Why absorption chillers

fail
Lithium bromide-based absorption refrigeration is a viable
system capable of providing large-tonnage central air
conditioning. Water is flash boiled under vacuum at low
temperatures. This boiling action cools evaporator or chilled
water coils (Fig. 1). As the flashed water vapor accumulates
inside the chiller, vacuum is lost.
BY RICHARD LEVINE, LBD ASSOCIATES, LLC, RANDOLPH, NJ DECEMBER 15, 2001
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Key concepts
Continuous air leaks
increase the corrosion rate
in chillers
Chemical additions can do
more harm than good
Restoration instead of
replacement may be an
option for failing chillers.
Sections: 
How Absorbers
Deteriorate 
Chemical additives 
Saving an absorption
chiller

Lithium bromide-based absorption refrigeration is a viable system capable of providing

large-tonnage central air conditioning. Water is flash boiled under vacuum at low
temperatures. This boiling action cools evaporator or chilled water coils. As the flashed
water vapor accumulates inside the chiller, vacuum is lost. Lithium bromide is added to
absorb the water vapor, maintaining the vacuum condition.
Fig. 1. Operation of a two-stage absorption chiller

Diluted lithium bromide cannot continue to absorb water and must be reconstituted to
perpetuate the cycle. Reconstituted lithium bromide is returned to absorb water once more,
and the boiled-off water is returned to be flashed again. The cycle is then complete.

This thermodynamic cycle would be relatively simple were it not for the fact that lithium
bromide, at 50% concentration, is highly corrosive to mild steel. The corrosion process
inside absorbers dissolves the chiller from the inside and creates all kinds of maintenance
difficulties as the heat exchanger and flash boiling components become fouled with
corrosion debris.

The only moving parts in an absorber are the various solution pumps, which circulate the
fluids. Even so, it is not uncommon to find, after several years of operation, that many
absorbers are performing poorly, cost disproportionate dollars to maintain, and are ready to
be scrapped.

How Absorbers Deteriorate

Air, or more specifically oxygen, is the culprit. As air leaks into any absorption chiller, it
introduces oxygen, which in turn provides the cathodic reaction essential for any metal to
corrode in aqueous systems.
As oxygen dissolves in water, it releases free electrons into solution. These free electrons
are readily consumed as the ferrous, or iron-containing, metals dissolve, forming first rust
and later the magnetic, black iron oxide commonly found abundantly inside all absorption
chillers.

An occasional air leak isn’t sufficient for dissolving enough iron to plug the fine orifices of
spray headers and heat exchangers, causing the chiller to fail. Instead, it is the continuous
air leak that causes so much damage in lithium bromide-based systems.

A basic air leak, once stopped, prevents more oxygen from getting into the aqueous
system. The corrosion process merely stops by itself.

Since the absorption chiller is very dependent upon its internal vacuum being maintained,
loss of vacuum from an air leak will cause system failure. The leak would have to be
detected and stopped before a vacuum was restored and the unit placed back on line.

In the real world, absorbers are tricky to maintain. These chillers require specialized service
personnel who are not readily found. Absorption maintenance by a qualified mechanic is a
type of wizardry unto itself. Listening to the various unique chiller noises, knowing what they
mean, touching the external surfaces, sensing internal temperatures and flows, and peering
into the chiller’s sight glass are highly developed skills essential to understanding the unit’s
operation.

When a chiller is failing, usually on a 90+ degree day, there just isn’t enough time to hunt
down troublesome air leaks and fix them properly. An external vacuum pump can be
attached to the absorber’s purging mechanism. This will augment the vacuum so
significantly that, in some cases, the absorber can even operate with a huge hole in its
shell.

If air leaks aren’t stopped, the system ultimately fails. The unit continues to work because
the external pump maintains its vacuum artificially. However, the corrosion becomes intense
from the continuous supply of oxygen into the lithium bromide charge. The external vacuum
pump, at first the unit’s savior, has now turned into its worst nightmare.

Chemical additives
There is another reason leading to the demise of absorption chillers — improper solution
chemistry. There have been many attempts to deal with this chemical problem by adding
various inhibitors to the lithium bromide charge.

All that is needed to produce the refrigeration cycle is lithium bromide and water, but over
the years, additional chemicals get added to the brine. These commonly include:

 48% hydrobromic acid


 lithium hydroxide

 lithium nitrate

 lithium chromate

 lithium arsenate

 lithium molybdate.
 Each compound has been introduced in an attempt to control internal
corrosion. And while each chemical does have some effect on internal
corrosion, without proper and continuous monitoring of the lithium bromide’s
chemistry, the chemical addition can actually do more harm than good.

There are essentially two metals inside an absorption chiller. These are the
iron or ferrous-based metals in the steel shell, etc., and the copper or
cuprous-based metals of the heat transfer tubes. Each of these metals reacts
with oxygen and corrodes under different conditions, and protecting one
metal usually causes the other to suffer.

Fig. 2. Corrosion inside an absorption chiller

The ferrous metals are attacked at low pH and solution alkalinity levels while
the cuprous components are spared, and vice versa. It becomes a tradeoff
trying to protect one metal or the other. A delicate balance needs to be
established where both metals can be simultaneously saved. This requires
chemical expertise.

Hydrobromic acid and lithium hydroxide modify the solution’s pH and

alkalinity. The acid lowers these values while the hydroxide increases them.
Other chemicals (nitrate, chromate, arsenate, and molybdate) are specific
inhibitors mainly designed to protect the ferrous metals.

The cuprous metals are naturally protected at low pH and low solution
alkalinities. It is the ferrous metals that suffer under these conditions. If low
pH and alkalinity are maintained in the lithium bromide brine, all that is
needed is an inhibitor to protect the steel.
Nitrate works by increasing the formation of iron oxide commonly found in all
absorbers. The idea is that this oxide will coat the steel surface and prevent
additional corrosive attack. It is a good concept, except that the oxide layer
becomes too thick, ultimately falling off the steel into the solution.

This debris then fouls all of the internal orifices, causing significant problems.
There is no way to control the amount of iron oxide produced when lithium
nitrate is added. The oxide layer continues to accumulate.

As the nitrate is consumed, it forms ammonia. Corroding steel generates

hydrogen gas. Hydrogen reacts directly with nitrate, reducing it to ammonia.
Ammonia is very harmful to cuprous materials. It increases the overall
corrosion rate of copper-based metals and can be a component of more
exotic corrosion failures, such as stress corrosion cracking.

Because nitrate has the ability to “calm” an absorption chiller by scavenging

the corrosion-generated hydrogen gas, service personnel, attempting to keep
chillers operating, have overused it. A casual addition of a pound or two of
extra nitrate into a chiller, while it may initially help to restore lost vacuum,
ultimately speeds up the chiller’s demise.

Similar to lithium nitrate is lithium arsenate. Used only in early two-stage

chillers, the arsenic didn’t really solve any corrosion problems. Since it did not
produce ammonia in the system, the copper tubes were spared from stress
corrosion failures. But the arsenic equivalent to ammonia is arsine gas, and
this causes stress-related failures in some stainless steel tubing. Also, since
arsine is toxic, its application was very short lived in absorption chemistry.

Lithium chromate and lithium molybdate protect steel without the formation of
ammonia or iron oxide. They don’t scavenge hydrogen gas formed when the
iron corrodes. They stop iron from corroding in the first place. These are
effective corrosion inhibitors in brine systems such as lithium bromide.

Since chromates are pollutants, their usage has been highly reduced over the
years. However, it is still quite reasonable to apply chromates in closed
systems such as absorption chillers, since nothing is being discharged into
the environment. The trend has been toward using molybdate instead. But
molybdate isn’t as effective a corrosion inhibitor as chromate, and it is a
mistake not to utilize chromates where they can be correctly applied.

Lithium bromide corrosion control in absorption refrigeration is a very complex

scheme of proper mechanical operation and the balance of added chemicals.
What complicates the situation still further is that there aren’t a large number
of highly skilled personnel available to service absorption systems.

These conditions lead to many absorption machines suffering from severe

corrosion. They are performing very poorly at best and many are ready to be
scrapped prematurely. But, these machines can be saved.
Saving an absorption chiller
Once an absorption chiller starts to corrode, it can degenerate quickly. Fine
particulates of rust, magnetic iron oxide, copper, and copper oxide can easily
plug spray header nozzles and heat exchangers, reducing efficiency. A large
amount of debris can foul pumps and reduce heat transfer.

When an absorption chiller no longer meets the needs of the facility, owners
must consider replacing the unit or continuing to maintain a marginal piece of
equipment.

It is not a simple process to remove and replace a chiller. These systems are
often very large, requiring that portions of the building housing the chiller be
demolished to get the old unit out and the replacement installed.

Often today’s replacement may not be available in a size equivalent to the

tonnage of the older unit, necessitating additional equipment. There is also
the piping retrofit to consider and disposal of the waste lithium bromide.

Faced with such overwhelming considerations, it becomes feasible to look

closely into restoration of the old chiller. In order to accomplish this, qualified
absorption service personnel capable of dealing with lithium bromide-based
refrigeration systems and their chemistries are required.

At an expense of 40-60% of replacement cost, a deteriorated chiller can be

restored. That means it would not be necessary to tear apart a building or refit
piping. With proper mechanical and chemical maintenance, a chiller should
last a long time and perform well.

Controlling the lithium bromide corrosion, cleaning up debris, and repairing

any mechanical damage is the recipe for saving any absorption machine.

— Edited by Joseph L. Foszcz, Senior Editor, 630-320-

7135, jfoszcz@cahners.com

Analytical tests for absorption chillers

Test Significance
Specific
Measure of strength of lithium bromide charge.Indicates
gravity/Lithium
operational status of absorber.
bromide
Indicator of possible air leakage into chiller.Affects metal
Alkalinity/pH
corrosion.
Dissolved copper Measure of corrosion of tubing and/or pump windings.
Dissolved Measure of corrosion of steel interior.Indicates degree of
iron/suspended internal fouling.
 solids
Lithium nitrate Measure of nitrate inhibitor strength.
Indicates amount of nitrate inhibitor reduced to
ammonia.Can indicate the degree of corrosion of copper
Ammonia
portions.Indicates potential for stress corrosion cracking of
copper tubing.
Lithium arsenite Measure of arsenite inhibitor strength.
Lithium chromate Measure of chromate inhibitor strength.
Lithium molybdate Measure of molybdate inhibitor strength.

CARLSBAD, CA (PRWEB) JULY 06, 2017

Industry leaders acknowledge the benefits of absorption chillers in CoGeneration systems and
Natural Gas Cooling for HVAC. With natural gas pricing low for the foreseeable future, and electric
rates on the rise, CoGeneration and Natural Gas Cooling have compelling return on investment.

So, why do absorption chillers represent such a small market in the USA, when worldwide,
absorption chillers represent a much larger application base, with well over 60,000 installations?

Shuangliang Eco-Energy, a world leader in the absorption chiller market since 1985, has many
patented and unique features which solve the problems associated with previous absorption chiller
designs.

ENRGISTX and Shuangliang Eco-Energy provide enhancements for the USA market, which add to
these existing design features, extending reliability, system life, and lowering operating costs over
alternative absorption or electric chillers solutions.

Shuangliang Eco-Energy has long been recognized for these quality design benefits, with
installations of over 25,000 absorption chillers in more than 100 countries.

Not only have end users recognized these benefits, companies such as Johnson Controls, York and
TRANE have sold Shuangliang Eco-Energy under their brand internationally through OEM
agreements, for over 20 years.

Historic Issues with Absorption Chiller Designs 

Plant managers previous experience with absorption chillers remember these problems: 
 Higher frequency of tube failures (this is a symptom, not the disease)
 Crystallization
 Complexity of service
 Lack of trained technicians
 Service controlled and limited by the manufacturer

Causes of Tube Failure 

For refrigerant and solution distribution, Shuangliang Eco-Energy utilizes a Two Pump 
design with 316 Stainless Steel Dripping Plates vs. a Three Pump and Spray Nozzle structure in
competitive designs. The Dripping Plate design results in more even distribution of refrigerant
leading to higher chiller efficiencies. In addition, Spray Nozzles are subject to erosion and clogging,
resulting in uneven solution and refrigerant distribution and tube erosion due to concentrated spray
areas. This problem is eliminated due to this unique Dripping Plate technology.

The other major reason for tube failure is the quality of condenser water. This is the responsibility of
the operators. However, Shuangliang uses 316 Stainless Steel for the absorber and condenser
water tubes, which outperforms copper and it’s compounds.

Crystallization 
Shuangliang Eco-Energy utilizes a Serial Solution Flow Design vs. Parallel Solution Flow. This
provides improved control over solution flow rate and concentration of the LiBr solution, reducing risk
of crystallization. This Serial Flow design enables the chiller to be custom designed and fitted for the
specific application where varying parameters can be taken into consideration. These include heat
source temperature and pressure drops, chilled water and cooling water temperature variations.

Shuangliang Eco-Energy has a unique approach to minimizing crystallization. Shuangliang

manufacturers its own LiBr solution, controlling the solution characteristics. This allows for tighter
control of the anti-crystallization Programmable Logic Control (PLC) Real Time process, and
improved reliability.

Shuangliang Eco-Energy chillers utilize an automated Real Time Safety Design control system,
preventing crystallization in all but rare cases. In the rare case of crystallization, there is an
automated de-crystallization process that delivers warming solution to the crystallized tubes,
returning the system to normal operation. Shuangliang Eco-Energy Real Time dynamic trend
analysis shows the operating point of the chiller relative to the crystallization point at all operational
conditions, and will automatically adjust the chiller operation to avoid crystallization.

Shuangliang Eco-Energy utilizes a Shell-Tube Heat Exchanger (STHE) in the absorption section vs.
Plate Heat Exchangers (PHE) used in competitive designs. Although a PHE has higher heat transfer
efficiency, the LiBr solution will lose more heat in the PHE when the temperature of the LiBr
becomes low and the concentration high, and the LiBr will more easily Crystallize, clogging the
tubes, as the gap between plates is narrow. If crystallization occurs in a PHE, it is very difficult to de-
crystallize. Whereas, with the STHE design, there is a lower probability of crystallization, and de-
crystallization is straight forward, easily accessible on the outside of the chiller, by just heating the
STHE.

By using a unique absorber-evaporator-absorber structure, the vapor generated in the evaporator

can be absorbed more efficiently, which leads to higher chiller COP, and only a small area of
insulation is needed for the Evaporator, as most of its area is surrounded by the absorber.

Shuangliang Eco-Energy utilizes a Vertical High Pressure Generator Water Tube Design (vs Long
Horizontal Fire Tube Design) –Shorter vertical arranged tubes and tube welding points surrounded
by solution results in lower thermal expansion on the tube welding points, thus decreasing the
probability of leakage. In addition, the whole tube chamber is surrounded by solution, so thermal
efficiency is higher and there is no need for insulation of the chamber. This vertical design also
enables a lower flue gas pressure drop through the unit, contributing to a higher electrical efficiency
for most turbine and reciprocating generators.

Shuangliang Eco-Energy is the only manufacturer which tests the complete chiller unit for Helium
leakage in a hard covered helium vacuum detection process. In addition, the leakage tests to four
orders of magnitude lower pressure than the nearest competitor’s component leakage tests.
Leakage rate limit of <1 x 10-10 m3 pa/s . This level of testing enables longer system life.
Shuangliang Eco-Energy, manufacturing chillers for over 30 years, has many units in operation
beyond 20 years.

Fabrication and Quality Manufacturing 

 Superior metallurgy: 316 Stainless Steel Condenser Water and Absorber Tubes, Drip Plates
and Eliminators; Carbon Steel High Pressure Generator; Stainless Steel Low Pressure
Generator
 Drip Plate liquid distribution with stainless steel filtration, no erosion
 Advanced manufacturing processes
 3-dimensional pipe bending, minimizing weld points
 CNC/Plasma cutting, automatic and semi-automatic welding
 Lithium Bromide manufactured by Shuangliang
 Double sealed mechanical valves, hermetic solution and refrigerant pumps

Operational Quality 
 Split Absorber: higher cooling capacity, lower $/ton
 Variable Frequency Drive for superior part load performance
 Marine style water boxes, with hinges and flanges connections
 Automatic Anti-Crystallization and De-Crystallization real time controls

Complexity of service - Lack of trained technicians - Service controlled by the manufacturer 

ENRGISTX, the USA distributor for Shuangliang Eco-Energy chillers, is establishing an independent
network of factory trained and certified absorption chiller technicians. Where ever a chiller is sold, a
qualified service operation will be factory trained and certified to maintain and service the chillers.
Service is backed up by real time factory monitoring and support.

Innovation and leadership in flue-gas absorption cooling 

Shuangliang developed the first flue-gas absorption chiller in 2004, and since has dominated this
solution market worldwide.

Shuangliang won the prestigious “Outstanding Contribution Award” for the 2008 Olympic Games in
Beijing. This award was in recognition for their flue-gas and hot water absorption chillers installed in
Combined Cooling Heating and Power (CCHP) systems at the Olympic Sports Center, Olympic
Conference Center, and Beijing South and West Railway Stations. Shuangliang Flue-gas chillers are
installed in more than 20 countries on 6 continents.

Shanghai Disney Resort depends on Shuangliang dual-fuel flue-gas and hot water chillers,
delivering 5,500 tons of cooling.

Your Shuangliang Eco-Energy absorption chiller lives long and your company will prosper.