulator
CORROSION LOOPS
Vent Gas
Product Stabilization
and
d Fractionation
F i i
Sour Water
LPG
Fin Fan Splitter

Condenser Accumulator
Naphtha
Splitter
Vent Gas
From Cold LP
Separator
L
Loop 6
Sour Water
Reboiler
Light Naphtha
Reboiler
Heavy Naphtha
TYPICAL MATERIALS OF CONSTRUCTION Recycle Gas
Compressor
Wash Water
Fired Heater Reactor Injection
Fin Fan Coolers KO Drum

Mixer
Cold HP
Vent Gas Separator
F d
Feed
Sour Water
Feed Surge Vent Gas

Drum
Feed/Effluent
Exchangers Cold LP
Separator
Feed Charge To Naphtha

Pump St bili
Stabilisor
Sour Water
Black: carbon steel (CS) Red: 321/347/316 SS

Hydrogen Make-Up
Green: Low alloy Cr-Mo steel Yellow: Alloy 825 (Incoloy)
KEY CORROSION ISSUES – COLD FEED SECTION
Aqueous corrosion - Entrained water

Aqueous phase separating at deadlegs
Cl pitting and SCC – Cl may present in feed and H2
makeup p
Dry out point & deadlegs
Dry
y out p
point:
¾ heating an NH4Cl-containing water phase to its dry point
¾ worst corrosion typically
yp y occurring
g at dryy p
point where a hot
concentrated salt solution forms
Sulfidic corrosion if temperature exceeds limit in feed
exchangers
h
Bypass lines, revamps/alterations
KEY CORROSION ISSUES – HOT FEED/EFFLUENT AND REACTION
High temperature hydrogen attack (HTHA)

High concentration H2 at high temperature and high pressure
Relying upon proper materials and IOW control
Sulfidic corrosion by H2/H2S
Large
L quantity
i off H2S iis produced
d d in i reactors
Use of high Cr alloy or stainless steel cladding/piping
Wet NH4Cl corrosion
Any Cl in the feed and hydrogen are converted into HCl (g)
All of significant
g N in the feed are converted into N
NH3 (g)
Wet feed and/or organic oxygen compounds (phenols, organic
acids) are converted to H2O (g)
Affects
ff when
h dew
d point is reachedh d e.g. in deadlegs
d dl
KEY CORROSION ISSUES – COLD EFFLUENT SECTION
Cl-SCC
In any 300 series SS components (or instrument tubing)
Corrosion by wet NH4Cl
In deadlegs and water wash injection
Corrosion by NH4HS
In air coolers, rundown lines, sour water systems, hydrocarbon liquid
andd vapor lines
li
Wet H2S cracking
Sulfide Stress Cracking
HIC and SOHIC
KEY CORROSION ISSUES - FRACTIONATION SECTION
Carryover of water (containing corrosives)

Liquid
Li id water
t containing
t i i NH4Cl saltlt iis entrained
t i d iin th
the
hydrocarbon phase
Main concern is p
prevention of fouling/corrosion
g/ in the column
and overhead system
High
h temperature sulfidic
lf d corrosion
Affects gas oil units or long residue units if bottoms
temperatures are greater than 300300°C C (570°F)
(570 F).
Affects units with fired heaters for feed preheat or for reboil
71
7.1
HYDROPROCESSING UNITS
Feed Preheat and Reaction Sections
FEED & REACTION SECTION CORROSION LOOPS
Loop-1: Cold Feed

Loop-2: Hot Feed (>230°C (or 450°F))
L
Loop-3:
3 FFeed
d Charge
Ch Heater
H t (and/or
( d/ Recycle
R l
Hydrogen Heater
Loop-4: Reactor(s) and
d their
h Effluents
ffl
Vessels/Exchangers: Cold Feed
CS
Wet H2S Mechanisms
Piping: Vent Gas
CS
Feed
Temp
p Limit
Feed Surge
Drum
Feed/Effluent
Exchangers
Feed Charge
CUI Pump
Hydrogen
y g Dry Out Point
Make-Up
Integrity Operating Window HCl Deadleg Corrosion

content
Exchangers: Feed Preheat
CS
1¼C ½M
1¼Cr-½Mo
1¼Cr-½Mo w/405SS clad
Cr-Mo w/321SS clad Sulfidic Corrosion
Piping:
CS
Naph Acid Corr
5 Cr
9 Cr
321 PTA-SCC
347
Chloride SCC
Temp Limit
NH4Cl Corr
H2 Part. Pres (in Deadlegs)
Sulfur
Brittle Fracture
- Temper Embrittlement
Naph Acid - Hydrogen Embrittlement
Integrity Operating Window

Charge Heater
Heater Tubes:
5 Cr
9 Cr
321
347 Sulfidic Corrosion
316Ti/316Nb
Fired Heater
Naph Acid Corr
Skin Temps
p
PTA-SCC
Pass Flows
Chloride SCC
H2 Part. Pres
S l h
Sulphur Creep
Heater Tubes:
5 Cr Recycle Gas (H2) Heater
9 Cr
321 SS
347 SS High Temp H2 Attack
Skin Temps Fired Heater Sulfidic Corrosion
Pass Flows
Creep
p
H2 Part. Pres
Polythionic
y Acid-SCC
Nap Acid
Sulphur

Reactor:
Temp(s) High Temperature Reaction C-0.5Mo w/405SS Clad
High Temp H2 Attack 1¼Cr-½Mo w/321SS Clad
R
Reactor
t
Fired Heater 2¼Cr-1Mo w/347SS Clad
H2 Part Pres
Sulfidic Corrosion
Piping:
Sulphur - Feed 5 Cr
9 Cr
Naphthenic Acid 12 Cr
Quench 321SS
TAN - Feed Hydrogen
PTA-SCC
PTA SCC
Shutdown Protect. Exchangers:
1¼Cr-½Mo
Chloride SCC 1¼Cr-½Mo w/405SS Clad
Cr-Mo w/321SS Clad
HCl – Makeup Gas
Feed/Effluent
F d/Effl t
Temper Embrittlement Exchangers Brittle Fracture
Startup Min Pres Temp
Hydrotest Procedures
Hydrogen Stress Cracking
Copyright of Shell Brands International AG
Integrity Operating Window November 2010 19
H2/H2S CORROSION
Couper-Gorman Corrosion Curves
Vaporized hydrocarbon
Li id hydrocarbon
Liquid h d b
H2/H2S CORROSION VS SULFIDATION (NO H2)
Couper-Gorman Corrosion Curve Modified Mconomy Curves

H2/H2S CORROSION vs SULFIDATION (No H2)
mpy
n Rate, m
orrosion
Couper-
Gorman
Corrosion
dicted Co
Curve Modified Mc
Conomy
Curves
Pred
Temperature, °F
Assuming
g 9Cr-1Mo steel, naphtha,
p 0.5 mole % H2S for Couper-Gorman
p and 0.5 and
1.5 wt% total sulfur content for Mc Conomy.
H2/H2S CORROSION PREVENTION / MITIGATION
Sulfidation in the presence of hydrogen

greatly
tl diff
differ to
t sulfidation
lfid ti without
ith t it
Carbon steel is acceptable up to 230ºC
(450ºF)
Chromium-Mo steels offer limited benefit over
carbon
b steell above
b 230ºC (450ºF)
18/8 stainless steels offer much better
resistance
REACTOR: STAINLESS STEEL OVERLAY WELDING
Purpose:
Protection from sulfidic
corrosion
i byb automatic i
internal weld overlay lining
Issues:
Dilution (chemistry)
Disbonding in service
S i i i (lead
Sensitization (l d to PTA)
Options:
1) Two Layers:
SAW 309 + ES 347
2) Two Layers:
SAW 309 + SAW 347
3) Single Layer:
ES 347 (to 180 mm strip)
SAW: Submergedg Arc Welding g
INSPECTION OF REACTOR LINING CRACKS
Dye Penetrant Test (PT):
PTA-SCC SUSCEPTIBILITY
Susceptible: only when sensitized
If T < 370°C (700°F), not in-service sensitization
Use stabilized Stainless steel grades, e.g.: 321,347, 316Ti
Weld overlay: less susceptible
Use portable instrument to check for Degree Of Sensitization
(DOS testing) after fabrication or in-service to determine
susceptibility (internals,
(internals flanges,
flanges hot circuit)
72
7.2
Brittle Fracture
IMPACT TEST SPECIMENS AND TEST
APPARATUS - SCHEMATICS
IMPACT TESTING MACHINE
IMPACT TEST SPECIMENS
High and Low Toughness
IMPACT TEST SPECIMENS SHOWING
DUCTILE / BRITTLE TRANSITION
TYPICAL TRANSITION CURVE
IMPACT TEST REQUIREMENT (ASME)
hree specimens
erage of th
Cv ft-lb (joule) Ave
W ll Thi
Wall Thickness
k
FIG. UG-84.1 CHARPY V-NOTCH IMPACT TEST REQUIREMENTS FOR FULL SIZE
SPECIMENS FOR CARBON AND LOW ALLOY STEELS, HAVING A SPECIFIED MINIMUM
TENSILE STRENGTH OF LESS THAN 95 ksi, LISTED IN TABLE UCS-23
IMPACT TEST REQUIREMENT (ASME)
CHARPY V-NOTCH
C V NO C IMPACT
C TEST
S REQUIREMENTS
QU N S
TEMPER EMBRITTLEMENT
TEMPER EMBRITTLEMENT
DUCTILE TO BRITTLE TRANSITION CURVES FOR VARIOUS
GRADES OF IMPURITY OF 2.1/4Cr-1Mo STEEL AFTER
EMBRITTLING HEAT TREATMENT
350
J FACTOR= (Si+Mn)(P+Sn) x10000
J=38
300
J=303
J=470
250
200
150
100
50
DATA FROM JSW (1994)
0
-100 -50 0 50 100 150
Temperature
TEMPER EMBRITTLEMENT PREVENTION / MITIGATION
Control amount of embrittlement elements:
For wrought plates, forgings and heavy-wall piping :

(%Si + %Mn)
(%S %M ) x (%
(%P + %S 04 < 100
%Sn)) x 10 00 %w (J factor)
ac o )
Cu content: 0.20 % w maximum
Ni content: 0.30 % w maximum
For the weld metal:

((10x%P + 5x%Sb + 4x%Sn + As)) < 0.15 %w ((X-factor))
%Mn + %Si < 1.1 %w
Cu is 0.20 % maximum
Ni is 0.30 % maximum
BRITTLE FAILURE PREVENTION - GENERAL
Steel properties
Limit flaws
Hydrotesting
Start-up, shut-down
procedures
Brittle fracture of a 0.5Mo vessel that failed after

10 years of service during a hydrotest.
BRITTLE FAILURE
BRITTLE FRACTURE DURING HYDROTESTING
BRITTLE FRACTURE OF THICK WALL EQUIPMENT
BRITTLE FRACTURE
Toughness
Flaw Size Tensile Stress
MIN. PRESSURIZATION TEMPERATURE (STARTUP/SHUTDOWN)
1. Maintain Pressure Stress < 50 MPa (7250 psi) when metal

temp is < 150°C (300°F)
2. Limit heat-up/cool-down rate to < 42°C/hr (76°F/hr)
----------------- or ----------------
More detailed review to account for:

• original properties of steel (impact tested)
• effect of Hydrogen embrittlement
• effect of temper embrittlement
• test block samples
TYPICAL MIN. PRESSURIZATION CURVE
DISSIMILAR METAL WELD CRACKING
HF-Mod CS
UT Crack Indication
DISSIMILAR METAL WELD CRACKING
Mixed materials result in compositional gradients
Microstructures usually include a local hard zone (LHZ)
Hydrogen charging can lead to cracking/disbonding
Hydrogen charging occurs in both hydroprocessing and

aqueous corrosive environments
During shutdowns off hydroprocessing units the hydrogen

solubility decreases and risk of cracking increases
Diff
Differential
i l thermal
h l expansion
i leads
l d to thermal
h l ffatigue
i
73
7.3
R t Effluent
Reactor Effl t & Water
W t Wash
W h
Combined M273 and M183 Course

M273 Advanced Refinery Corrosion
REACTOR EFFLUENT & FRACTIONATION CORROSION LOOPS
Loop-5: Cooled Reactor Effluent to CHPS

Salt Deposition / Wet NH4Cl Salt Corrosion
Water Dew Point Corrosion
Ammonium Bisulfide Corrosion
Water Wash Design
Loop-6: LPS to Stabilizer

bl Column
l
Water Entrainment/Dry Out Point
Loop-7: Recycle & Make-up Gas

Salt Deposition / Wet NH4Cl Salt Corrosion
Ammonium Bisulfide Corrosion
Cooled Reactor Effluent & HPS
Wet NH4Cl/HCl Wash Water
Piping:
Injection CS E h
Exchangers:
321SS Carbon Steel
NH4HS Corr Duplex Duplex SS
Fin Fan Coolers KOSS
Drum
Mi
Mixer Incoloy 825 Incoloy 825
Wet H2S Cracking
Vessels:
CS (PWHT)
Chloride SCC Cold HP CS w/alloy clad
Separator
T (dewpoint)
Sour Water
P(H2)
Vent Gas
Feed/Effluent NH4HS
Exchangers Cold LP
Separator
WW Rate
To Naphtha
Stabilisor WW Quality

Sour Water
DEPOSITION OF NH4- SALTS
log (([NH3] x [HX])

40 70 100 130 160 190 220 250 280 310 340 370 400
T (ºF)
TEMPERATURE EFFECT OF NH3/NH4+
100
90
Lower solubility of NH3 in water 80
at higher temperatures (i.e. less 70

conversion of NH3 to NH4+ at NH4+ in Water
higher temperatures) 60
e Ammonia
NH4HS concentration highest 50
NOTES:
b l
below 75°C (167°F)
- Ionic equilibrium calculated with the HCR02 program
% Mole
- Main process conditions:
Configuration : Single stage HCU & 4 sep. system
Fresh feed rate : 8000 t/d
Presence of HCl increase NH3

Wash water rate : 1000 t/d
40 Wash oil rate : 4000 t/d
Recycle gas rate : 1200 Nm3/ton f.f.
HPS pressure : 170 bar
solubilityy in water
Feed Nitrogen : 2900 ppm wt
Feed Sulfur : 2.9 % wt
30
20
NH3 in Water
NH3 in Vapor Phase
10
NH3 in HC Liquid
0
°C 150 125 100 75 50 25
°F 302 257 212 167 122 77
Air Cooler Temp., °C, °F
F
AMMONIUM CHLORIDE SALT FOULING
“Completely dry” NH4Cl is non-corrosive

NH4Cl foulingg occurs where the local temperature
p drops
p below the salt
deposition temperature. NH4Cl fouling occurs in effluent heat exchangers
and piping
Cold
C ld d
dead
d legs
l in
i hot
h systems are esp. susceptible
ibl to NH4Cl saltl ffouling.
li
The last heat exchanger before the water wash is the most likely place.
In effluent air cooler with insufficient amount of wash water or wash

water has mal-distribution.
Reactor
R t effluent
ffl t exchangers
h can b
be water-washed
t h d intermittently
i t itt tl tot remove
NH4Cl deposits and reduce pressure drop. Special procedures are key to
the success of intermittent water wash
C ld FFeed/Reactor
Coldest d/R Effl
Effluent EExchanger
h
The tube metal temperature, not the bulk flowing temperature,

is what determines the potential location of NH4Cl deposition
Guidelines for maintenance of 20°F higher process tube metal
temperature above the NH4Cl deposition temperature to avoid
f li
fouling
This exchanger operated within potential NH4Cl deposition
zone all of the time without on line mitigation capability (No
continuous/intermittent Water Wash capability)
INTERMITTENT WATER WASH
The NH4Cl deposits can be extremely corrosive when wet

The cumulative damage could be significant if washing is done incorrectly
Key to intermittent water wash
Minimize frequency - wash only when required based upon U-value
and/or
d/ DP monitoring
it i
Minimize the duration of wash – use copious amount of water
Wash completely – ensure proper distribution or wash exchangers
individually, monitor chlorides in the separator sour water until it levels
out.
Remove
R water
t completely
l t l - positive
iti isolation
i l ti (double
(d bl block
bl k & bleed
bl d or
blind) and drain/purge the system thoroughly
WET AMMONIUM CHLORIDE CORROSION
Dry NH4Cll deposits
d become
b corrosive when
h theh temperature reaches
h the
h
dew point of the four component system consists of H2O, NH3, HCl and
hydrocarbon
y vapour.
p
Corrosion rates can be extremely high (~5,000 mpy (or 125 mm/yr)), esp.
at high temperatures
L
Locations
i where
h wet NH4Cl corrosion
i can b be expected:
d
Deadlegs in the reactor effluent systems, especially non-self-draining deadlegs
Last effluent exchangers, esp
esp. subject to repeat intermittently water wash
Continuous water wash injection points and the piping immediately downstream
Top row of the reactor effluent air coolers (REAC)
Cold high pressure separator hydrocarbon feed preheat exchanger to stripper
or fractionator
74
7.4
AMMONIUM BISULFIDE

AMMONIUM BISULFIDE SALT FOULING
Solid NH4HS fouling occurs where the local temperature drops

below the salt deposition temperature. NH4HS deposition
temperatures can be predicted.
predicted
NH4HS precipitation occurs at much lower temperatures than

NH4Cl.
Cl
NH4HS fouling may occur in reactor effluent air coolers that are not
continuouslyy water washed.
Continuous water washing is applied in REAC’s to prevent NH4HS

fouling.
g
Wet NH4HS is corrosive. Dry deposits become corrosive when the

temperature reaches the aqueous dew point
IS A WATER WASH NEEDED?
Process Conditions Water W ash Decision

No water dew point, no salt deposition No water wash needed
Water dew point, but resulting aqueous No water wash needed

salt concentration within Metallurgical
limits
Water dew point, with resulting aqueous Continuous water wash

salt concentration exceeding
metallurgical limits
Salt deposition and surface temperature Continuous water wash

<40°F above water dew point (potential
for wet salts)
Salt deposition and surface temperature Intermittent water wash

> 40°F above water dew p point ((dryy salt
expected)
Note: Safety factor of 20°F for salt deposition and 40°F for water dew point
AREAS MOST SUSCEPTIBLE TO NH4HS CORROSION
General
Condensing and cooling equipment
High velocity and turbulent flow conditions (e
(e.g.,
g letdown valves)
Points of sour water impingement
elbows, tees, weld protrusions
Hydroprocessing Specific
Reactor effluent air coolers ((REACs)) and water coolers
Especially outlet passes where temperatures are cooler
REAC / water cooler outlet piping
Separator outlet level control valves and piping
Cold separator vent and H2 recycle piping
H2S stripper / fractionator overhead condensing system and reflux system
NH4HS SALT AQUEOUS SOLUTION:
- NH4HS Concentration
- H2S dominant systems (H2S:NH3 in Rxt Effluent > 2 mol/mol)
- Equal molar concentrations of NH4+ and HS- in hydroprocessing
units with sour waters at moderate pH (7 – 9)
- NH3 dominant systems (H2S:NH3 in Rxt Effluent < 2 mol/mol)
- NH4HS is less than the stoichiometric amount of NH3
Takeaway Æ Don Don’tt overestimate NH4HS concentration
- Limited solubility of NH3 in water at high temperatures means NH4HS
corrosion is usually a lesser concern at water injection points and air
cooler
l iinlet
l t piping
i i
Takeaway Æ Don’t overestimate NH4HS concentration
FACTORS INFLUENCING NH4HS CORROSION
Affected by:
NH4HS Concentration
Wall Shear Stress (various flow parameters, not velocity per se)
H2S Partial Pressure
Presence of Hydrocarbon
Temperature
Material
M t i l selection
l ti
Wash water distribution
Not strongly affected by:
Chloride concentration
NH4Clhas no effect on NH4HS corrosion but can be corrosive itself
when wet
Cyanides (from stripped SW)
REACTOR EFFLUENT AIR COOLER (REAC) CORROSION
NH3 has low solubility in hot water; therefore, the NH4HS

concentration of the water tends to increase as it goes through
the REAC
The highest concentration, most corrosive NH4HS is at the outlet
of the REAC
Therefore:
Corrosion at or near the REAC inlet is almost always due to wet
NH4Cl or aqueous HCl corrosion.
Corrosion at the REAC outlet and in downstream
piping/equipment is almost always due to NH4HS corrosion.
NH4HS CORROSION PATTERN
May be generalized thinning
Much more likely to be localized in areas of high
turbulence, e.g., around control valves
A Cat Feed Hydrotreater HPLT 1”

1 CS spool upstream LCV
Combined hydrocarbon and sour water exit separator
8 wt% NH4HS
130 psia H2S pp
Predicted NH4HS corrosion
~ 50 % HC/ 50% Sour
S H2O Æ ~ 25 mpy
100% Sour H2O Æ 256 mpy
Actual ~ 400 mpy
py
Upgraded to Alloy 2205
Predict 9.5 mpy 9
EXAMPLE OF REAC NH4HS CORROSION
HCU Reactor Effluent Air Cooler

S
Severe corrosion off the
h outlet
l header
h d box
b
NH4HS – 6 – 8%wt
H2S Partial Pressure – unknown
EXAMPLE OF REAC NH4HS CORROSION
FLOW PATTERN ALSO RELEVANT:

This corrosion occurred only at the top of
the CS piping downstream the injection
point of continuous water wash and was
attributed to Stratified Wave flow with
liquid at the bottom and gases travelling
much faster at the top and hence causing
faster corrosion. Injection
j p
point was
placed too far away from the air cooler.
Annular or Slug Annular flow regime
((a)) preferred
RELATIONSHIP
B
Between concentration,
i velocity,
l i and d H2S pp on NH4HS corrosion
i rate in
i CS
Aqueous
queous Ammonium
o u Bisulfide
su de so
solutions
u o s
Below 2 wt% concentration
Ammonium bisulfide Corrosion
Mildly corrosive to CS
Not very velocity sensitive
Sensitive to H2S partial pressure
2 wt% to 8 wt% concentration
Moderately
M d t l corrosive
i tot CS,
CS increasing
i i CS 2%
with concentration
orros ion
CS 5%
Velocity sensitive
CS 8%
Increasingly sensitive to H2S partial
pressure Co Alloy 8%
Above 8 wt% concentration

Very corrosive to CS,
CS even at low velocity
Increasingly sensitive to H2S partial
pressure Velocity
KEY CONSIDERATIONS FOR CONTINUOUS WATER WASH
Use enough water to lower a NH4HS concentration suitable

for the material of the REAC and downstream piping
pp g
Use sufficient amount water so that
at least 25% of water remains as liquid water after evaporation upon
injection, sometimes via the
h use off recycled
l d sour water (Watch
h out for
f
Good Mixing & Flow Pattern)
Distribute sufficient water to all air cooler tubes (Watch out for Flow
Regime)
If there are significant concentrations of chlorides:
Inject the water so that it quickly scrubs the chlorides out of the effluent
vapor, via the use of spray nozzle and/or static mixers
Alloy
All up the
th piping
i i downstream
d t off the
th injection
i j ti point
i t until
til the
th
scrubbing is sufficiently complete
INJECTION – COUNTER CURRENT SPRAY, NO MIXER
INJECTION – COCURRENT SPRAY
& STATIC MIXER
AIR COOLER - INLET HEADER ARRANGEMENTS
Inlet symmetric, and hydraulically balanced

y y balanced
Outlet hydraulically
Inlet symmetric, but not hydraulically balanced
Outlet hydraulically balanced
Inlet line
Inlet line
Outlet line
Outlet line
Distribution of the process flow through multi-bank air coolers is

highly dependent upon the piping configuration
Balanced flow through the air cooler banks and inlet & outlet piping is
important to reduce the potential for localized corrosion and fouling
of the piping and air cooler tubes.
Corrosion is dependent upon the materials of construction and the
process fluid characteristics However, fouling is independent of
material of construction
A
An unbalanced
b l d flow
fl can create
t high
hi h flow
fl rates
t ini some banks
b k and d low
l
flow rates in others, and variations in the water distribution. These
influence the type, amount, and location of corrosion and fouling
Piping configurations
f that
h increase pressure drop
d through
h h a particular
l
air cooler bank can cause maldistribution of the process flow
Use of a balanced inlet and outlet p
piping
p g configuration
g is the most
common approach to help assure proper distribution to each bank of
the REAC
NH4HS CORROSION
REACTOR EFFLUENT AIR COOLER OUTLET PIPING
Hydrocarbon/Sour Water
mixtures
Substantial
S b t ti l iincrease iin
protection as %vol HC
increases up to 25%, beyond
which it increases gradually.
gradually
Benefit only taken for
turbulent flow regimes
Æ Vapor REACs much more
susceptible than those in 2
separator systems.
systems
General thinning at REAC

outlet piping elbow
75
7.5
WASH WATER QUALITY

WASH WATER QUALITY
Oxygen content < 50 ppb

Enhances chloride pitting
Could form solid sulfur
Wash water delivery
y tanks should be designed
g to exclude
oxygen
pH: 7.0-9.0
Main concern is to avoid
d acidic
d conditions
d and
d avoid
d ffree
caustic
Total Hardness < 2 ppmw as Ca
(< 20 ppb if fluoride is in system)
WASH WATER QUALITY (CONT)
Iron (Fe): < 1ppmw

Concern is fouling
g
Cyanides: nil
Avoid water from SWS that contain sour water from catalytic
crackers and cokers
Chlorides: < 100 ppmw
Any
A chlorides
hl d in the
h water willll not contribute
b to h
halide
l d severity
unless the water totally evaporates
WASH WATER QUALITY (CONT)
Total suspended solids - free of solids that would plug injector
or cause excessive fouling.
A
Ammonia and
d Sulfides
S lf d – case by b case.
Piping and air cooler must be designed for levels experienced
TTotall Dissolved
Di l d S Solids
lid (TDS) – Minimize
Mi i i
Hydrocarbons:
Avoid
A id high
hi h concentration
i off different
diff hydrocarbons
h d b than
h normally
ll found
f d
in reactor effluent
Hydrocarbons can take up volume that was really intended for water
and reduce intended water wash
USE OF SOUR WATER RECYCLE
Used to achieve a 25 %wt minimum liquid water remaining

after injection
Used in systems where primary objective of water wash is
to control NH4Cl corrosion, not NH4HS
Results in higher NH4HS concentration in the air cooler
inlet p
piping,
p g, depending
p g upon
p % vaporization
p
Results in higher dry tube NH4HS concentration
Preferable to use all fresh water if water sources are

available and if sour water stripping system can handle.
LOSS OF WASH WATER
Plugging A/C tubes

Salts remains when water is reintroduced,, resulting
g corrosion,,
mainly by NH4Cl
Plugged tubes in the top row may be subject to “pull-outs” when
unitit is
i restarted
t t d
Freeze rupture in cold climate
Work-hardening
W k h d i by b freezing
f i may resultlt in
i sulfide
lfid stress
t cracking
ki
upon restart
Hi h corrosion
High i rates
t
A/C inlet - HCl and/or wet NH4Cl
A/C outlet
tl t if d
dew
w point
i t iis reached
h d - NH4HS
LOSS OF WASH WATER, CONT’D
Each Unit should have a procedure for response to loss

off wash
h water
t
Cut-out fresh feed or fixed period of time for continued
operation without wash water
For spared wash water pumps, put priority on pump
repairs Limit risks associated with having only the spare
repairs.
pump serviceable
p
For unspared wash water ppumps,
p , have plan
p in place
p
before pump failure occurs
REAC AND WATER WASHING CHALLENGES
Ongoing challenges:
• Inadequate amount of wash water

• Maldistribution of wash water (single/multiple injections)
• Fouling by iron sulfide corrosion products
Business-driven changes
g to increase profitability:
p y
• Increased unit throughput

• Lower quality feeds
• Higher activity/severity catalysts
• More demanding finished product specifications
REAC AND WATER WASHING CHALLENGES
Historical approach – cope with known changes:

Heavy reliance on rules of thumb (concentration & velocity limits)
Increased inspection (more frequent & extensive)
Many changes not recognized (“process creep”):
Inadequate
q process
p monitoring
g
Inadequate inspection to detect very localized corrosion
Impact of changes on corrosion not understood
Industry record indicates approach not adequate:
Unscheduled shutdowns
shutdowns, major loss-of-containment incidents
Case for action – develop & implement best practices
INSPECTION
Focus on detecting very localized damage:

Erosion-corrosion
Erosion corrosion producing grooving or washouts (NH4HS)
Pitting or under-deposit attack (NH4Cl)
Wet H2S cracking
May need to look for fouling deposits
Corrosion and fouling patterns can vary widely:
From system to system
Within the same system
Related to flow regime present (multi-phase systems)
INSPECTION
Inspection challenge – find very localized damage when presence

and location are not very predictable
Appropriate inspection methods (spot UT is most often
inadequate)
Extensive coverage
Areas of high velocity, turbulence, impingement
Areas of stagnant or low flow (dead legs !!)
REAC header boxes very difficult to inspect properly
76
7.6
COLD LPS TO STABILIZER COLUMN

Cold LPS to Stabilizer Column Piping:
CS
Ammonium Bisulfide
Exchangers:
Wet NH4Cl Salts Carbon Steel
Cold HP
Separator 5 Cr
Wet HCl (dry out) Vessels:

Naphtha
Stabilisor
CS (PWHT)
Sour Water
CS w/alloy clad
Vent Gas
Cold LP
Separator
Wet H2S Mechanisms
Sour Water
Integrity Operating Window NH4HS pH Reboiler

Chlorides
COLUMN FEED PREHEAT EXCHANGERS
Cases
It couldn’t have occurred without water 1. Exchanger tubes failed
due to Chloride SCC
2. Exchange
g tubes failed
by NH4Cl corrosion
3. Completely blocked by
NH4Cl fouling
Recycle Gas Recycle Gas
Piping:
Compressor CS
Ammonium Bisulfide Reactor

Compressor:
CS
Wet NH4Cl Salts KO Drum
D
Vessels:
CS (PWHT)
Wet H2S Mechanisms Cold HP
Vent Gas Separator
Feed
Dissimilar Weld Cracking

Feed Surge
Drum
NH4HS
HPS Temp
Feed Charge
Pump
H t Tracing
Heat T i

Hydrogen
y g Make-Up
p
77
7.7
Product Stripping and

S bili i
Stabilization
Combined
b d M273 and d M183 Course
Original Session 4.3, in this package is 7.3
PRODUCT TREATING CORROSION LOOPS
• Loop-8:
p Stabilizer Bottoms/Fractionator
/ Btms
Sulfidic Corrosion
• L
Loop-9:
9 Stabilizer
St bili Overhead
O h d & LPG
HCl dew point and ammonium chloride corrosion
Ammonium bisulfide corrosion
Wet H2S cracking
Brittle fracture
NAPHTHA HYDROTREATER STABILIZER/SPLITTER SECTION
Naphtha Fin Fan Trim Stabilisor

Stabilisor Condenser Cooler Accumulator
Vent Gas
Sour Water
LPG
Fin Fan Splitter

Condenser Accumulator
Naphtha
Splitter
Vent Gas
From Cold
F C ld LP
Separator
Sour Water
Reboiler
Light Naphtha
Reboiler
Heavy Naphtha
Stabilizer Bottom Piping:
CS
Naphtha
N hth 5C
Cr
Stabilisor
9 Cr
Sulfidic Corrosion
Exchangers:
CS
CUI
Naphtha 5 Cr
Splitter
CS w/alloy
/ ll clad
l d
From Cold LP
Separator
Vessels:
CS
CS w/alloy clad
Reboiler
Temp
Sulfur
SULFIDIC CORROSION
• Higher
g e corrosion
co os o rates
a es than
a predicted
p ed c ed by McCo
McConomy
o y cu
curves
ves for
o CS, 5Cr,
5C ,
9Cr in fractionator/distillation equipment in Hydrotreaters and
Hydrocrackers
U
Upgrades
d tot 5Cr,
5C 9Cr
9C show
h continued
ti d corrosion
i
Corrosion most aggressive in furnace tubes, piping
phase separation in reboiler furnace tubes (stratified flow –
convection tubes)
P ibl mercaptans,
Possibly t di lfid H2S
di-sulfides,
NACE DATA
SULFIDATION IN HYDROTREATER REBOILERS
Wet NH4Cl Salts Stabilizer Overhead & LPG Piping:
CS
Inhibitor Injection
Fin Fan Trim Stabilisor

Exchangers:
Wet HCl Corrosion Condenser Cooler Accumulator
CS
Naphtha
p
Vent Gas
Stabilisor Duplex SS
Ammonium Bisulfide
Vessels:
CS (PWHT)
Sour Water
Wet H2S Mechanisms

LPG
Brittle Fracture Temp (Col NH4HS

(Autorefrigeration) Top)
From Cold LP Inhibitor Chloride

Separator
S lt Temp
Salt T HPS Separation
S ti

Reboiler
SOURCES OF OVERHEAD CORROSIVES
• H2S, HCl & NH3 carryover:

– In HT and LT separator liquid streams
– Water carryover from LT separators
STABILIZER OVERHEAD CORROSION MECHANISMS
HCl dewpoint and wet NH4Cl corrosion:

Cold
C ld nozzles
l ini stripper/stabilizer
ti / t bili upper column
l
Overhead piping, especially cold deadlegs
Air cooler tube inlet
Ammonium Bisulfide corrosion:

Air cooler tube outlet
Rundown piping
STABILIZER OVERHEAD CRACKING MECHANISMS
Wet H2S Cracking:
HIC/SOHIC/Blistering
HIC/SOHIC/Bli i
SSC
Brittle fracture in case of low temperature due to

depressurization
DEAD LEG ON VGO-HT STABILIZER OVERHEAD LINE
DEBUT COL. O/H PIPING LAYOUT
Wash water and inhibitor

distribution is problematic
SUMMARY
Successful Corrosion Abatement requires:
Monitoring of Cl, pH, Iron, corrosion

Essential
Monitoring Stabilizer overhead temperature against

dewpoint
p temperature
p
Essential
Application of Neutralizers
Use correct type
Application of Filming Additives

O l if strictly
Only i l needed
d d
78
7.8
DEVELOPING A SITE SPECIFIC BEST
PRACTICE ON WATER WASH FOR
Additional details
IMPORTANCE OF WATER WASH
IMPLEMENTATION OF WATER WASHING BEST PRACTICE
IN AN OPERATING UNIT
1. Conduct a thorough review of water wash and integrity

management practices in HCU’s and HTU’s:
• Multi-discipline team of specialists
• Focus on ammonium salts fouling and corrosion
• Identify and assess risks
• Develop recommendations to mitigate significant risks
IMPLEMENTATION OF BEST PRACTICE (2)
2. Review all aspects

p of the REAC system:
y
Process data and process simulation
y
Analytical data and methods used
Corrosion data and inspection histories
Materials selection
Design and operation of water washes
g considerations
Other related design
Monitoring of key process parameters
Inspection strategies
3. Identify deviations from best practices
4. Perform risk-based gap analysis to determine which deviations are

significant and warrant mitigation
5. Identify and agree an optimum set of strategies that:
Meet unit operating plan
Achieve desired level of risk mitigation and unit reliability
Strategies may involve:

Clearly defined IOW
Materials of construction upgrades
Design improvements
Inspection methods,
methods coverage,
coverage and frequency
6. Use risk assessment tools used to:

Evaluate options
Rank alternatives
Assist in capital expenditure decisions
IMPLEMENTATION OF BEST PRACTICE VIA A “HEALTH CHECK”
¾ Assessment to determine whether unit has significant

gaps comparedd to best
b practices
¾ Identify units with highest potential reliability risks
¾ Assess priority for conducting detailed water wash
reviews
¾ Applicability of “health check” confirmed
IMPLEMENTATION OF BEST PRACTICE VIA A “HEALTH CHECK”
HYDROPROCESSING FOCUS AREA

DHT REACTOR EFFLUENT CORROSION AND FOULING REVIEW
GAP IDENTIFICATION AND RISK ASSESSMENT
THE REVIEW PROGRAM CONSISTS OF 4 PROCESS STEPS
HYDROPROCESSING FOCUS AREA

DHT REACTOR EFFLUENT CORROSION AND FOULING REVIEW
GAP IDENTIFICATION AND RISK ASSESSMENT
Gather Compute Evaluate Document
|
|
Process simulations Document
Calculations Review
Summary Feedback
Wrap-up
THE REVIEW PROGRAM CONSISTS OF 4 PROCESS STEPS
The water wash review is just the first step...
WW Sustained
e e
Review Implement
Operation
| |
|
Summary Solution Development Routine Monitoring
p
Gaps Procedures
MOC
Recommendations Hardware
d
Monitoring
Inspection
CONCLUSIONS
Water wash best practices have been developed and successfully

implemented
p to improve
p integrity
g y and reliabilityy of REAC systems
y in
hydroprocessing units
Key elements include:
o Multi-discipline
M l i di i li approach
h
o State-of-the-art process modeling tools
o NH4HS corrosion
i prediction
di i model
d l ffrom S
Sour W
Water JIP
o Clearly defined Integrity Operating Window
o Routine
R i monitoring/control
i i / l off kkey process parameters
o Improved inspection techniques and strategies focused toward
very localized corrosion
Copyright of Shell Brands International AG 115

INTEGRITY OPERATING WINDOW (IOW)
Defined set of process parameter limits based on:

• System
y design
g
• Materials of construction
• Assessment of integrity
g y risk (threats)
( )
Each process unit has a specific set of key process parameters with limiting
values
Two key
k aspects off IOW:
• Requires routine process monitoring of key parameters
• R
Requires
i corrosion
i rate prediction
di i (i
(i.e., understanding
d di off
relationship between key process parameter values and
corrosion rate)
INTEGRITY OPERATING WINDOW
Routine process monitoring of key parameters:

• Take samples at correct locations
• Use proper sampling/handling procedures
• Analyze by proper methods (complex sour water solutions)
• Appropriate
pp p monitoring
g frequency
q y
• Leads to timely operator response
Operation outside IOW requires Management Of Change (MOC)
considerations
Shell Projects & Technology, Westhollow Technology Center November 2010 118

7.0 Corrosion in Hydroprocessing Units

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7.0 Corrosion in Hydroprocessing Units

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70

Combined M273 Advanced Refinery Corrosion & M183

Feedstock enters at top

Fin Fan Splitter

Fin Fan Coolers KO Drum

Feed Surge Vent Gas

Feed Charge To Naphtha

Black: carbon steel (CS) Red: 321/347/316 SS

Aqueous corrosion - Entrained water

High temperature hydrogen attack (HTHA)

Carryover of water (containing corrosives)

Combined M273 Advanced Refinery Corrosion & M183

Loop-1: Cold Feed

Integrity Operating Window HCl Deadleg Corrosion

Integrity Operating Window

Integrity Operating Window

Skin Temps Fired Heater Sulfidic Corrosion

Integrity Operating Window

Couper-Gorman Corrosion Curve Modified Mconomy Curves

 Sulfidation in the presence of hydrogen

Dye Penetrant Test (PT):

Control amount of embrittlement elements:

For wrought plates, forgings and heavy-wall piping :

For the weld metal:

Brittle fracture of a 0.5Mo vessel that failed after

Flaw Size Tensile Stress

1. Maintain Pressure Stress < 50 MPa (7250 psi) when metal

More detailed review to account for:

 Mixed materials result in compositional gradients

 Microstructures usually include a local hard zone (LHZ)

 Hydrogen charging can lead to cracking/disbonding

 Hydrogen charging occurs in both hydroprocessing and

 During shutdowns off hydroprocessing units the hydrogen

Combined M273 and M183 Course

Loop-5: Cooled Reactor Effluent to CHPS

Loop-6: LPS to Stabilizer

Loop-7: Recycle & Make-up Gas

Integrity Operating Window

log (([NH3] x [HX])

 Lower solubility of NH3 in water 80

at higher temperatures (i.e. less 70

 Presence of HCl increase NH3

“Completely dry” NH4Cl is non-corrosive

 In effluent air cooler with insufficient amount of wash water or wash

 The tube metal temperature, not the bulk flowing temperature,

The NH4Cl deposits can be extremely corrosive when wet

Combined M273 and M183 Course

 Solid NH4HS fouling occurs where the local temperature drops

 NH4HS precipitation occurs at much lower temperatures than

 Continuous water washing is applied in REAC’s to prevent NH4HS

 Wet NH4HS is corrosive. Dry deposits become corrosive when the

Process Conditions Water W ash Decision

Water dew point, but resulting aqueous No water wash needed

Water dew point, with resulting aqueous Continuous water wash

Salt deposition and surface temperature Continuous water wash

Salt deposition and surface temperature Intermittent water wash

 NH3 has low solubility in hot water; therefore, the NH4HS

A Cat Feed Hydrotreater HPLT 1”

HCU Reactor Effluent Air Cooler

FLOW PATTERN ALSO RELEVANT:

Above 8 wt% concentration

Use enough water to lower a NH4HS concentration suitable

Inlet symmetric, and hydraulically balanced

 Distribution of the process flow through multi-bank air coolers is

Sulfidation in the presence of hydrogen

Mixed materials result in compositional gradients

Microstructures usually include a local hard zone (LHZ)

Hydrogen charging can lead to cracking/disbonding

Hydrogen charging occurs in both hydroprocessing and

During shutdowns off hydroprocessing units the hydrogen

Lower solubility of NH3 in water 80

Presence of HCl increase NH3

In effluent air cooler with insufficient amount of wash water or wash

The tube metal temperature, not the bulk flowing temperature,

Solid NH4HS fouling occurs where the local temperature drops

NH4HS precipitation occurs at much lower temperatures than

Continuous water washing is applied in REAC’s to prevent NH4HS

Wet NH4HS is corrosive. Dry deposits become corrosive when the

NH3 has low solubility in hot water; therefore, the NH4HS

Distribution of the process flow through multi-bank air coolers is

Used to achieve a 25 %wt minimum liquid water remaining

Preferable to use all fresh water if water sources are

Air cooler tube inlet

Monitoring of Cl, pH, Iron, corrosion

Monitoring Stabilizer overhead temperature against

Application of Filming Additives

Water wash best practices have been developed and successfully