Improve Glass-Lined Reactor

Efficiency with Safe,

Effective Cleaning
of the Reactor Jacket
James P. McIntyre
BetzDearborn
Horsham, PA USA

Technical Paper

IMPROVE GLASS-LINED REACTOR EFFICIENCY WITH SAFE, EFFECTIVE

CLEANING OF THE REACTOR JACKET
ABSTRACT

Comparison of Corrosion Resistance

This paper details a process for cleaning glass-lined

reactor jackets that functions at neutral pH and is safe
for workers, equipment and the environment. This
unique chemistry successfully dissolves rust and
scale, resulting in clean, passivated reactor jackets
and increased production efficiency. This process provides all of these benefits without the risk of nonrepairable spalling (a.k.a. fishscaling) damage to the
glass lining.

OXIDIZING

REDUCING

CHLORIDES

GLASTEEL
TANTALUM
FLUOROCARBONS
FIBER-REINFORCED PLASTICS
ZIRCONIUM
HASTELLOY B
TITANIUM-PALLADIUM
TITANIUM
HASTELLOY C
MONEL
HASTELLOY G
NO CHLORIDES

ZIRCONIUM

INTRODUCTION
Glass-lined reactors are used in virtually all of the
world's pharmaceutical manufacturing facilities. There
are several key reasons for their selection by design
engineers.

HASTELLOY C
CARPENTER 20 Cb-3
MONEL
INCONEL
STAINLESS STEEL
OXIDIZING

REDUCING

Figure 1: Glass lining has the widest range of corrosion

resistance of any material used for equipment.

In a pharmaceutical process, cleanability is critical.

Between batches, each reactor and its associated
process equipment must be thoroughly cleaned in
order to assure product quality and minimize heat
transfer resistance caused by product buildup.
Fortunately, glass has a high degree of surface
smoothness which makes it easy to clean using noncorrosive, low pressure cleaning systems .

In a typical application steam, cooling water and a

chilled solution might all be used in the same jacket at
different points in the reaction cycle. It is very efficient
from a production standpoint but it is also potentially
damaging from a mechanical standpoint. In short,
good process designs can and do result in poor
designs for corrosion and deposit control.
To see how this can occur, one has only to think about
the process. There is an endless variety of reaction
schemes in use, so for the sake of brevity, we will
examine just a few of the many possible scenarios.

Glass is also chemically resistant and as a result, can

serve for many years in environments that would
quickly render most metal vessels unserviceable.
Aggressive reaction environments also tend to dissolve metals from unlined mild steel or alloy reactors.
These metals can compromise product quality in an
industry where purity is essential. By comparison, the
glass-lining protects the base metal so effectively that
the relatively benign heat transfer fluids used in the
jacket space will generally attack the jacket and reactor exterior long before the reaction environment compromises the glass-lined interior of the vessel.

Let's consider the process of heating a batch.

Frequently, steam is injected directly into the jacket
space until the target reaction temperature is reached.
If the target temperature is below boiling, the steam
will be condensed to what is essentially, pure water.
This condensate is very aggressive to mild steel and
will act to corrode the metal in the jacket space.
Once the heating cycle is complete, our hypothetical
reaction proceeds. If heat must be removed from the
reaction mass, cooling fluid is passed through the
jacket in order to precisely control the reaction temperature. The cooling fluid is often common plant service water and can contain a high level of dissolved
minerals including calcium, magnesium, silica, iron
and alkalinity. These minerals have retrograde solubility with temperature. In other words, instead of
becoming more soluble at high temperatures, (like
table salt), these minerals become less soluble at high
temperatures. Under high heat fluxes at the reactor
wall, the skin temperatures will be elevated. That high
skin temperature promotes mineral deposition on the
reactor wall within the jacket space.

The technology certainly exists to minimize corrosion

in the jacket space , but it is not often implemented.
There are many reasons for this but the major factor is
that productivity is usually a higher priority. Reaction
schemes are designed to be as brief as possible in
order to maximize production. From the standpoint of
corrosion and deposition, it would be ideal to have one
properly inhibited fluid that could serve as both a heating and cooling medium. However, there are faster
methods of heating and cooling. Steam is commonly
used because it heats reactors very quickly and water
is used for cooling because it cools reactors very
quickly. For rapid chilling to lower temperatures, there
are mechanically chilled glycol solutions or salt brines.
1

Deposition of minerals onto steel is a problem for two

reasons: first, the mineral scale impedes heat transfer
which can extend batch times thereby limiting production; second, soluble ions in the water such as chlorides and sulfates tend to concentrate underneath the
deposit. These ions increase the solubility of iron and
result in what is typically called underdeposit corrosion. Underdeposit corrosion is really just a special
case of crevice corrosion. Both phenomena are manifestations of concentration-cell corrosion. This type
of corrosion can result in highly localized metal loss.
In addition to introducing minerals into the reactor jacket space, cooling water usually brings in dissolved oxygen as well. Oxygen, like most gases, is more soluble
at lower temperatures than it is at higher temperatures.
When the cool water contacts the hot reactor wall, oxygen is liberated from the water. Since corrosion is
nothing more than a special type of oxidation, and oxygen is an oxidizing agent, it contributes to corrosion.
This phenomenon is so common that it has its own
name. It is generally recognized as oxygen pitting or
oxygen corrosion. Oxygen pitting is a common cause
of metal perforation in heating zones of water systems.

Figure 2: Damage to glass lining during cleanup

(spalling).

for specific maximum pressure. If the wall thickness is

too severely reduced, the vessel may be required by
code to be de-rated to a lower pressure. If the pressure is lower than that required in the process, the
reactor may have to be removed from service.

After our hypothetical reaction is complete, there is a

cooling cycle during which the temperature is reduced
to a predetermined target. Once the product is cool
and it is transferred out of the vessel, the reactor is
prepared for another run. As jacket fouling builds up
over the years, both heating and cooling cycle times
can be extended significantly because of the added
resistance to heat transfer.

These problems are nothing new to operators of glasslined reactors. The problems have been occurring for
decades and corrective action has been required for
decades. The most commonly used corrective action
is acidic cleaning In fact, pharmaceutical companies
have been performing them for many years. Acidic
cleaning, however, carries with it the inherent risk of
glass damage. Such damage can cause considerable
downtime.

The significance of this comes down to one thing - production. Corrosion and fouling directly increase cycle
time and reduce the efficiency of the production facility. There are, however, other, more serious problems
that can result from corrosion. In cases of extreme
metal loss, a reaction vessel may need to be removed
from service. Glass-lined reactors are typically rated

Glass damage occurs as a result of monatomic hydrogen (H0) permeating the steel from the jacket side.
Because monatomic hydrogen is chargeless and very
small, it is able to travel through the steel. When the

Figure 3

hydrogen atoms reach the metal/glass interface, they

react to form molecular hydrogen(H2). Along with this
reaction comes a roughly five-fold increase in volume.
In time, the resulting pressure causes the glass to
chip. Because the initial chip is crescent shaped and
closely resembles a small fishscale, the term "fishscaling" is commonly used . It is important to note that
fishscale damage extends from the substrate metal
through the glass coating to the surface. As a result,
the integrity of the glass lining with respect to corrosion
resistance is completely compromised.

effect on the mineral scales which need to be removed

in order to restore heat transfer.
One neutral pH cleaning program has been identified
and in fact, is recommended by the major
manufacturers of glass-lined equipment, as the only
safe and effective way to clean the reactor jacket
space. This neutral pH cleaning service is designed to
remove iron or calcium-based fouling while
maintaining a pH between 6.5 and 7.5. This cleaning
solution has been documented as generating no
measurable hydrogen flux through mild steel . As a
result, the risk of fishscaling glass damage is almost
non-existent. To date there are no known glass
failures from the use of this material.

Because fishscale-type spallation often extends over a

considerable area. For that reason it is almost impossible to repair on-site. Practically speaking, it can only
be repaired at a qualified repair facility.
The process involves removing the vessel from service and shipping it to the repair facility where the
jacket is removed and the reactor is grit-blasted to
remove the original glass surface and any deposits
that may have built up in the jacket space. It is then
inspected to ensure that the reactor can be repaired to
the original code specifications. If corrosion has been
severe and wall thickness has been reduced over
large areas, it may be cost-prohibitive to repair the
vessel. Replacement may be a more economical
option.

CASE STUDY: IRON OXIDE FOULED

PHARMACEUTICAL REACTOR
A leading pharmaceutical manufacturer relied on several glass-lined steel reactors in its production
process. As is common, the plant was operating at full
capacity within the constraints of current process cycle
times. The production process had very stringent
heating and cooling requirements. Variations in heating and cooling times negatively impacted product
quality and product yield. The reaction equipment was
serviced by multiple utility fluids including steam and
cooling water. Over years of use, the reactors became
considerably iron oxide fouled resulting in production
problems. Because of reactor jacket fouling, the stringent heating and cooling requirements were not met.
Process batch cycle times became extended and
product quality suffered. At the same time, batches
could not be produced as quickly, so production suffered a substantial decline.

After that determination is made, the necessary metal

repairs are completed and the vessel interior is again
grit blasted in preparation for re-glassing. The correct
number of glass coatings is applied, with a thorough
integrity inspection between each coat. After a final
glass inspection, the jacket is welded onto the reactor,
the exterior is painted and any required accessory
items are installed. The vessel is now ready for shipment back to the owner. The owner must then reinstall
the reactor along with its associated piping and controls. This process is very costly in terms of downtime
and the actual cost of the re-glassing. It is important
to remember that these costs could have been avoided through the correct selection of jacket cleaning
materials and procedures.

Plant personnel knew that they needed to remove the

offending deposits from the reactor jacket space. They
knew that, short of replacing the reactors, it was the
only way to restore productivity. Being familiar with the
danger of fishscaling, they were understandably reluctant to undertake any type of acidic cleaning. In addition to concern for the integrity of the glass lining, there
was expressed concern about excessive acid corrosion of the mild steel jacket. This concern was well
founded because if acid cleanings are not properly
neutralized, flushed and rechecked, acid hideout can
cause severe metal loss. Substantial metal loss might
preclude the use of the vessels at the required pressure.

SAFELY RESTORING REACTOR HEAT

TRANSFER
The risk of fishscaling is proportional to the rate of
hydrogen permeation through the reactor wall and the
contact time of the jacket cleaning media. Hydrogen
permeation has been shown to be significant whether
using strong mineral acids, or milder, inhibited organic
acids . It follows that the safest reactor jacket cleaning
would be neutral or alkaline, rather than acidic. In
practice though, alkaline cleaning products have little

In the past, the plant had attempted caustic-based

cleaning. While it was quite safe with respect to protecting the glass-lining, and it was safe with respect to
the base metal, it was ineffective. The caustic-based
3

impact of the cleanings on its production process, the

benefits were quite impressive.

cleaning agent was unable to remove the mineral

scales that were robbing the facility of its production
capacity.

The savings realized was calculated to be $430,000

annually.

The plant consulted with several glass-lined reactor

experts including the manufacturer of the plant's reactors. They recommended the new, neutral pH cleaning service as the only safe and effective means of
removing the iron oxide fouling.

Production increased by more than 5%. As a result

of shorter batch times, the plant could now produce
more batches per month.
Product quality was improved through better temperature control. Process temperature was now
more responsive because of the newly increased
heat transfer coefficient.

The service was scheduled for a five-day period

including set-up, cleaning and post-inspection of the
glass lining. Prior to conducting the on-site service,
the cleaning service examined a sample of the jacket
space deposits and analyzed it to determine the cause
of the fouling and to match the foulant with the appropriate neutral pH cleaning chemicals.

Equipment life was increased by effective removal

of corrosion sites and deposits. Active corrosion
cells were halted. With the deposits now removed,
corrosion inhibitors could reach the metal surface
and promote the formation of a passive film.

Prior to initiating the cleaning, the cleaning team took

ultrasonic thickness measurements of the vessel wall
and the jacket itself to determine the extent of the
damage. Vessel entry was performed to inspect the
interior of the reactor for any existing glass damage,
wear patterns, chipping or etching. In addition, spark
testing was performed to ensure that there were no
"holidays" (pin holes) in the glass lining. Glass thickness was also measured in order to confirm that the
lining was within specification.

The plant's production personnel were so impressed

with the results that they have planned to clean all
remaining reactors on a regular basis.

CASE STUDY: IRON OXIDE FOULED

CHEMICAL REACTOR
A chemical manufacturer in Tennessee uses glasslined reactors in their production process. A combination of steam and cooling tower water is used to heat
and cool the reactors. The constant switching
between steam and cool water accelerates iron corrosion. Iron oxide deposits built up to the point where
heat transfer was seriously hampered. Batch times
were increased as a direct result of fouling.

The cleaning team then embarked on the actual cleaning. They connected a custom-built cleaning skid to
the jacket piping and recirculated the cleaning solution
through the jacket over the course of 72 hours. During
this time, cleaning solution pH and concentration were
carefully monitored. In addition, the iron level in the
cleaning solution was measured to verify that the solution was removing iron oxide. Iron levels will rise while
corrosion products are being removed from the jacket
and reactor walls. Once the system is down to bare
metal, iron concentrations in the cleaning fluid no
longer increase.

Removal of iron oxide deposits was indicated as the

only way to regain lost reactor efficiency. As in the previous case study, acidic cleaning was discouraged by
the reactor manufacturer because of the significant
risk of glass damage. Upon consulting with glasslined equipment manufacturers, the plant learned of
the novel, neutral pH approach and opted to proceed.

After the cleaning phase was completed, the cleaning

solution was flushed from the system and disposed to
drain. Unlike acidic cleanings, there was no need for
hazardous waste disposal, and there was no need for
a separate neutralization step. Prior to reconnecting
the system piping, the condition and direction of the
agitating nozzles and impingement plates was
assessed. The cleaning team recommended several
ways to improve reactor life and water treatment in the
jacket system. The reactor was then returned to service.

Again, careful inspections of reactor jacket conditions

were performed including deposit composition determinations. The cleaning then proceeded for 72 hours
with all the critical parameters under close scrutiny. At
the end of the cleaning, the reactor was again inspected to ensure that the cleaning was successful.
Calculations on the composition of the spent cleaning
fluid revealed that the cleaning had removed approximately 30 pounds (13.5 kg) of iron corrosion products
from the system.

As a direct result of the cleaning , reactor operating

efficiency increased more than 30%. Cool-down times
for each batch decreased by 45%. Heat-up times
decreased by 27%. When the plant assessed the full

The vessel was then returned to service. Heat transfer rates were observed to increase by more than
30%. Reaction times were improved by more than 30
minutes per batch. This was a significant improve4

ment over previous operation and was achieved without the risk of glass damage

6. A. Dito, A. Marshall, W. M. Walker, "Neutral pH

Cleaning of Glass Lined Reactor Jackets",
Proceedings of the 8th European Federation of
Corrosion, September 18-22, 1995, Ferrara Italy

CONCLUSION
Glass-lined reactors are widely used because they
work where lesser materials simply fail. In the quest
for optimum production efficiency, jacket space corrosion and deposit control are frequently neglected or
forgotten until problems arise. Corrosion and deposition result from the high temperatures, low flows and
variable operating conditions within the jacket.
Resulting fouling robs the production process of efficiency. Heating and cooling times are extended and
product quality can be compromised.
Traditional methods of reactor jacket cleaning are risky
or ineffective. Acidic cleanings put the reactor's glass
lining at risk for fishscaling damage while alkaline
cleanings do not effectively remove iron and calcium
based deposits.
A novel, neutral pH cleaning program has demonstrated the ability to improve plant reactor efficiency
significantly. It does so by removing mineral deposits
without risking damage to the glass lining or the reactor base metal and is recommended by the major manufacturers of glass-lined equipment as the only safe
and effective means of glass-lined reactor jacket
cleaning.

REFERENCES
The author gratefully acknowledges the assistance
and contributions of Mr. Donald H. De Clerck, consultant for Pfaudler, Inc.
1. Donald De Clerck, "The Care and Feeding of
Glass-lined Steel", Chemical Engineering, October
1998
2. A. Marshall, W. M. Walker, A. Dito, "Solving
Corrosion Problems In Reaction Vessel Jacket
Cooling Systems", Corrosion 91, Paper 301,
Cincinnati, Ohio
3. Betz Handbook of Industrial Water Conditioning,
Betz Laboratories, Inc., 1991, 9th edition p. 215
4. Donald De Clerck, "The Care and Feeding of
Glass-lined Steel", Chemical Engineering, October
1998
5. A. Dito, A. Marshall, W. M. Walker, "Neutral pH
Cleaning of Glass Lined Reactor Jackets",
Proceedings of the 8th European Federation of
Corrosion, September 18-22, 1995, Ferrara Italy

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