Chemical analysis in amine system

operations
The array of contaminants that can disrupt the operation of alkanolamine
systems needs to be precisely characterised and analysed

Scott Waite, Arthur Cummings and Glen Smith MPR Services

C
hemical analysis opens the door to under- beyond the scope of this article.) This simplified
standing, responding to and preventing view of amine systems and operational condi-
alkanolamine (amine) system operational tions is the basis on which the most common
difficulties. Unfortunately, the link between the analytical methods were developed.
analysis report and the amine system operation If no contaminants accumulated in the amine
is often unclear. The uncertainty results from system, this could be the extent of the analytical
several factors that can lead to information required to operate. Unfortunately,
misunderstandings, misinterpretations, frustra- contaminants do accumulate in amine systems
tions and mistrust of the lab. This article and affect equipment longevity as well as the
attempts to provide clear definitions of analytical success of the operation of the amine system.
terms, link them to their operational impor- More unfortunate is the fact that the contami-
tance, translate terminology from different nants can affect the results of the fundamental
sources to a uniform set of terms, and expose analytical methods, misleading the operator, and
analytical methods that can mislead you. This yet the operator continues to rely on these few
article also provides questions you can ask your simple tests for day-to-day operations.
chemist, lab analyst or amine vendor to avoid Increased awareness of the effects of contami-
operational pitfalls and get the information you nants on operations has led to an increased
need from the analysis reports. understanding of the variety and identity of
An alkanolamine acid gas scrubbing system is contaminants that exist in amine systems.
a simple concept: a solution of water and alkan- Common analytical methods have been adapted,
olamine absorbs acid gases from petroleum gas modified and sometimes misapplied to contami-
or liquid and is pumped to a heated regenerator nant analysis. Contaminant-specific analytical
that releases the acid gases, and then the amine methods have multiplied. The amine system
is cooled as it returns to the absorber. The amine operator can now be confronted with a maze of
solution can continuously circulate. The simple analytical parameters, a blur of analytical results,
acid base chemistry of the process can be moni- and a host of analyte names and acronyms that
tored by a few analytical titrations (see Table 1), can be ambiguous, confusing and even misleading.
and operators need only to
monitor temperatures, pres-
Fundamental analytical parameters of amine solutions
sures and flow rates to balance
the amine absorbing capacity Parameter Analyte Description
with the acid gas removal Amine strength Free amine (FA) Amine available for acid gas absorption
requirement of the incoming Acid gas loading (AGL) Rich loading (RL) Acid gas (H2S & CO2) in the solution exiting the absorber
Lean loading (LL) Acid gas(H2S & CO2) in the solution exiting the
petroleum gas or liquid. (The regenerator
acid gas content of the sweet- Water Water The remainder of the solution (if no contaminants)
ened product is, of course, the
ultimate control measure, but is Table 1

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 nants. Thus, contaminants may
4.5 cause errors.
1% formate, 1% acetate
4.0
0% formate, 0% acetate
Error, wt% free amine 3.5 Understanding analyses
3.0
With knowledge of the preced-
ing information, the engineer
2.5 Methyl purple
indicator range responsible for the amine
2.0 system can now ask the analyti-
1.5 cal chemist or operator, “What
Bromphenol blue endpoint indicator do you use
1.0 indicator range
0.5 for the amine strength titra-
tion?” If the chemist responds
0
“Bromophenol blue” or “pH
–0.5
3.0 3.5 4.0 4.5 5.0 5.5 6.0 6.5
4.5”, the engineer knows that
pH at endpoint
amine strength results are prob-
ably higher than their actual
level, unless there are no weak
Figure 1 Endpoint pH affects accuracy of free amine titration acids in the amine solution.
The better titration methods
Better analytical methods needed require the tracking of pH or conductivity during
A prime example of misleading results is illus- the titration and determination of the endpoints
trated in Figure 1 and Table 2. When weak acids by inflexion points in the first or second deriva-
(such as formic acid, acetic acid, and so on) have tive, respectively. Both pH and conductivity can
accumulated in the amine solution, forming heat provide accurate free amine results, but conduc-
stable salts (HSS), the titration to determine free tivity is preferred because it also provides clear
amine can also respond to the weak acid anions. endpoints for the weak acids.1,2
The choice of pH for the endpoint of the titra- Before we seek to understand analytical meth-
tion determines whether the free amine titration ods, let us clarify our understanding of the
is accurate or over-estimates the amine strength. amine solvent itself.
A pH or colour indicator that provides accurate
amine strength in a clean amine solution can Amine system is supposed to make salts
grossly over-estimate the amine strength of a The chemistry of alkanolamine solutions is quite
solution that contains weak acid anions (HSS or simple, but is often described in terms that lead
LL). Note, for example, in Figure 1, that Methyl to an incorrect view of amine interactions with
purple and Bromothymol blue are both accept- acid gases and contaminants. Consequently, the
able indicators for the titration of clean amine understanding of analytical results becomes
solutions, but fail miserably if the solution more difficult.
contains significant weak acid HSS. The same is Alkanolamines are bases. Bases react with acids
true for a pH “dead-stop” titration. The most to make salts. Acid gases are absorbed and held
common amine strength titration methods were in amine solutions because the amine forms a salt
developed for amine solutions with no contami- with the acid gas. The acid gas becomes an anion
(negatively charged ion) and is
Error of fixed pH endpoint titration 45 wt% MDEA associated with an amine cation
(positively charged ion). The acid
Acetate, Formate, Sodium, Actual free Found free amine, wt% at endpoint pH
gas ion is no longer in a gaseous
wt% wt% wt% amine, wt% 4.5 3.5 3.2 state and it cannot leave the
0 0 0 45.0 45.0 45.1 45.2 amine solution as long as it
1 1 0 40.3 42.0 44.0 44.5
1 0 0 43.0 44.3 45.0 45.1 remains as an anion.
1 1 0.5 42.9 44.6 46.6 47.1 The regenerable salts in Table
1 0 0.5 45.0 46.9 47.6 47.7
3 and the HSS in Table 4 are
written to emphasis the sepa-
Table 2 rateness of the ions. A cation is a

2 PTQ Q3 2013 www.digitalrefining.com/article/1000821

positively charged molecule that
Regenerable salts from acids gases in amine solutions
is physically disconnected from
its neighbouring anion, which is
Acid + vase → cation + anion
an independent molecule with a
negative charge. Anions and cati- Acid Base Salt Salt name
H2S Free amine (“Am”) AmH+ + HS- Aminium bisulphide
ons must be in equal numbers CO2 + H2O → H2CO3 Am AmH+ + HCO3- Aminium bicarbonate
and uniformly distributed HCO3- Am 2AmH+ + CO3= Aminium carbonate
CO2 Am + Am AmH+ + AmCO2- Aminium amine carbamate
throughout the solution, but they
are continually changing part-
ners. This view of ions is critical Table 3
to the understanding of amine
acid gas absorption and regeneration. In words: WAA consume H+ (making an acid
For example, H2S absorbed in an amine solu- molecule); SAA do not.
tion is not bound to the amine. Rather, the The last four entries in Table 4 exemplify
amine has taken a hydrogen ion (H+) from the non-amine HSS: salts whose cation is a strong
H2S, creating an AmH+ cation and an HS- anion, cation such as sodium or potassium. These are
which cannot escape from the solution. The often called inorganic HSS (IHSS) and are
amine is bound to the H+, and does not readily formed in amine solutions from the addition of
release it. The only way for the HS- to escape the caustics (sodium or potassium hydroxide or
solution is to take an H+ from an AmH+, thereby carbonate). The last two entries illustrate that an
recreating H2S, which has low solubility and excessive concentration of strong cations makes
high volatility and will exit the solution, unless HSS of the anions of acid gases, causing the lean
another amine molecule reacts with it and loading of the regenerated amine to rise. Strong
removes one of its H+ to form another salt. cations must never be allowed to rise to the level
Acid gases are readily released from the thin that any acid gas becomes heat stable. This
films of liquid amine solution in an amine system starts to occur when the molar ratio of strong
regenerator, not because temperature “breaks the cations to HSS anions reaches approximately
salts” but because at higher temperatures and 0.66.
lower pressures AmH+ more readily releases its Acid gas regeneration is aided by a low
H+, and the anions of the acid gases readily take concentration of amine HSS, because they
the H+, creating gases that are less soluble and increase the population of AmH+ by decreasing
more volatile at the elevated temperature and the pH. The anions of acid gases then have a
decreased pressure of the regenerator. higher probability of obtaining H+ to convert
HSS, such as those in Table 4, do not leave the back to the gaseous state and escape the solution
amine solution in the amine system regenerator. of amine.
The acids of these salts are
generally stronger acids than HSS from acids in amine solutions
the acid gases (thus they do not
as readily accept the H+ offered Acid + base → cation + anion
by the AmH+), and are more
Acid Base Salt Salt name
soluble and less volatile than Formic Am AmH+ + formate- Aminium formate
the acid gases (thus they do not Acetic Am AmH+ + acetate- Aminium acetate
leave the solution). The HSS Propionic Am AmH +
+ propionate- Aminium propionate
Thiocyanic Am AmH + SCN
+ -
Aminium thiocyanate
anions can be classed as weak Thiosulphuric Am + Am AmH+ + S2O3= + AmH+ Aminium thiosulphate
acid anions (WAA) and strong Hydrochloric (HCl) Am AmH+ + Cl- Aminium chloride
Sulphuric Am + Am AmH+ + SO4= + AmH+ Aminium sulphate
acid anions (SAA). The func- Formic NaOH Na+ + formate- Sodium formate
tional distinction between WAA Acetate NaOH Na+ + acetate- Sodium acetate
and SAA is seen in titration with
Acid gases are heat stable with caustics; for example:
acid in water: H2S NaOH Na+ + HS- + H2O Sodium bisulphide
HCO3- KOH K+ + CO3= + H2O Potassium carbonate

WAA- + H+ → HWAA; SAA- + H+ → SAA- + H+ Table 4

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 Solvent parameters of amine solutions
The trends in the amine
system should be monitored on a
Parameter Analyte Description and role
regular basis. When BA rises or
Amine strength Free amine (FA); Amine available for acid gas absorption TA plus water departs signifi-
regenerable free base (RFB) cantly from near 100%, the
Reacted amine Bound amine (BA) Amine that has reacted with an acid
and now carries a hydrogen ion: AmH+. amine system could be becoming
Total amine Total amine (TA) = FA + BA; contaminated and more infor-
actual total base (ATB) All the amine in the solution
mation is needed. The
Activators Proprietary additives that enhance the second-tier analyses — for
amine solution’s absorption rate or
selectivity. Generally are included in FA,
dissolved substances — are listed
BA and TA results in Table 6.
Water Water Water is essential for acid gas absorption The numerous analytes listed
Physical properties Density, Physical properties of the solution provide in Table 6 can be daunting. The
viscosity, monitors of compositional changes in the several analytes may each show
conductivity, amine solution that affect absorption,
surface tension, regeneration, heat demand, corrosivity
a different result, or overlap, or
and appearance equipment longevity. even disagree with one another,
requiring informed interpreta-
tion of the respective results.
Table 5 Many of the dissolved
substances cause corrosion or
Acid gas regeneration can be hampered by enhance corrosion by attacking the protective
strong cations, because they have no H+ to give. iron sulphide layer. Iron carbonate can form
Anions of acid gases are attracted to the strong protective layers, but most often creates
cations because of their positive charge, and suspended solids. Corrosion products create
then must remain in the amine solution because solids in the amine solution, and along with other
they cannot obtain an H+ from the strong cation. insoluble or semi-soluble substances create the
HSS reduce amine strength, increase corrosiv- third tier of analytical problems listed in Table 7.
ity, increase viscosity, increase density and All of the contaminants in Tables 6 and 7 have
displace water from the amine solution.3,4 All their effects on amine solvent performance and/
these have deleterious effects on amine system or the amine system hardware. Contaminants can
operations. It is thus very important to know change the physical properties (density, viscosity,
what and how much salt is accumulating in your surface tension, thermal conductivity, electrical
amine system. conductivity and foaming tendency) and the
water content, which can influence film absorp-
What analyses are needed? tion and desorption rates. Longer-term effects
The first-tier parameters affecting amine system include corrosion, plugging, flow restriction,
performance are free amine and water content. foaming and inhibited processing rates. Given the
The free amine represents the carrying capacity importance of the short- and long-term character-
of the solution, and the water content affects the istic effects of these contaminants, it is very
acid gas absorption and desorption rates. The important to have regular analytical reports. But
amine solvent supplier, amine system designer how do you make sense of them?
or the amine technical support person typically
provides operators with recommended ranges of Reconciling various analytical methods
free amine and water for the particular applica- When you compare reports from two different
tion. If there are no contaminants in the amine labs, there may appear to be inexplicable differ-
system, the Table 1 analyses would be sufficient ences in apparently the same analyte. Some of
— water could even be determined by difference. the confusion results from differences in termi-
However, contaminants are common in amines nology and some from differences in lab
systems and a more detailed analysis is required. procedural definition of analytes of the same
Table 5 shows several parameters requiring name. For example, the question “What is the
analysis for the proper operation of clean amine HSS content of this sample” could have the
systems. following correct answers:

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HSS anions 14 609 ppm(m) Dissolved substances in amine solutions (other than solvent amine)
Total HSS 3.13% as DEA
HSAS 1.49% as DEA
Type
Analytes Description and role
IHSS 1.63% as DEA Acid gas (AG)
Rich loading (RL) Acid gas (H2S & CO2) in the solution exiting the absorber
Total HSS/total amine 11.14% of DEA Lean loading (LL) Acid gas (H2S & CO2) in the solution exiting the
0.1114 mol/mol regenerator
H2S, CO2, The acid gases measured separately; in amine solution
From 1.5 to 11%! No wonder acid gas loading (AGL) are ionic: HS-, HCO3-, CO32- and carbamate ions
we are confused. Notice the Acids - organic HSS; total HSS; Acids that accumulate in the amine solution by
importance of the prepositions absorption
and inorganic, BA; HSAS; IHSS; and chemical reactions within the amine solution. They
“as” and “of”, which are some- also called heat individual anions*; reduce amine capacity, contribute to corrosion, increase
times not included in stable salts (HSS) ATB-RFB; conductivity density and viscosity, and conductivity. Two general
conversation or reports. We types:
weak acid anion (WAA) and strong acid anions (SAA)
prefer the first two in the above
list, because they are direct Acids - amino Bicine; total amino Amino acid derivatives of amines by reactions within the
(AA) acids; BA amine solution; may be included among HSS; amino
expressions of the two acids
parts of the total HSS: the titrate as BA and as TA. Amino acids strongly enhance
anions and the amine equivalent corrosion

cations. The others have good Cations, Strong cations (SC), Alkali cations that accumulate in the amine solutions
utility, however, and need to be inorganic, also eg, K+, Na+; from cooling water leaks or deliberate caustic addition;
called strong corrosion metal ions corrosion metals result from aggressive acid gases,
understood. cations (SC) (Fe, Cr, Ni, etc) erosion, enhanced by HSS and amino acids
As can be seen in Table 8, inorganic HSS (IHSS)
there are a large number of Basic Total base (TB); total Amines and amine dimers that result from chemical
parameters that are measured degradation amine base (TAB); degradation of the solvent amine; have some acid
by a variety of techniques, and a products (BDP) actual total base (ATB); gas absorbing capacity. Amine dimers enhance corrosion
total nitrogen (TN);
thorough understanding of the TB-ATB; dimers
terminology is required to (THEED, HEED, HEP,
etc), ureas
correctly interpret amine analy-
sis reports and to take action Neutral Amides, formylamines, Non-ion results of chemical degradation of the solvent
based on the analysis. degradation oxazolidones; amine; amides are in active reversible equilibrium with
products (NDP) hydrolysables their corresponding organic acid HSS anion
total nitrogen (TN);
Questions to ensure TN-TB
measurements are clear *HSS anions most commonly determined individually include formate, acetate, propionate, glycolate, oxalate,
and understood chloride, thiocyanate, thiosulphate, sulphate and sulphite .

Proper sampling is essential to

achieving good analysis results,
and understanding how the Table 6
sample was taken is essential in
helping you interpret the Insoluble, partially soluble or dispersed substances in amine solutions
results. The following questions
should be suitably answered Type Analytes Description and role
before the analyst or operator Solids Total suspended solids (TSS) From corrosion products, chemical and physical;
TSS contribute to further corrosion, flow
takes a sample: restrictions, and plugging. TSS stabilise foam
• Was the dead leg flushed Hydrocarbons Total petroleum hydrocarbons TPH carryover from contact with petroleum gas
(TPH) or liquid. TPH may contribute to or inhibit foam
before taking the sampling? Surfactants Foaming tendency, break time, Polar/non-polar molecules that cause foaming.
• Were the operating conditions foaming potential; surface typically in very low concentrations but have large
tension physical effects inhibiting acid gas absorption
of the unit recorded when the and stripping Surfactants cause system upsets
samples were taken? Is there a and solvent losses
plant upset or unique operating Antifoam Si (confirm presence of silicone Antifoam is deliberately added to
reduce foaming;
conditions? antifoams only); no direct note: excess antifoam can cause foam
• Was the reason for sample analyses
collection recorded (routine or
non-routine troubleshooting)? Table 7

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 • Where was the sample taken? Upstream or ■ How are strong cations removed before anal-

downstream of the filters and carbon beds? ysis or how is their effect accounted for in the
You should make sure that the measurements final HSS result? Caution: some acidification and
for free amine (FA) or amine strength are correct back titration methods detect WAA HSS (not SAA
so you know how much amine is available for HSS) and detect only the strong cations, which
acid gas adsorption. The following questions are exceed the equivalent of the total HSS. Such
helpful to interpret the results: methods estimate HSAS, not total HSS.
• Is it a titration with acid? If yes, good. Strong cations can enter amine systems unin-
• Is the endpoint of the titration determined by tentionally through heat exchanger leaks, from
inflection points in a conductivity or pH curve? the treated product or intentionally by the addi-
If yes, good tion of caustic to neutralise HSS. Proper analysis
• Is the endpoint determined by colour indica- is important to make sure they do not contribute
tor? If yes, worry about accuracy to high lean loading and stripping difficulties or
• Is the endpoint determined by “dead-stop” at a contribute to viscosity and corrosion problems.
specified pH? If yes, worry about accuracy There are several methods of analysis for strong
• Spiking with acetic acid before titration can cations, and the following questions should be
help get a more accurate endpoint for FA. asked:
An important parameter for operational • How are strong cations (sodium, potassium
control is the total concentration of the amine in and calcium, for instance) determined?
the unit. The questions below should be asked so • If by IC or ICP:
you can understand how the total level of amine ■ Was the signal within the calibration range?

was determined: ■ Are there any false highs due to interfer-

• How is the total amine test done (GC, IC, ences (such as amine with K+ in IC)
HPLC, titration or other)? • If by titration:
• If GC, IC or HPLC, what amines are quantified ■ Was a sufficient strong-base anion exchange

and are there noteworthy not quantified/uniden- resin used to absorb all the LL and HSS anions
tified peaks? (at least two times the equivalent)?
• If titration, are other basic species such as ■ Has the titration been checked against ICP

amino acids or piperazine are subtracted from or IC for this amine system? (It is a good check
the reported total amine number? If the number on endpoint determination technique. Rarely,
is reported as titrated, the total amine number is but it has happened, the titration method will
actually a total base number. grossly exceed the actual strong cations concen-
One of the most important analyses in amine tration for unknown reasons)
systems is the measurement of HSS. A number of ■ Only strong alkali and alkaline earth metals

methods can be used for this analysis, and it is are detected by titration.
recommended that more than one method be used It is important to measure metals in order to
and the results compared to make sure accurate have an early detection system for possible oper-
results are obtained. These questions are useful in ational difficulties due to corrosion products or
obtaining a good understanding of the results: loss of metal integrity in the unit. Metals are
• How is the HSS measurement made (IC or measured by ICP and AA, and there are several
titration)? relevant questions you should ask and items you
• If by IC, the individual analysis of species should consider:
should be available. See if the common anions • Was the sample filtered or digested?
are analysed for formate, acetate, propionate, (Dissolved or total metals?) High dissolved
glycolate, oxalate, chloride, thiocyanate, thiosul- metals in lean amine samples indicate the pres-
phate, sulphate and nitrate ence of HSS, amino acids and/or polymeric
• If by titration: amines (BDP)
■ Is a direct titration of the amine sample with • Sample preparation of ICP samples, espe-
base? If so, the result is BA. cially for solutions that contain solids, will
■ How is lean loading (AGL) removed? If via affect the results. If the sample is just filtered
boiling of a direct sample, worry about false high before the digestion of the liquid sample, the
results measurement is of only the dissolved metals

6 PTQ Q3 2013 www.digitalrefining.com/article/1000821

• If the samples are not filtered Analytical symptoms of some amine system problems
until after acid digestion, the
metals in the solids (total Symptom Possible Interpretations
metals) are included in the FA decreasing - Amine losses (carryover, entrainment, valve error, etc)
metals report - Water purge out of balance (total solution volume increasing)
- HSS ingress
• Generally, it is more instruc- - NDP forming: amides, if primary or secondary amine;
tive to determine the metals in oxazolidones if in high-pressure CO2 service
Total HSS increasing - HSS ingress
the filtered solids separately - Water content decreasing
from the liquid, so solids and - Corrosivity increasing
- Need HSS removed
dissolved solids profiles can be FA increasing while BA increasing - FA analysis error: FA report includes weak acid HSS
determined. LL rise with no change in operating - Greater AG load in absorbers
Performing a mass balance or conditions - Strong cations ingress into solvent
Total HSS > BA - Caustic ingress or addition
“residue calculation” can be - Cooling water leak into amine solution
instructive. It requires an accu- BA > total HSS - Amino acids present (not included in total HSS)
- BA includes high LL
rate water analysis by Karl Thiosulphate HSS - Oxygen ingress
Fisher titration, an accurate - SO2 breakthrough (Claus tail gas)
total amine measurement, an Bicine (and other amino acids) - Oxygen ingress (gas plants)
- O2, SO2 and/or S2O3= attack (refinery)
accurate knowledge of the Strong cations - Caustic addition
amine molecular weight (which - “Amine slops” added to amine and included some caustic
- Cooling water leak into amine
may be difficult if it is a blended - “Hidden” HSS
or formulated amine), and an - Foaming tendency increasing (soaps)
Formate HSS - Caused cyanide or carbon monoxide ingress
accurate analysis of strong cati-
- If primary or secondary amine, amides increase as formate
ons, HSS, amino acids, AGL, increases, so total amine and free amine reduced => apparent
BDP, NDP and amides. A mass amine loss, but it can be recovered (do not throw it away)
Acetate HSS - Acetonitrile ingress
balance of less than 100% can - Oxygen ingress
indicate that there are contami- Thiocyanate (SCN-) HSS - Cyanide reacting with H2S
Chloride HSS - Cooling water leak
nants present that have not - HCl ingress
been analysed. A mass balance Solids (TSS) rising - Corrosion
of greater or less than 100% can - Filters inadequate or spent
TPH - Hydrocarbon carryover into amine: inadequate knock-out drum
also indicate errors in the analy- “Residue” increasing, but BA not - Caustic ingress or addition
sis methods, especially for total - Cooling water leak into amine solution
- Amine chemical degradation
amine and water.
If your lab does not have the
capability of running all the
tests, do not hesitate to use an Table 9
outside lab to complement your
in-house testing. It is also a good idea to have a Summary
complete analysis done by an outside lab once a We have discussed both the simplicity of the
year to check your in-house analysis results. If amine system and the complicated array of
contaminants are growing or changing, you may contaminants that pollute amine solutions and
be advised to have outside analysis done on a cause problems for amine system function and
more frequent basis. Remember that HSS, longevity. The even larger array of analytical
amino acids and BDP contribute to corrosion methods employed to determine contaminant
and can cause severe damage to the amine treat- concentrations in amine solutions can lead to
ing unit. confusion if the analytical reports are not prop-
erly understood and interpreted. While there is
What information is revealed some duplication among the tables, each
by analysis of contaminants? provides a different perspective and thus can
By closely monitoring trends in the analytical possibly provide aid to different people in the
data, you can detect possible operational prob- variety of situations amine systems present to
lems before they become a big problem for the focus on the analytical methods and data that
unit. Table 9 provides some examples. are most instructive for the need at hand.

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 The fundamental focus for amine analysis must References
be on the following, which can be tracked with 1 Tunnell D, Asquith J, Bela F, Buzuik F, Eguren R, Cosma G,
relatively few, well-selected analytical methods: Hatcher N, Keller A, Kennedy B, Schendel R, Smith C, Stern L,
free amine (FA), total amine (TA), bound amine Welch B, Zacher M, Evaluation of amine analytical methods
part one: amine strength, Brimstone Sulphur Symposia, Vail,
(BA), H2S and CO2, total HSS, including WAA
Colorado, 2004.
and SAA estimates from conductivity titrations,
2 Tunnell D, Asquith J, Bela F, Buzuik F, Eguren R, Cosma G, Hatcher
strong cations (SC), chloride, thiocyanate, amino N, Keller A, Kennedy B, Schendel R, Smith C, Stern L, Welch B,
acids, amides and water. With the exception of Zacher M, Choices for determining amine strength: effects on
CO2, these can all be done with an autotitrator. operations and optimization, Brimstone Sulphur Symposia, Vail,
A mass balance or residue calculation using Colorado, 2005.
the analysis in the previous paragraph yields an 3 Rooney P, Bacon T, Dupart M, Effect of heat stable salts on MDEA
estimate of basic degradation products (BDP) solution corrosivity: part 1, Hydrocarbon Processing, Mar 1996,
and neutral degradation products (NDP). 95-103.
Instrumental methods can be added to meas- 4 Rooney P, Bacon T, Dupart M, Effect of heat stable salts on MDEA
ure total nitrogen (TN), amine species by GC or solution corrosivity: part 2, Hydrocarbon Processing, Apr 1997,
65-71.
IC, and HSS speciation by IC. Then, by “amine
balance” and “nitrogen balance”, BDP and NDP
Scott Waite is Vice President of Technology with MPR Services,
estimates might be segregated. These can be
Inc., Dickinson, Texas. He has managed the R&D process to
supported by HPLC and GC identification of develop new and improved methods for amine and glycol
specific BDP and NDP species. reclamation, and treatment of produced and flow backwater. He
Other important measurements that can is currently an Adjunct Professor of Chemistry at University of
provide information on the health of the amine Nevada, Reno, and holds a BS in chemistry from the University
include total suspended solids (TSS), total petro- of Arizona and a PhD in physical/analytical chemistry from the
leum hydrocarbons (TPH), foaming tendency, University of Utah.
foam break time, density, pH, conductivity, Arthur Cummings retired from MPR Services in July 2012. During
viscosity and surface tension. his 21 years as Vice President of Technology, MPR helped
Tracking and graphing various data over long hundreds of refineries, gas plants, ammonia plants, syngas
plants, chemical plants and steel mills improve the operation of
periods of time makes it easier to spot trends, to
their amine units. He holds a PhD in analytical-physical chemistry
gain a sense for normal analytical/sampling vari-
from Brigham Young University.
ability, to recognise possible errors, to key in on Glen Smith is Technical Manager with MPR Services. He managed
unexpected results, and to track cause and effect MPR’s laboratory from 2005 through 2012, and helped develop
on unit operations. and improve methods of analysis for amines and glycols. He
A plant needs to have locally only an auto- holds a PhD in inorganic chemistry from Purdue University.
matic titrator, conductivity meter and probe, pH
meter and probe, sulphide ion-selective elec-
trode and reference electrode, CO2 analyser, and
Karl Fischer titrator in order to provide the most
important analyses (free amine, total amine,
bound amine, H2S, CO2, total HSS, strong cati-
ons, chloride, thiocyanate and water). The other LINKS
analytes can be done monthly, quarterly or as
needed by your company’s central analytical lab, More articles from: MPR Services
amine vendor or reclaimer. More articles from the following categories:
Corrosion/Fouling Control
A further table (Table 8) providing comprehensive reconciliation Gas Processing/ Treatment Heavy/Sour Crudes
of analytical methods and their reports is included in the web Laboratory/R&D/Quality Control
version of this article. Go to www.eptq.com

8 PTQ Q3 2013 www.digitalrefining.com/article/1000821