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Technical

Bulletin

Max-Amine* 70B
Controls Amine System Foaming
Key Points: • Coke oven gas processing
• Max-Amine 70B is uniquely formulated to reduce • Cryogenic gas processing and
foaming in amine systems using MEA, DEA, • Synthesis gas purification.
MDEA, DGA and formulated amine solvents.
Max-Amine 70B is newest generation defoamer of
• The research and technology division for a major
GE Water & Process Technologies for use in amine
oil refiner has approved Max-Amine 70B for use
treating gas and liquid hydrocarbons. Max-Amine
in amine systems including those upstream to
70B should be considered as an alternative to
alkylation and other sensitive process units.
upgrading equipment to control hydrocarbon
• Max-Amine 70B has been proven to be more entrainment, amine losses or for incremental
cost effective than silicone, polyglycol or alcohol increases in unit throughput.
based products.
• In contrast to silicone based defoamers, Max- Max-Amine 70B has proven to be effective in field
Amine 70B does not increase equipment fouling, and laboratory tests in MEA, DEA, MDEA, DGA and
particulate filtration costs and the emulsification formulated amine solvents.
tendency of the amine.
Experience In Europe
• In contrast to many polyglycol based defoam-
ers, Max-Amine 70B does not degrade to fatty The following write up has been taken from an
acid soaps that increase foaming. internal newsletter distributed worldwide by the
• In contrast to alcohol based defoamers, Max- research and technology division for this refining
Amine 70B does not degrade to organic acids. company. Changes were made only to remove the
name of the operating company, refinery location
Superior foam control combined with negligible side and the addition of American units. This application
effects make Max-Amine 70B an excellent product resulted in an immediate savings of US$250,000 for
to use for controlling foaming problems in amine a chemical cost of only US$6,500, a return of over
systems. 4,000%.

Applications “In April 1998, a refinery in the United Kingdom


switched to a novel antifoaming agent, a product
Max-Amine 70B is a defoamer (or antifoam) formu- called Max-Amine 70B, supplied by GE. The switch
lated for use in amine systems that remove carbon followed a period of extreme foaming, which
dioxide (CO2) and hydrogen sulphide (H2S) in gas caused their amine system to have serious opera-
processing applications such as: tional difficulties. The result has been dramatic with
• Natural gas processing the complete elimination of operational upsets due
to foaming and flooding.
• Refinery amine systems
• Hydrogen production This refinery amine system has an inventory of
200 tons (441,000 lbs) of 40 wt% DIPA, circulates
• Ammonia manufacture

Find a contact near you by Global Headquarters Americas Europe/Middle East/Africa Asia/Pacific
visiting gewater.com or Trevose, PA Watertown, MA Heverlee, Belgium Shanghai, China
e-mailing custhelp@ge.com. +1-215-355-3300 +1-617-926-2500 +32-16-40-20-00 +86 (0) 411-8366-6489

©2006, General Electric Company. All rights reserved.


*Trademark of General Electric Company; may be registered in one or more countries. HPG718EN 0605
440 gpm (100 m3/h) of solvent to 3 treaters: a dry
gas absorber and LPG treater on the cat cracker
gas plant and a propane treater on one of their
crude distiller units.
Following a major turnaround in February 1998,
severe problems with foaming and flooding of both
the amine regenerator column and dry gas
absorber were encountered. Part of the problem
was traced to problems with the regenerator col- Figure 1
umn internals, which had been replaced at the
shutdown. These were subsequently rectified. It shot feeding 6 kg (1.6 gal) every 48 hours. This
was recognized though that, for reasons still not served to show that the antifoam was effective for
fully understood, the foaming tendency of the between 36 and 48 hours. (Figure 1). The loss of
amine solvent was intrinsically high. effectiveness is at least in part attributed to absorp-
tion onto the activated carbon filter in the system
Like most other amine units, this refinery had been but GE also claims that the product slowly breaks
using a silicone-based antifoam to alleviate the down to alcohols which are removed by the bleed
problems of foaming; relying on the intervention of from the regenerator column reflux.
operators to stabilise the system during foaming
events by shot dosing of antifoam. Such antifoams, A move was made to continuous dosing, first at
however, have always had two drawbacks: 3 kg/day (0.8 gal) and now at 2 kg/day (0.5 gal). The
1. They cannot be dosed in a manner which will results have been very positive, reducing the vari-
prevent foaming so rely on careful operator ance in daily dP from over 200 mbar (3 psi) to less
attention to act in time, than 25 mbar (0.36 psi).
2. If overdosed they can start to contribute to The main concern at the refinery with Max-Amine
foaming. 70B was that since it has a high molecular weight
molecule containing nearly 30% by weight oxygen,
It was almost by chance that the refinery learned of
it could partition into the LPG stream in the LPG
a novel antifoaming agent, Max-Amine 70B, a high
treater and give problems with the HF alkylation
molecular weight polyalkyl oxalate, marketed by
unit and Butamer units downstream. An analytical
GE. This product is fundamentally different from
method was therefore developed for Max-Amine
silicone-based antifoams in that it is designed to be
70B and tests were conducted on HF alkylation unit
added continuously to reduce the intrinsic foaming
feed. These tests showed that the Max-Amine does
tendency of the solvent and hence eliminate foam-
not extract to any significant extent into LPG.
ing. GE could only provide one reference for this
product in Europe, but the xperience of this refinery Apart from the improved stability, the only other
was very positive. noticeable impact of Max-Amine 70B has been an
increase in pressure drop, about 15 mbar (0.2 psi), in
On the basis of this reference, the refinery started a
the dry gas absorber, which in itself has not created
trial with Max-Amine 70B and has now een using
a problem. The refinery continues to evaluate the
the antifoam since April 1998. Without Max-Amine
performance of the antifoam and are now review-
70B addition, the amine roduces a foam, which
ing whether Max-Amine eliminates the need for
typically takes 30 to 40 seconds to break following
activated carbon filtration.
vigorous shaking in bottle. With Max-Amine 70B
added at a daily rate of 10 ppm (mg/L) based on The conclusion – for amine systems which suffer
solvent volume, foam tability is reduced to between from foaming problems which do not respond well
three and four seconds. This has both eliminated to silicone-based antifoam – Max-Amine 70B would
foaming and enabled higher stripping steam rates seem well worth a try.
to be used in the regenerator.
In line with GE advice, the antifoam is injected into
the rich amine return to regenerator column. At
first, dosing was done on an intermittent basis with
Page 2 HPG718EN 0605
Foaming in Amine Solutions amine solution increases the foaming tendency
and stability of the solution.
Foaming occurs as the result of the physical inclu- 3. Solids, particularly those less than 5 micron,
sion of gas bubbles enveloped by the amine solu- concentrate on the liquid surface and increase
tion. Clean amine solutions have a low tendency to surface viscosity and slow drainage. Particles
foam because they are very polar and have high that have anionic or cationic bonding sites, such
surface tensions. Clean amine solutions also pro- as iron based corrosion products or activated
duce foams with little stability because they have carbon particles, will have a greater effect on
low viscosity. Foaming problems in amine units are slowing bubble drainage in polar solutions.
due to contamination by materials that reduce sur-
face tension and increase viscosity. While hydrocarbons, acids and solids are easily
identified materials that increase foaming in amine
Low surface tension is usually associated with a solutions, any chemical species that lowers the sur-
high foaming tendency. This is because a low sur- face tension of the liquid film increases foaming
face tension liquid allows the surface of a bubble to tendency while any species that inhibits liquid
expand easily. Liquid from the bulk solution readily drainage or increases viscosity increases foam sta-
flows to the surface, allowing the bubble to form. bility.
Amine solutions, like most polar liquids, have a high
surface tension as compared to hydrocarbons Antifoam - Defoamer
which are essentially non-polar. Thus, hydrocar-
bons are the most likely cause for an increase in the Antifoams or defoamers are chemicals which are
tendency of an amine solution to foam. formulated to increase the elasticity of the liquid
film on the bubble. By allowing the liquid film to
An amine solution that readily foams is not a prob-
expand, thin spots form allowing the bubble to rup-
lem unless the foam is stable. Increasing the viscos-
ture. Foam made from such an elastic film will be
ity of the amine solution results in slower drainage
unstable. For any material to be an effective
of the liquid from the bubble surface. The longer it
defoamer, it must have extremely low solubility in
takes for the liquid to drain from the bubble, the
the amine solution. If it is soluble, it will not concen-
longer the bubble will last. Three types of com-
trate at the surface film and it would be able to
pounds common in amine systems – hydrocarbons,
migrate to the film as the bubble expands – repair-
acids and solids - will increase foaming tendency.
ing the thin spots.
1. Hydrocarbons that are dissolved in the amine
solution can increase the solution viscosity and Max-Amine 70B
slow drainage from the surface film. The impact
of hydrocarbons on foaming in amin solutions Max-Amine 70B is a defoamer designed by GE to
is different for each amine solvent because of out perform silicone, polyglycol or alcohol based
the difference in hydrocarbon solubility. MEA products and avoid the side effects common to
and DEA solutions have the lowest hydrocarbon these materials. Max-Amine 70B is a non-ionic
solubility and are little effected by clean hydro- polymer made of repeated polyoxyethylene and
carbons. MDEA, on the other hand, has a much polyoxypropylene chemical groups. It is resistant to
greater affinity for hydrocarbons and foam sta- degradation and forms shorter chain length poly-
bility is greatly increased by the presence of mers upon degradation. Max-Amine 70B is removed
liquid hydrocarbon. to some extent by activated carbon filtration but is
2. Acids, particularly organic acids, greatly also removed in the flash drum (3-phase separator).
increase foam stability. First, organic acids can
increase the solubility of hydrocarbons in the Testing conducted in GE’s Research Laboratories
amine solution. Organic acids can also stabilize reveal that Max-Amine 70B out performs silicone,
a hydrocarbon/amine solution emulsion that polyglycol and alcohol based products in foam
will slow bubble drainage. Organic acids also tests conducted using both laboratory amine solu-
increase the viscosity of the amine solution and tions and actual plant amine solutions. Figure 2 and
promote the formation of a gel like bubble sur- Table 1 illustrates the performance advantage of
face film. Thus increasing acid content in the Max-Amine 70B in two refinery amine samples.

HPG718EN 0605 Page 3


Similar testing conducted by a major amine manu-
facturer support the results of this testing.
While Max-Amine 70B outperforms other defoamer Silicone Antifoams
and antifoam products, the most important benefit
Silicone based defoamers are composed of a sili-
of this product is the absence of the following side
cone compound (such as dimethyl polysiloxane)
effects:
emulsified in water or hydrocarbon oil. (methyl
1. Max-Amine 70B does not increase equipment acrylic acid is most often used to form the disper-
fouling, particulate filtration costs or the emul- sion). Silicone based products are used for foam
sion tendency of the amine solution, in contrast control in a wide range of process systems includ-
to silicone based products. ing cokers, sour water strippers and amine systems.
2. Max-Amine 70B does not breakdown to fatty Most of these systems are “once-through” and no
acids or fatty acid soaps that increase foaming, serious side effects will be noted. Amine systems
in contrast to polyglycol ester based products. are not once-through and defoamers tend to
3. Max-Amine 70B does not breakdown to form remain in the system for several days. Silicone
organic acids, in contrast to alcohol based based products, in particular, tend to coat metal
products. surfaces, filter media, and particles in the system.
These products also increase the emulsification
As of November 1998, 29 amine systems located in tendency of the amine. These side effects lead to
the United States and Europe were using equipment fouling, increased filtration costs and
Max-Amine 70B. Of these, 23 are refinery amine higher amine losses.
units, 2 are coke oven gas plants and 4 are natural
gas processing plants. Additional systems in Can- Polyglycol Antifoams
ada, South America, Africa and Asia are using Max-
Amine 70B. Polygylcol based defoamers include a large num-
ber of compounds based on polyethylene glycol
(PEG) and polypropylene glycol (PPG). These
defoamers may also contain co-solvents to pro-
duce a uniform product. A polyglycol ester is the
reaction product of a polyglycol and a fatty acid.
Polyglycol esters (such as PEG DOT) are often much
better defoaming agents than the non-ester poly-
glycol. Unfortunately, the ester readily hydrolyses
back to the polyglycol and fatty acid. The fatty acid
soaponifies – it forms a soap with very strong
Figure 2: Defoamer performance in refinery amine samples foaming properties. The formation of soaponified
(treatment required to completely suppress foam) fatty acids in once-through systems (such as a sour
water stripper) is of little importance but in a closed
Table 1: Defoamer Performance and Sludging Potential system, like an amine unit, it creates a cycle of
Defoamer Refinery Refinery Surface increasing foaming severity.
MDEA 140F 75F (ppm) Appearance
(ppm) DEA (after 12 hours)
silicone 74 500 floating flocs
polyglycol >2000 250 clear liquid
polyglycol 150 900 no surface layer
ester
alcohol 1135 750 clear liquid
Max-Amine 51 125 clear liquid
70B
nitrogen flow at 800 ml/min, size D frit.
ppm based on actives required to completely suppress foam

Page 4 HPG718EN 0605


Alcohol Defoamers resolve the problem. Hydrocarbons that vaporize
overhead should be removed by purging the reflux
Alcohol based defoamers are made of unsaturated accumulator to the waste water system.
fatty alcohols with about 16 to 20 carbon atoms.
Oleyl alcohol is a common example. Like silicone As with any foaming control chemical, the presence
and polyglycol based products, co-solvents may be of other antifoams may have a negative side effect
included to produce a uniform product. As com- on performance. Whenever possible, allow several
pared to silicone based products, alcohol defoam- hours or even days for one antifoam product to exit
ers are generally less effective but less expensive. the system prior to injecting a new product. Max-
The problem with alcohol based defoamers is their Amine 70B has been found to be compatible with
rapid degradation to organic acids. Formic and ace- most polyglycol and alcohol type of antifoams but
tic acids are common degradation products but high concentrations of silicone based products
longer chain acids are also formed. The longer reduce its performance.
chain length acids can result in more serious foam-
ing problems. Determination of Foaming Tendency
and Stability
Max-Amine 70B Application
This is a simple procedure that can be used to
The most common location for foaming in an amine determine the foaming tendency and stability of an
system is in gas treaters or absorbers. Foaming in amine solution. If the defoamer products are to be
amine absorbers can result in reduced treating evaluated, the amine solution should be allowed to
capacity, off specification products and high amine settle in a separatory funnel for at least one hour
losses. If the problem is condensing hydrocarbons, before the bottom layer is used for the evaluation.
the foaming may be resolved by increasing the The amine solution should be heated to 100°F
Lean Amine temperature. If hydrocarbons are (37.8°C) or the Lean Amine feed temperature to the
entrained in the gas feed, increasing the tempera- absorber.
ture may have little or no effect.
Equipment
The injection of Max-Amine 70B into the Lean
Amine feed to the absorber(s) should resolve the 1 liter graduated cylinder gas flow meter (500 to
foaming. It can be injected with “shot feed” injection 5000 ml/min) gas supply – nitrogen or air timing
equipment or with a chemical injection pump. For device connecting tubing hot water bath sparger
shot feed applications, two to four quarts are tube – sintered glass, metal or ceramic.
injected at a time. The dosage for a continuous in-
jection system is typically 10 to 50 ppm (mg/L)/day Procedure
based on system volume. 1. Pour 200 ml of 100°F (37.8°C) amine solution
into the graduated cylinder.
The use of Max-Amine 70B has also been beneficial
in improving the separation of gas, liquid hydrocar- 2. Establish gas flow at 4,000 ml/min. Insert spar-
bon and amine solution when injected into the Rich ger tube and begin timing.
Amine upstream to the Flash Drum. 3. Record foam height after one minute. Stop gas
flow and reset timer.
One of the most serious locations for foaming is in 4. Record time required for foam to break to a liq-
the regenerator. Foaming in the regenerator usually uid surface.
corresponds with a loss of liquid level in the bottom
of the tower, reduced tower top temperature and a 5. Thoroughly clean cylinder and sparger tube
higher Lean Amine loading. Reducing the steam before and after each use.
rate may allow the hydrocarbon to descend in the 6. Repeat, adding defoamer product at desired
tower, reducing the foaming by reducing vapor concentration.
traffic. Alternately, a small amount of Max-Amine Note: If foam exceeds height of cylinder, repeat us-
70B injected into the Rich Amine or Reflux can help ing a lower gas rate.

HPG718EN 0605 Page 5

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