Corrosion: Various types of corrosion can result from Most contaminants can be categorized into three basic groups
contaminated amine solutions. Increased circulation rates can Amine Degradation Products: Amine degradation
cause erosion corrosion, the physical wearing away of metals products are compounds which are formed either by the
by the abrasive action of the solution. This is of greatest direct reaction of the amine and constituents of the feed gas
concern where restrictions or changes in direction of flow (such as carbon dioxide, carbonyl sulfide, carbon monoxide,
are encountered. Corrosion rates increase with velocity and oxygen, carbon disulfide) or by thermal decomposition of the
even mildly corrosive solutions can produce extremely high amine. Conversion of the amine, irrespective of the
mechanism, represents a loss of active and valuable
corrosion rates if erosive conditions are present. amine. Furthermore, some of these degradation products
Amines may be degraded through excessive heat or contact may cause foaming, corrosion and reduced gas treating
with oxygen, CO2, or other contaminants. The resulting capacity.
degradation products may increase the tendency for fouling
and corrosion to occur in the system. Concentration cells
can be set up beneath fouling deposits or scale, leading to Heat Stable Salts: During the normal absorption/
high localized corrosion rates. Chlorides entering the amine regeneration process, the amine solution, which is basic,
plant via poor inlet filtration or cooling water exchanger leaks reacts with acid gases entering with the raw feed gas. In the
can accelerate general and pitting corrosion, and can induce case of H2S and CO2, the amine salts are thermally
stress corrosion cracking in stainless steel components. High regenerable. If other anionic species and/or stronger acidic
levels of other inorganic and organic acid salts can also components are present in the raw feed gas, they too form
contribute significantly to corrosion. amine salts. However, these compounds are not thermally
regenerable and are hence designated as “heat stable
All types of corrosion reduce the life expectancy of amine salts”. Both inorganic and organic heat stable salts
processing units and can result in major financial losses. occur. Heat stable salts can reduce plant throughput and
increase corrosion rates.
Continued., Using Monoethanolamine as much CO2 per unit volume as a Carbamate are in solution, heat is
virgin solution would, reasonable applied in the stripper to shift the
By the very nature of the chemistry levels of CO2 removal ranging from equilibrium to the left, back towards
of MEA, it is susceptible to 75% to 90% of its initial MEA and CO2. The regenerated
degradation through the introduction of concentration in the flue gas, are MEA is recycled to the absorber
sulphur oxides, nitrogen oxides and being achieved with these systems. where it picks up more carbon
oxygen. At present, it is common The advantage to operating these dioxide, while the CO2 liberated in
place to have pretreatment of the semi-lean units is related to the the stripper column is sent on to
flue gas in upstream units to lower energy requirement to drive dehydration and compression. The
lower the SOx and NOx down to the bulk of the CO2 from the sol- compressed CO2 can then be
acceptable levels of 10 ppmv and 20 vent. directed to an end use as mentioned
ppmv, respectively. Proprietary previously.
corrosion inhibitors that are added
to the high concentration MEA units As seen in the following primary
also utilize oxygen in their activation, reactions associated with CO2
so not only is the equipment removal with MEA, two moles of
protected but the effect of oxygen MEA are needed for every mole of
on degrading the MEA is lowered as carbon dioxide that is captured: Continued on page 7
well. Even with such safe guards in Once the Protonated MEA and MEA
place, degradation products will build
up over time and require removal to
regain solvent processing capacity.
Long term operating advantages and
cost savings can be achieved by
integrating a CCR Reclaimer with the
regeneration loop thereby keeping the
solvent at peak operating
performance at all times.
As with MEA, all of these new solvents will have the need to
remove degradation products from the solution over time.
CCR Technologies Ltd. (CCR) is uniquely qualified to
provide a built-to-order, integrated solvent reclaimer for
your MEA or alternative solvent Flue Gas CO2 capture
system. There are multiple configurations possible, with the
Page 8 Th e R e c l a i m e r
Aqueous diethanolamine (DEA) has been traditionally used Oxalate 250 ppm
in both refinery and natural gas sweetening processes. It is a
preferred amine to use in refineries where sulfur compounds Chloride 500 ppm
such as carbonyl sulfide and carbon disulfide are present Formate 500 ppm
because DEA will react minimally with these compounds to
form degradation products. DEA is more of a non-selective Glycolate 500 ppm
amine that will remove both H2S and CO2 acid gases Malonate 500 ppm
effectively vs. the more selective MDEA or specialty-MDEA
formulas. DEA is generally used in the 10 to 30 percent by Sulfate 500 ppm
weight range in the aqueous solution. Sulfite 500 ppm
Just like all amines, DEA does degrade over time in gas Acetate 1,000 ppm
sweetening duty. Factors which will influence the rate of Succinate 1,000 ppm
DEA degradation are temperatures, CO2 partial pressures,
and higher concentrations of DEA in solution nearing 30 Ammonia 10,000 ppm
wt%. Some of the major degradation products of DEA are: Thiocyanate 10,000 ppm
Thiosulfate 10,000 ppm
BHEP – N,N’-bis(2-hydroxyethyl) piperazine Sodium 2,000 ppm
HEOD – 3-(2-hydroxyethyl) oxazolidone All Other Metals 100 ppm
THEED – N,N,N’-tris(2-hydroxyethyl)ethylene-diamine
Formyl DEA (Formamides) – reaction of formate anions CCR’s Overall Solvent Quality Guidelines for DEA are:
(when present) and DEA
Bicine – Bis-(hydroxyethyl) glycine;
Free DEA 30 wt% max
Water 60 wt% min
Studies have shown that DEA degradation appears to limit
itself once BHEP equilibrium is established. The presence of Total HSS Anions < 1.2 wt% solution – or –
H2S also appears to inhibit DEA degradation. But it should < 2.5 wt% DEA
also be noted that in the presence of CO2, DEA is more
likely to degrade than other amines like MEA or MDEA. Bicine 250 ppm max
Formyl DEA (DEA-F) < 3.0 wt% solution max
DEA solution corrosivity is directly affected by an increase in
THEED < 1.5 wt% solution max
the levels of DEA degradation products, heat stable salt
anions, and CO2 absorption. All of these factors will lower
the DEA solution pH. Some studies also claim that DEA Ion Exchange and electrodialysis are not able to remove
degradation products and the presence of metals together non-ionic compounds such as the DEA degradation products
will act as chelating agents, further contributing to listed above, certain metals, hydrocarbons and particulates.
corrosivity and adversely affecting solvent performance. Only distillation is able to remove these undesirable
contaminants. Bicine, in particular, is a degradation product
The good news is that DEA can be used successfully, with formed in the presence of DEA and unstable chemical
low degradation and low corrosivity, if the proper CO2 intermediates. It is considered corrosive and can be
loadings, solvent strength and heat stable salt guidelines are removed by vacuum distillation. It has been shown that ion
maintained. Individual HSS anion contaminant guidelines exchange is not very effective in removing this compound
most commonly reported by amine suppliers for DEA since it is dipolar or a zwitterion (meaning that it may
behave as an anion or a cation depending on the pH of the
solutions (based upon maintaining carbon steel corrosion solution).
Page 9 Th e R e c l a i m e r
With over 600 reclamation projects for over Business Development Managers
80 customers, CCR Technologies has Donald Aromando
demonstrated its unique ability to offer Phone: (281) 988-5800
custom-tailored solutions to reclaiming Fax: (281) 988-5858
challenges anywhere in the world – on-land Mobile: (830) 832-8497
or off-shore. E-mail: daromando@reclaim.com CCR Technologies Ltd. – CANADA
10655 Southport Road SW , Suite 440
Calgary, Alberta T2W 4Y1
If you have any needs, questions or Julie Fox
Main Toll Free: 800-820-4682
comments regarding CCR‘s mobile Phone: (281) 988-5800
Main Local: 403-543-6699
reclaiming services or our engineered Fax: (281) 988-5858 Main Fax: 403-252-2941
reclaiming systems, please contact any of our Mobile: (713) 252-1585
business development managers. E-mail: jfox@reclaim.com CCR Technologies, Inc. – USA
1500 CityWest Boulevard, Suite 550
John Sczesny Houston, TX 77042
Main Toll Free: 866-280-3073
Phone: (281) 988-5800
Main Local: 281-988-5800
Fax: (281) 988-5858
Main Fax: 281-988-5858
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