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/ 17
INSPECTION
TRAINING MANUAL
AMINE
TREATING UNIT709001
XXII-1
General
The removal of hydrogen sulfide (HS) from liquid and gaseous
hydrocarbon streams has Tong been desired to reduce the malodorous
and corrosive characteristics of streams rich in this compound.
More recently, governmental legislation requiring reduced sulfur
pollutant emissions to the atmosphere from various fuels is becoming
more and more prevalent throughout the world. To date, the most
economical and widely used process to etticiently remove HS and
other acidic contaminants is a continuous absorption/regenerat ion
process employing an aqueous solution of basic alkanol amine. The
alkanol amines most commonly used are:
Monethanolamine (MEA): HOCH2CHoNH2
or
Diethanolamine (DEA): (HOCHaCH?)2NH
These ethanol amines have high affinity for HeS and low solubility
in hydrocarbons which enhances their suitability in this process.
While these instructions will be concentrated on H2S removal, they
are generally also applicable to COp removal. Since both HS and
C02 are frequently present in feedstocks treated by ethanol amines,
throughout the discussion the term “acid gas" will often be used,
which will mean HgS, COz or both.
MEA OR DEA?
The choice of which amine to use is made by the designer of the
amine treating unit after carefully weighing the following factors:709001
XXII-2
1, Solubility in Liquid Hydrocarbons
DEA has a significantly lower solubility in liquid hydrocarbons than
does MEA. Therefore, to minimize amine losses, DEA is the preferred
solvent when treating liquid hydrocarbons.
2. Volatility
DEA has a lower vapor pressure than MEA. This property will result
‘in lower vapor losses with DEA than with MEA when treating gases.
3. Acid Gas Capacity
MEA has greater capacity for acid gases on a weight per unit volume
hacis Thus, for a given HeS removal requirement, a lowor
Volumetric rate of MEA circulation would be required in comparison
to DEA. This means lower utilities and slightly smaller equipment.
where the liquid rate governs.
4. Presence of Carbony] Sulfide
Ine presence ot appreciable concentrations of carbonyl suitide
(COS), as might be found in the fuel gases or LPG products from
cracking units which process high aulfur content feed stocks, may
dictate the use of DEA to reduce chemical losses of amine. Both DEA
and MFA will remove most of the COS, but MEA will also chemically
react with COS to form heat-stable compounds that cannot be
completely decomposed, even with reclaiming. DEA will also react
with COS but is recovered during normal regeneration.709001
XXII-3
5. Reclaiming Capability
The presence of strong acid contaminants in the absorber feed can
result in reactions which form strong, heat-stable compleaes which
neutralize the amine. Fatty acids, cyanides, S02, N02, HCI, et al,
wil] react with amine ta farm thair recpactive amine ealte. Oxygen
will react with HpS to form heat-stable thiosulfate. When MEA is
used, the dissolved heat-stable salts can be contacted with sodium
carbonate, a strong base, in a slip stream reclaimer to liberate the
weaker base, MEA, which can subsequently be distilled under stripper
Pressure and recovered (see REclaimer Operations). DEA, unfortu-
nately, becomes thermally unstable before its atmospheric boiling
point 1s reached and will decompose. Reclaiming of DEA can only be
done under vacuum or other techniques. Thus, if trace acidic
contaminants are expected, MCA 1s the preferred ethanu? amine.
BASIC CHEMISTRY
For simplicity, only the chemistry involved in HS removal will be
discussed. It should be realized, however, that other acid gases
(such as C02) will also undergo similar reactions.
Hydrogen sulfide, HgS or HSH, is a weak acid and ionizes in water to
form hydrogen ions and sulfide ions:
Hy + HO >
Hg0"+ HS" Q)
Since it is a fairly weak acid, only a fraction of the HgS will
jonize. Similar ionization will occur for the other acidic
compounds present, for example COz:
(02 + Hy == Ht + HCO3” (la)709001
XXIT-4
Ethanol amines are weak bases and ionize in water to form amine ions
and hydroxyl ions:
For MEA:
HOCHCHNH2 + Hog) =>
HOCH2CHoNHa* + OH” @)
For DEA:
(HOCH CH) NH + HO
(HOCH2CHy) 2NHy* + OH” (2a)
When Hg dissolves into the solution containing the amine ions, it
will react to forma weakly bonded salt of the acid and the base.
For MEA
HOCHCHDNHg+ + HS” =—*
HOCHaCH>NHaSH a)
For DEA:
(HOCHCH2) gNHg* + HS” ==>
(HOcHaCHp) gNHySH (3a)
The sulfide ion is thus absorbed by the amine solution.
This salt formation reaction does not go to completion. As the
icate, an equilibrium level of hydrogen sulfide romaine in
the hydrocarbon stream. The overall reaction can be summarized by
the following equations:
For HEA:
HOCH2CHaNH, + Hos ——
HOCH2CHNH3SH 4)703001
XXII-5
For DEA:
(HoctigcH) NH + Hys
(HOCHaCH2) 2NHigSH (4a)
Operating variables are adjusted to favor the forward reaction of
equation (4) in the absorption step of the process and, conversely,
adjusted to favor the reverse reaction in the amine regeneration
step of the process. It is the reversibility of this reaction that
permits solvent regeneration and continuous removal of HS by amine
treating.
General Flow Schene
Refer to Figure 1.
Regenerated, or lean, amine solution is pumped by the lean amine
circulation pump through the lean amine cooler and the filtration
system to the top of the HS absorber column on flow control. In
the absorber, amine descending down the column is contacted
counter-currently with ascending gas or liquid hydrocarbon which
enters near the absorber bottom. Treated hydrocarbon exits from the
absorber top, usually on pressure control. The amine, rich in HS,
and for that reason called rich amine, exits from the absorber
bottom, usually on level control.
Whore multiple absorbers are used for amine treating several
different hydrocarbon streams, the rich amine is sometimes pressured
from each absorber to a common vessel prior to being returned to the
amine stripper colum for regeneration. This common vessel may be
the bottom of the lowest pressure absorber column or may be an
independent vessel called the amine flash drum. In either case,
some of the dissolved hydrocarbons are released prior to
regeneration.709001
XXIT-6
From either the absorber or the flash drum, the rich amine is
Pressured or pumped through the amine stripper feed/bottoms
exchanger to increase its temperature and then through a level
control valve into the ton side nf the amino stripper column. The709001
XXII-7
FIGURE 1
‘AMINE PROCESS FLOW
ACID GAS
one R
pw Low H2s PRODUCT
A s
LEAN
sare REFLUX
LR
HIGH HoS REDOILER
FEED =>| tac
STEAM
RICH AMINE
LEGEND
‘A = ABSORBER
S = STRIPPER
L/R = LEAN/RICH EXCHANGE
LAC = LEAN AMINE COOLER
OHC = OVERHEAD CONDENSER
R = RECEIVER
rich amine solution descends through the column, is heated to its
boiling point, and is stripped of HyS by rising steam generated in
the reboiler. Lean amine, substantially free of HS, is collected
in the stripper colum bottom, cooled first in the feed/bottoms
exchanger, then in the lean amine cooler, and circulated once again
back Lu tie absorber.
The Hp rich acid gas and stripping steam pass out the top of the
stripper to an overhead condenser and receiver where condensed water
is collected. The condensed water is pumped on level control back
to the stripper as reflux. Since HS is less soluble in water than709001
XXIT-8
in amine solution, a good HS separation is achieved in the overhead
receiver. The HzS rich acid gas passes from the top ot the receiver
on pressure control to downstream sulfur recovery or incineration.
Process Variables
Absorption
The absorption of HgS into the amine solution 1s favored by:
Low temperature
Low acid gas loading
High amine concentration
High HzS partial pressure in the feed stream
Intimate contacting
In general practice, items 4 and 5 are not operating variables, per
se, having been fixed by the design criteria for the unit and choice
of equipment in the absorber design. Be aware, however, that low
feed rates cause poorer tray efficiency and thus somewhat poorer H2S
removal than will be possible at or near design flow rates.
1. Low Temperature
The lower the temperature of the lean amine solution, the better the
HpS removal. When treating a hydrocarbon gas, however, the lean
amine temperature is limited by the temperature of the gas being
treated. The lean amine temperature must be maintained 5°F (3°C)
higher than the temperature of the gas feed stream to avoid any
possible condensation of these hydrocarbon vapors. The lean amine
is usually cooled to between 80 and 105°F (27-49°C).709001
XXII-9
2. cid Gas Loading
Good acid gas removal efficiency depends on good amine solution
regeneration, as will be discussed later. However, it also depends
on restricting the HS loading in the rich amine to favor the
forward direction of the reaction given in equation (4). The HoS
loading of the amine solution is controlled by adjustment of the
amine circulation rate. In most cases, unless special design
considerations have been employed, the rich amine acid gas loading
(HS plus C02) should not exceed 0.3 to 0.4 mols total acid gas per
mo] of amine present.
The concentration of uncombined amine is favored by high amine
concentration in the amine solution. good regeneration. and freedom
from strong acids. Practical and economical considerations
confirmed by field experience concentration is between 15 to 20 wt-%
amine, with target values of 15 wt-% for MEA and 20 wt-% for DEA.
This is based on the lowest heat requirement for the desired HS
removal, the lowest chemical losses, and the fewest operational
problems.
The available amine concentration in the Jean amine is mainly
affected by the offi
lower the sulfide content of the lean amine, the greater the
available amine concentration for removal of H2S. In most cases,
properly regenerated lean amine will contain more than 0.03 mol HS
per mol amine nor more than 0.1 mol COz per mol amine.
joncy and control of amine regenoration. The709001
XXII-10
Regeneration
The regeneration of the amine solution, actually the breakdown of
the weakly bonded amine-hydrosulfide salt, is favored by:
1. High temperature
2. Low pressure
3. High stripping steam rates
4. Low amine concentration
Intimate contacting
These conditions are controlled in the amine stripping column,
subject to the following limitations. Item 5 is not an operating
variable and is fixed during plant design.
1, High Temper:
The breakdown of the amine-hydrosulfide salt into HzS and amine, the
reverse reaction of equation (4), 15 promoted by higher
temperatures. However, the ethanol amines can be thermally
decomposed at temperatures beginning at about 250°F (125*C) and
becoming excessive at 30°F (150°C). MEA is thermally more stable
than DEA and can withstand somewhat higher temperatures. The
decomposition temperature need not be approached to provide adequate
regeneration of ethanol amine solutions. The stripper reboiler
outlet temperature is generally less than 250°F (120°C). This
temperature is subject to variation with column operating pressure,
amine concentration, and acid gas loadings.
Tt should be noted that aminc solutions are mostly water.
Therefore, temperature changes with composition are small and it is
the operating pressure of the stripper that determines the
temperature of operation.709001
XXIT-11
2. Low Pressure
The stripping column is operated at the lowest overhead receiver
Pressure possible consistent with downstream acid gas processing
requirements. Generally, 5 to 15 psig (35 to 100 kPa) at the base
of the stripper is sufficient pressure to feed the acid gas to an
incinerator or sulfur recovery unit. As noted above, the lower the
Pressure, the lower the stripper temperature.
3. High Strippi
The liberation of the HS from its amine salt by temperature is
assisted by the generation of steam in the stripper reboller. The
steam dilutes and carries away HpS vapor as it is dissociated from
the amine. The resulting decreae in HgS concentration in tho vapor
allows for further amine-hydrosulfide dissociation. Normal stripper
operations require a heat input at the stripper rebotler of 1 to 1.2
Pounds of reboiler steam per gallon of ethanol amine solution
circulated through the absorber system (120 to 140 kg or reboiler
steam per m of amine solution circulated). This reboiler steam
rate will result in a reflux rate of approximately 3 to 5 LV-% of
the circulating amine rate.
4. Low Amine Concentration
Higher amine concentrations favor the retention of acid gac in
solution. Thus, the amine concentration is chosen to be high enough
for efficient absorption but low enough for efficient regeneration.
Unless special considerations are provided for during design, most
units will operate most efficiently at between 15 to 20 wt-® amine
concentration.709001
XXII-12
In most units, more water is lost with the acid gas than is intro-
duced with the absorber feedstocks. Thus, a live steam injection
point is usually provided directly into the reboiler outlet line to
enable the addition of water to avoid amine concentration increases.
In some units. more water is brought into the unit than ic Inct with
the acid gas. A slip stream of reflux liquid can be drawn off the
reflux pump and sent to the sour water stripper to eliminate the
excess water buildup that would otherwise cause excessive dilution
of the amine solution inventory.nanny
XXII-13
TABLE
PROPERT)
‘MONOETHANOLAMINE (MEA)
URE COMPOUND
FORMULA HOCH2CHQNH2
MOLECULAR WEIGHT 61.09
BOILING POINT AT 1 ATM 170°C (340°F)
FREEZING POINT AT 4 ATM 10.9°C (51°F)
VAPOR PRESSURE AT 20°C 0.36 MM Hg
SPECIFIC GRAVITY AT 20°C 1.0179
AQUEOUS SOLUTION, 15 MEA
AQUEOUS SOLUTION, 15 WT-% MEA
BOILING POINT AT 1 ATM 102°C (215°)
FREEZING POINT AT 1 ATM -4.4°C (24°F)
SPECIFIC GRAVITY AT 20°C (68°F) 1.006
TABLE 2
PROPERTIES OF
DIETHANOLAMINE (DEA)
PURE COMPOUND
FORMULA (HOCH2CH2)2NH
MOLECULAR WEIGHT 105.14
BOILING POINT AT 1 ATM* 271°C (520°F)
FREEZING POINT AT 1 2TM 28°C (82°F)
VAPOR PRESSURE AT 20°C
