Question 25: What are your key factors around amine contactor

operation in hydrotreating units?

JOE RYDBERG (CITGO)
The biggest key factor in amine contactor operation in hydroprocessing units is controlling the lean
amine flow and the lean and rich amine loading. We have seen corrosion in rich amine piping likely due
to elevated H2S loadings and higher velocities (both lean and rich), especially when unit rates are
changed quickly.

Adjust amine circulation to maintain desired rich amine loading (Typically 0.3-0.45 mol total acid gas /
mol of amine loading). Ensure sufficient amine by:
o Sampling rich amine and determining H2S loading for optimization (reduce amine circulation)
o Controlling lean amine flow based on temperature rise of amine coming in or out of contactor
(relatively new )
o Set minimum amine circulation based on maximum H2S recycle content
o When pushing unit rates, amine loading, fluctuations in pressures and flows can “overwhelm” the
amine and H2S can breakthrough.
o Develop calculation tools to estimate sulfur load and set lean flow rates accordingly.

Adjust amine regenerator to maintain desired lean amine loading to meet FG H2S specifications.

There have been upsets in the sulfur unit due to hydrocarbon carryover into the amine. Typically this is
caused by large hydrocarbon carryover events (Loss of HPS levels, upstream Hydrocarbon
fractionators). Hydrocarbons cause foaming, solids will contribute to that as well. The amine system has
to be kept clean (filtered).
• Amine temperature typically controlled to 120-130F for H2S control (less critical for MDEA based
systems)
• Properly designed wash water trays designed and installed to minimize entrainment / carryover of
amine into recycle gas compressor (4 trays, with a water circulation to provide adequate tray loading)
• Process inlet temp should be maintained 10 degF above amine temp for vapor hydrocarbon systems
to prevent condensing
o Less of a risk of condensing Hydrocarbons in Recycle H2 amine contactors

ROBERT STEINBERG (Motiva Enterprises)

Amine absorbers that remove H2S from a gas phase stream need to be operated with the proper
amount of amine, at the right temperature and without liquid hydrocarbons.

Amine rates need to be high enough to remove the H2S in the sour gas and to keep the H2S
concentration in the rich amine low enough to avoid corrosion. In low pressure service, such as a
stripper offgas going to fuel gas, only a limited amount of H2S can be captured by the amine and the
amine rate needs to be adjusted to control the H2S content of the sweet gas.

In a higher pressure contactor, such as in the recycle gas loop of most hydrotreaters, high
concentrations of H2S can be captured by the amine. Allowing the rich amine to be saturated with H2S
in a Recycle Gas Scrubber would lead to excess corrosion in carbon steel lines and equipment.
Normally, the amine rate has to be adjusted to maintain the H2S loading in the rich amine within
acceptable limits. Typically, at these amine rates there is minimal H2S remaining in the sweet gas and
changes in the amine rate have negligible impact on the remaining H2S in the sweet gas. The maximum
H2S loading in rich amine is normally expressed in units of moles H2S per mole of amine, the maximum
acceptable limit depends on the type of amine used.

Liquid hydrocarbons should be avoided in gas-phase amine contactors as they tend to cause foaming.
Liquid hydrocarbons are prevented by:

• Avoid carryover of liquid hydrocarbons in the sour gas to the scrubber. This requires proper sizing of
the upstream separation vessel like a Cold Separator with good internals. As a minimum there should be
some sort of inlet device to help separate gas and liquid in the Cold Separator and a mesh pad below
the vapor outlet nozzle. In some cases, particularly if the unit charge rate has been increased, more
sophisticated devices like a cyclone separator in the Cold Separator are needed. If the Cold Separator is
not large enough, an additional knockout vessel on the vapor line between the Cold Separator and the
scrubber may be helpful, such a vessel normally has internal cyclones to remove liquid carried over from
the Cold Separator.
• Keep the lean amine to the scrubber hotter than the sour gas to the scrubber to prevent
condensation of hydrocarbons. A minimum 10°F margin is typically used but in some cases such as
very high pressure units, margins of 20-30°F may be needed. It is often a good practice to provide a
lean amine heater to heat the amine up to required temperatures as there may be limited ability to
provide additional cooling of the sour gas in the upstream Reactor Effluent Air Condenser (REAC). A
lean amine heater would generally be provided upstream of the Lean Amine Pump so it can be a low
pressure exchanger. Low pressure steam is normally an adequate heating mechanism. Avoid using
higher temperature heating sources that would result in high skin temperatures and potentially degrade
the amine – limiting maximum skin temperatures to less than 260°F or simply keeping temperatures
lower than in the Amine Regenerator Reboiler is a good practice.
• Provide facilities to skim hydrocarbons from the sump at the bottom of the scrubber. Even with good
upstream separation and high lean amine temperatures, some hydrocarbons will often accumulate.
These hydrocarbons are generally insoluble in aqueous solutions and form a separate liquid phase,
since the hydrocarbons have a lower density than amine solutions they tend to accumulate on top of the
rich amine. Level control devices using a dP transmitter will give a false low level if a significant
hydrocarbon layer is present. Measuring the hydrocarbon layer can be difficult as the amount of
hydrocarbons in an external level gauge will not be the same as in the tower. Using a gauge with a small
level range by first lowering the level until it is drained and then raising the level to the middle of the
gauge will give the same amount of hydrocarbon in the gauge as in the vessel, this information can be
used to decide how much material to skim. Alternatively, an overflow device can be provided in the
vessel sump at around the 50-60% level to continuously skim whatever liquid is at this elevation.

ALFREDO VILLA (Haldor Topsoe, Inc.)

Several operating conditions should be maintained and evaluated to determine the condition of the
amine system. A properly operating amine contactor will yield a clean recycle hydrogen stream and
minimize impact to downstream amine regeneration equipment.
Operating with a clean amine should mitigate potential foaming, corrosion, and heat stable salt build-up
in the absorber system. Monitoring the concentration and circulation rate of the amine used is crucial to
maintaining good operation in the absorber. These parameters will allow for adequate hydrogen sulfide
absorption and maintain target recycle gas concentration. An adequate concentration of amine will
reduce the potential of corrosion in the system by maintaining low rich amine loadings. A target amine
strength will depend on the type of amine circulated and should be discussed with the amine vendor.
Periodic visual inspection of the amine should be conducted to note changes in color and solids content.
Typically, lean amine has a pale-yellow color and should be relatively free of solids, a change in color
could indicate an increase in corrosion rates. For example, a change from pale-yellow to dark green
could indicate a change in the iron sulfide content of the amine and an increased solids content. Solids
in the system could lead to erosion of the iron sulfide scale protecting the inside of the piping. Removal
of this scale exposes unprotected metal, which could lead to further corrosion. Along with the removal of
the iron sulfide scale, solids in the system could stabilize foam.
Temperature control is of importance in any amine contactor system as it can lead to poor acid gas
absorption. The loading capacity of the amine is directly impacted by the lean amine temperature, the
cooler the lean amine the greater its H2S removal capacity. However, it is recommended that the lean
amine temperature is maintained warmer than the gas feed. Lean amine temperatures which are too
low, increase the potential for condensed hydrocarbons, which could lead to foaming in the contactor.
Feed gas temperature control is also recommended as a high feed gas temperature leads to a higher
lean amine temperature, which reduces the capacity of H2S removal.

GARY BOWERBANK (Shell Global Solutions)

Solvent hygiene is high on the list. Poor solvent quality, which is often measured in terms of high
degradation products (Heat Stable Salts) or high suspended solids, can lead to both corrosion and
fouling of the system but also increase the risk of foaming events. These foaming events are the most
common issue to impact operations of any amine contactor, which can result in losses of solvent (if
carried over beyond KO vessel) or off specification product. Sites may often focus on treating the
symptom by dosing an anti-foaming agent, however we prefer to understand the root cause and tackle
that. If not linked to solvent quality; then entrainment or condensation of hydrocarbons in the contactors
is the most common root cause. So, having high efficiency gas/liquid separators upstream and
maintaining lean solvent at least 5oC above the gas temperature are critical.

ERIC LIN (Norton Engineering Consultants, Inc.)

Other than the type of amine used, the most important operational factors for amine gas contactors are
temperature and pressure drop. Lean amine coming to the column should be at least 10°F (6°C) hotter
than the sour gas to prevent condensation of hydrocarbons and cause possible foaming. Sometimes a
LP Steam heater may be necessary if the lean amine is too cold from the ARU. On the other hand, if the
lean amine is too hot (~25°F greater than the sour gas), there exists the possibility of appreciable
amounts of amine carryover into the sweet gas. Contactors should also have alarms indicating high
pressure drop normally caused by foaming. Most contactors should have the capability of periodically
skimming the oil from the top of the rich amine in order to proactively prevent this from happening.

PRASAD HARDIKAR (Honeywell UOP)

The primary purpose of an amine contactor /amine scrubber is to remove H2S from the circulating
recycle gas stream or remove H2S from hydrotreating unit off gases before blending hydrogen rich gas
with fuel gas.

Here are key factors to be considered in various stages:

Design/ Commissioning Stage:
• Remove oil or rust inhibitors present from construction
UOP always recommend degreasing of new/modified amine column with 2 wt% soda ash neutralization
solution before putting it in service. Degreasing removes grease or protective oil layer on amine
contactor /scrubber trays and internals which can contribute to foaming. Hydrocarbon layer is meant for
protecting trays/internals from rusting during transportation and storage.
Operation:
• Limit hydrocarbons entering with recycle gas:
• Keep lean amine 3-5°C (5-9°F) warmer than inlet gas to prevent hydrocarbon condensation and
consequent foaming
• Ensure mesh blanket in upstream knockout drum is working
• Lean and Rich amine loading:
Amine loading is expressed as mole loading of H2S per mole of Amine. Lean amine loading indicates
efficiency of amine regeneration unit and capacity of lean amine to absorb H2S. Rich amine loading sets
maximum H2S capacity for rich amine.
Higher rich amine loading increases potential for erosion in the rich amine lines due to two phase flow in
the rich amine lines especially from downstream of rich amine control valve. This can have negative
effect on the operation of the amine regeneration system as the lean amine will eventually become more
contaminated with iron particles and have deficient performance. It is recommended to maintain rich
amine loading < 0.4 mol acid gas/mol MDEA with KCS metallurgy lines.
It is quite tempting to reduce lean amine flow during operation from an optimization perspective.
However, such reduction in flow with same acid gas (H2S) content increases rich amine concentration
well beyond acceptable rich amine loading as amine will continue to absorb acid gas till saturation.
Hence monitoring rich amine loading is a critical factor in amine contactor operation.
• Amine Appearance and Quality
Amine appearance and quality is one of the critical aspects to monitor.
It is observed that increase in total dissolved solids (TDS), total suspended solids (TSS), heat stable
salts (HSS) enhances foaming tendency in lean amine. TSS are expected to be NIL and HSS at < 0.5%
for lean amine solutions. These parameters are better controlled with mechanical filtration (with activated
charcoal) and it may require replacement if foaming issue persists.
Lean amine displaying a green color is indicative of the presence of solubilized iron sulfides in the amine
due to corrosion or issues with amine system filtering. Lean amine with a slight green color will continue
to remove H2S from recycle gas adequately, but if soluble iron sulfide buildup in the amine is not
eliminated, foaming could be a potential concern.
• Amine Color Guideline:
– Light straw = amine is in good condition
– Black or dark green = corrosion is taking place
– Light green rich amine = small particulates present
• Avoid excessive foaming inhibitor as this with increase foaming tendency
• As an operational task, regularly skim out hydrocarbon layer before it starts to build up
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