Hydroprocessing

Units
 Common Types of
Hydroprocessing Units

• Hydrotreaters
• Hydrocrackers
• Hydrogenators
• Hydrofiners
 Hydrotreating
• Hydrogen injected into feed
• Sulfur and nitrogen organic compounds
converted to H2S and NH3
• Effluent is cooled, sent to separator vessels
• Water injected upstream of air cooled
exchangers to control corrosion
• Gases recycled through compressor
• Liquid hydrocarbons sent to fractionation
section
Fig 7.1 Simplified Flow Diagram of
Hydrotreater Unit
 Hydrocracking

• Feedstock mixed with hydrogen

• Mixture is heated
• Passed through catalyst-filled reactors
• Reactor effluent then cooled
• Gases recycled back; liquid sent to
distillation
Fig 7.2 Flow Diagram of Single-Stage
Hydrocracking Unit
Variations on Hydroprocessing

• Vacuum resid desulfurizers

• High-pressure amine absorbers

• Distillation systems can vary by unit

High-Temperature Hydrogen
Attack
• Decarburization can weaken metal
• Methane can form at interstices
• Cr and Mo alloys can reduce potential
damage
• Base materials also need protection

Chapter 1
High-Temperature Hydrogen
Attack
Fig 1.10 and Appendix O (API 941)
 C – ½ Mo Steel in HTHA Service
• Unexpected failures below old curves on API 941
• Thought explained by carbide stability which is a
function of heat treatment temperature – still not
well understood
• Worst damage is often at weld HAZs. Difficult to
inspect for – requires special shear wave UT
• Most owners are removing C-1/2Mo piping and
equipment where possible. Replacement is 1-1/4
Cr-1/2 Mo steel.

Chapter 1
 High-Temperature H2–H2S
• Sulfur compounds converted to H2S under
reactor conditions
• Areas susceptible:
– Reactor feed downstream from hydrogen
mix point
• Reactor
• Reactor effluent
• Recycle hydrogen gas
– Presence of hydrogen increases H2–H2S
corrosion rates
Chapter 1
Figure 1.9 Corrosion Rate Curves for
H2S/H2 Environments

Chapter 1
High-Temperature H2-H2S (cont)
• Alloys with up to 5% Cr yield no
corrosion protection
• 9% Cr alloys provide only marginal
protection
• 12% Cr is somewhat resistant, difficult
to fabricate, may embrittle
• Austenitic stainless steels (18% Cr)
provide best protection
 High-Temperature H2S
(without Hydrogen)

• Occurs upstream of hydrogen injection point

• Occurs in some fractionator sections, after
hydrogen removal
• Temperatures > 500°F (260°C)
• Hydrogen partial pressures < 50 psi (< 4
kg/cm2)

Chapter 1
 Naphthenic Acid Corrosion
• Affects hot feed piping and equipment
• Vulnerable at high TAN >450°F (232°C)
– Carbon steels
– Cr-Mo steels
– Some 300 series stainless steels
• Best resistance offered by 316L stainless/high-
moly alloys (>2% to 3% Mo)

Chapter 1
 NH4HS Corrosion
• Occurs as reactor effluent stream cools
down
• HIGHLY corrosive to carbon steel tubing
• Accelerated by
– Increased NH4HS concentration
– Velocity
– Oxygen
– Poor flow

Chapter 1
 Ammonium Salt Corrosion

• If chloride partial pressure is high enough,

NH4Cl salts will form when the temperature
falls below the sublimation point
• Wet NH4Cl salts are highly corrosive to
carbon and stainless steels
• Corrosion is localized and difficult to detect.
Low flow areas are especially susceptible

Chapter 1
 Chloride SCC
• Conditions
• Water
• Temperatures >1400F (600C)
• Chlorides present, when concentrated
• Oxygen present
• Tensile stresses present
• Failures often happen after startup
following turnarounds
• Occurs in stainless steel piping in reactor
feed/effluent systems

Chapter 1
 PTA SCC
• Occurs only on austenitic stainless
steels and a few austenitic alloys
• Happens when alloys have become
sensitized by:
– Welding
– Postweld heat treatment
– Exposure to temperatures > 700°F to
750°F (371°C to 454°C )

Chapter 1
 Mitigating PTA SCC
• Stainless steels
– Type 304 or 316
– Type 304L or 316L
– Type 321
– Type 347
– HF Modified
• Nitrogen blanketing
• Keeping metal above the dew point
• Washing with soda ash solutions
 Cracking in Wet H2S
• Sulfide Stress Cracking (SSC)

• Hydrogen Induced Cracking (HIC)

• Stress-Oriented Hydrogen Induced

Cracking (SOHIC)
 SSC
• Affects high-strength ferritic or martensitic
steels
• Affects steels above
– 621 N/mm2 (90,000 psi) in yield strength
– Rockwell C (Rc) 20 to 22 in hardness
• Common in valve stems and trim
• Occurs in rotor materials in centrifugal
recycle gas compressors
• Occurs in hard weldments
Chapter 1
 HIC
• Aqueous corrosion in carbon steel
equipment; H2S >50 ppmw in water phase
• Stepwise cracks linking up hydrogen blisters
• Associated with weldments; primarily in
plates
• Use high quality CS and special fabrication
or 300 series SS clad
• Minimize aqueous corrosion in system

Chapter 1
 SOHIC
• Aqueous corrosion in carbon steel
equipment; H2S >50 ppmw in water phase
• Enhanced by cyanide >20 ppmw in water
phase
• Cracking is dependent on stress
• Associated with weldments; commonly in
HAZ
• Use high quality CS and special fabrication
(w/PWHT) or 300 series SS
• Minimize aqueous corrosion in system
Chapter 1
 Temper Embrittlement
• Occurs in low-alloy steels (2-1/4 Cr-1 Mo)
heated for a long time from 700°F to 1050°F
(371°C to 565°C)
• Brittle fracture occurs near ambient temperature
• Managed by
– Limiting pressurization to 25% until equipment is
above transition temperature
– Restricting residual elements, such as tin, arsenic,
antimony, phosphorus

Chapter 1
Temper Embrittlement

40 Ft-Lb = 54 N-m
(joules)
 Hydrogen Embrittlement
• Dissolved hydrogen trapped within reactor
walls as the metal cools during shutdown
• Embrittlement happens only at
temperatures below 300°F (149°C)
• Occurs only if trapped dissolved hydrogen
is not allowed to escape (is reversible)
• Solution – special cooling procedures
(cooling rates of 50°F/hr to 100°F/hr
[28°C/hr to 56°C/hr])
Chapter 1
 High-Temperature Creep
• At high temperatures, applying a stress
below the yield point causes the metal to
stretch permanently as long as the load is
applied
• Creep eventually causes metal failure
• Feed heater is susceptible

Chapter 1
 Creep Rupture of 347 SS
HSGO HydrofinerTube
Photomicrograph
of sample as
received.
Longitudinal
cracking is visible
in bulged area.

Close up of
longitudinal
cracking on
exterior of
tube.
 Reactor Loop
Must resist the following forms of corrosion:
• High-temperature hydrogen attack
• High-temperature hydrogen sulfide
corrosion
• Aqueous corrosion by ammonium bisulfide
• Stress corrosion cracking (SCC) by
chlorides, sulfur acids
• Wet H2S Cracking
Reactor Feed System Materials
• Use alloys with 5% chrome or better for
sulfidation corrosion (w/o H2)
• After point of recycle hydrogen addition,
higher alloys are required
– Austenitic steels for piping and
exchangers
– Type 321 stainless for exchanger bundles
– Type 321 or 347 stainless for cladding
Reactor Feed Furnace Materials

• Tubes and return bends

– Type 347 stainless steel
– Type 321 stainless steel
• Return bends should be wrought
rather than cast
 Reactor Materials

• Low-alloy steel
• Austenitic stainless steel weld overlays
(Usually too thick for roll-bond cladding)
• 2-1/4 Cr-1 Mo is most common base metal
• 3Cr-1Mo and 1-1/4 Cr-1Mo can be used
• Austenitic stainless (321 or 347) for internals
• Aluminum diffusion coating sometimes
specified for catalyst support screens
Reactor Effluent System Materials
• From reactor outlet temperature down to
500°F (260°C)
– Type 321 for piping and exchanger bundles
– Type 321-clad or type 347-clad for exchanger
shells
– 2.25 Cr-1 Mo / 1.25 Cr-0.5 Mo for exchanger
shell base metal
• Carbon steel for temperatures < 450°F
(< 232°C)
 Effluent Air Cooler Materials
• Many built with carbon steel tubes
• Upgraded to Alloy 825, Alloy 800, or Alloy 400
• Duplex stainless (types 2205/2507) for tubes
and header boxes
• Stainless steel ferrules for inlet/outlet ends of
steel tubes
• Alloy header boxes recommended with alloy
tubes
Ammonium Bisulfide Corrosion
• Occurs in carbon steel when NH4HS
concentration is above about 2%
• Injection water quality is important. Good flow
distribution is critical – use balanced process
piping configuration
• Keep velocity in CS below 20 fps (6 mps) in
piping and exchangers
• Corrosion is often localized. Effluent air cooler
tubes are vulnerable

Chapter 1
 Flow

Tube outlet and header plug (12% NH4HS)

 Effluent Air Cooler Inlet and
Outlet Piping Materials
• Carbon steel piping with 20 ft/s (6 m/s ) limit
• Alloy 800, alloy 825, type 316L stainless,
Alloy 20, and Alloy 2205
• Carbon steel with corrosion allowance of
1/4 in. (6.4 mm)
• 18 Cr-8 Mo stainless steel trim for areas
prone to sulfide stress cracking
High and Low Pressure Separator
Vessel Materials
• Hot separator should be stainless-clad
• Cold separators usually have low corrosion
rates overall
• Shell or heads are most vulnerable to NH4HS
corrosion, from incoming process fluid
• Cold separators with sour water
– HIC-resistant steel
– Entirely clad with type 300 series stainless
Recycle Hydrogen System Materials

• Limit strength and hardness of recycle

gas compressor material
• Keep compressor unit dry
• Use 18 Cr-8 Ni stainless steel for valve
trim
 Distillation Section Materials

• Prone to high-temperature H2S corrosion

• Alloy for temperatures above 500°F to

600°F (260°C to 316°C )
• Carbon steel for temperatures below
500°F (260°C) or absence of H2S
 Reactor Effluent-Distillation
Feed Exchanger Materials
• Tube life highly variable, depending on temperature
and amount of salt
• Cr-Mo steels or austenitic stainless steels generally
perform no better than carbon
• New plant construction often specifies carbon steel
• Alternatives are expensive, sometimes warranted
• Alloy 825
• 6 Moly austenitic stainless steel
• Alloy 625
Corrosion Mechanisms Of Particular
Concern in Hydroprocessing Units
High Temperature Sulfidation Corrosion
• Reactor feed equipment and piping
before recycle hydrogen
• Fractionator Heaters, Columns, and
piping above 500oF (260oC)
Corrosion Mechanisms Of Particular
Concern in Hydroprocessing Units
 High Temperature H2-H2S Corrosion
• High pressure loop above 450oF (232oC)
(Reactor feed piping after recycle
hydrogen, heater, reactor, effluent piping
and exchangers, hot separators)
Corrosion Mechanisms Of Particular
Concern in Hydroprocessing Units
High Temperature Hydrogen Attack
• High pressure loop above 450oF
(232oC) (Reactor feed piping after
recycle hydrogen, heater, reactor,
effluent piping and exchangers, hot
separators)
Corrosion Mechanisms Of Particular
Concern in Hydroprocessing Units
Creep
• Heaters
 
NH4HS Corrosion
• Reactor effluent piping, vessels and exchangers
(severity depends on concentration and velocity)
• Fractionator column overhead equipment and
piping
Corrosion Mechanisms Of Particular
Concern in Hydroprocessing Units
Chloride Corrosion
• Cl SCC in 3xx SS anywhere with liquid water
• Cl salt corrosion in dry point areas (reactor
effluent equipment and piping, hydrogen
recycle equipment and piping, fractionator
feed exchangers)
Corrosion Mechanisms Of Particular
Concern in Hydroprocessing Units

Polythionic Acid Stress Corrosion Cracking

• Sensitized 3xx or 800 in reactor and
reactor effluent stream