Flue gas heat recovery through the acid

dew point
Polymer based heat exchange technology enables more heat recovery from flue
gas by addressing acid corrosion issues

PIM VAN KEEP and ROBERT SAKKO

HeatMatrix Group

rude oil refining is an energy

C intensive process. On average,

the thermal energy consump-
tion of a refinery is in the order of
150
140
130
350-400 MJ/bbl, based on 2017 data
from environmental agencies in the 120
Acid dew point, ºC

Netherlands, with some refiners 110

achieving a higher energy efficiency 100
than others. In order to reduce oper- 90
ational expenditure as well as the 80 Okkes
carbon footprint, refiners engage Verhoff
70
in projects to improve energy effi- ZareNezhad
ciency and process sustainability. 60
For a 100 000 b/d refinery, the typ-
0 500 1000 1500 2000
0 3.5 7.0 10.5 14.0
ical thermal energy consumption SOx, mg/Nm3
equates to 400 MW. Of this energy, SO3, ppm v (assuming 2% of SOx)
most is consumed in endother-
mic processes. Approximately 10% Okkes:
however is lost through the stack as TDEW (°C) = 203.25 + 27.6log10(pH2O) + 10.83log10(pSO3) + 1.06(log10(pSO3) + 8)2.19
waste heat. Historically, these stack where,
pH2O = volume fraction H2O in m3/m3
losses of flue gas being emitted at pSO3 = volume fraction SO3 in m3/m3
high temperatures were accepted as Verhoff:
a given because further heat recov- TDEW (K) = 1000/[2.276 - 0.02943 ln(pH2O) – 0.0858 ln(pSO3) + 0.00626 ln(pH2O.pSO3)]
ery would lead to acid corrosion and ZareNezhad:
related operational reliability issues. TDEW (°C) = 150 + 8.1328 ln(pH2O) + 11.664 ln(pSO3) - 0.38226 ln(pH2O)ln(pSO3)
where,
These corrosion and reliability con- pH2O = partial pressure H2O in mm Hg (= [volume fraction] × [pressure in mm Hg])
cerns can now be overcome, allowing pSO3 = partial pressure SO3 in mm Hg (= [volume fraction] × [pressure in mm Hg])
refiners to recover about a third of
the waste heat from their flue gases Figure 1 Acid dew point H2SO4
(14 MW/100 000 b/d) in an economi-
cal way. As a result, an improvement ranging from natural gas, off-gases, depends on the levels of reactants
of the overall refinery energy effi- LPG to naphtha and fuel oil. Most present in the flue gas. It generally
ciency of 3-4% can be achieved. of these fuels contain sulphur com- lies in the range 100-150°C. Figure
In this article, we look at the issues ponents like H2S, mercaptans and 1 shows the relationship between
traditionally linked to recovering thiophenes, which are readily con- the ADP and the SO3 level, calcu-
heat from flue gases. We review verted to SOx in the combustion lated at a typical H2O level of 15
the solution that allows more heat chamber. Mainly SO2 is formed, vol% by using a number of differ-
to be recovered by cooling the flue but part of this SO2 (typically about ent approaches proposed in the
gas down to temperatures below 2-4%) oxidises further to SO3. This literature.
the acid dew point, and we discuss SO3 reacts with H2O in a condens- Sulphuric acid is highly corrosive
what the implications are for existing ing reaction to form sulphuric acid, and affects susceptible equipment
downstream equipment. when the flue gas cools below the surfaces. For example, on cold sur-
acid dew point (ADP): faces in metal air preheaters, local
What is the issue with corrosive temperatures drop below the ADP,
flue gas? SO3 (g) + H2O (g) -> H2SO4 (l) [1] leading to sulphuric acid condensa-
In refineries, a wide range of fuels tion, which results in rapid corro-
are combusted in thermal processes, The acid dew point temperature sion and breakdown of plates and

www.eptq.com PTQ Q2 2019 93

 costs of steam and reduces the heat
recovery. Both of these mitigation
approaches still limit the recovery
of the heat in the flue gas to approx-
Water
Acid imately 20°C above the acid dew
dew point
dew point point.
Rate of corrosion

To recover more energy from the

flue gas, it has to be cooled down
below the original acid dew point.
Around the acid dew point, cor-
rosion rates are high, but as the
flue gas is cooled further down
40 60 90 100 120 140 160 through the corrosive temperature
Metal surface temperature, ºC range (see Figure 2), rates of cor-
rosion become manageable again.
Figure 2 Rate of sulphuric acid corrosion Below 90-100°C, the corrosive-
ness of the flue gas is significantly
tubes. This phenomenon is known resulting in loss of equipment lower compared to the corrosive-
as cold spot corrosion. The degrada- integrity and a reduction in plant ness just below the acid dew point
tion will go unnoticed for a period, performance. temperature.
but in the end leaks will result in a Under the acid condensing con-
short cut between combustion air What are the challenges with ditions arising from cooling down
and flue gas and thereby an energy conventional equipment? through the acid dew point, stand-
loss through a loss in recovery effi- To deal with acid corrosion, the ard metal heat exchangers are not
ciency as well as an increase in industry has implemented different suitable. Special alloys need to be
power consumption by the combus- approaches with mixed success. The used. The cost of these, however,
tion air fan. The leakage can impact first approach is to stay away from makes the heat recovery uneconom-
the production rate, once the com- the acid dew point by keeping stack ical. Alternative materials of con-
bustion air fan reaches its limitation. temperatures up. But as described struction like glass or enamel coated
Such cold spots can occur even if above, variations in fuel sulphur metal have been implemented at
the flue gas bulk temperature is still levels and localised cold spots can times. These solutions are, how-
as high as 250°C, because of the cold still lead to corrosion. To avoid ever, susceptible to flow induced
ambient air at the other side of the over-cooling of exchange surfaces vibrations and thermal shocks,
air preheater surface. The excessive by cold air, part of the heated com- which lead to damaged enamel
cooling leads to flue gas side sur- bustion air can be recycled to the coatings (allowing the acid to reach
face temperatures below the acid inlet of the forced draught air fan the underlying metal surface and
dew point. Cold spot corrosion can which will lift the air temperature in corrode it away), tube breakage
be aggravated by varying levels the air preheater and thereby reduce or rupture. The subsequent short
of sulphur in the fuels. As sulphur the risk of cold spot corrosion. This cut between combustion air and
levels increase, the acid dew point however requires extra ducting, flue gas reduces heat recovery and
increases accordingly. Even if the demands more power on the air fan increases the load on the air fan as
refiner targets to remain 10-20°C and reduces the heat recovery on described before.
above the typical acid dew point, the air preheater. Alternatively, the
these variations in fuel sulphur con- combustion air can be first warmed Polymer heat exchanging tube
tent can lead to sulphuric acid con- up with a steam air preheater. This bundles
densation during sulphur peaks, approach results in additional HeatMatrix Group has developed
an innovative polymer based heat
exchange technology that allows
recovery of heat from corrosive
and/or fouling flue and exhaust
gases, to preheat combustion air
and thereby improve overall pro-
cess energy efficiency. This tech-
nology allows operators to recover
even more heat from the flue gas
down to temperatures well below
the acid dew point, or replace their
existing glass tube or glass lined
air preheater or steam air pre-
heater with a reliable, more efficient
Figure 3 HeatMatrix Polymer Honeycomb technology solution.

94 PTQ Q2 2019 www.eptq.com

 The HeatMatrix APH air pre-
heater is based on Polymer
Honeycomb technology. In this
technology, multiple tubes are con-
nected to each other over a signif-
icant length of the tube, forming a
honeycomb modular bundle (see
Figure 3, left). Multiple corrosion
resistant polymer tube bundles are
mounted into a metal casing (see
Figure 3, right) to give the required
heat exchange area.
Polymer Honeycomb technol-
ogy provides a strong and rigid
heat exchange matrix that is able
to resist high gas velocities and
thermal shocks. The geometry cre- Figure 4 HeatMatrix APH examples: cylindrical (L) and box (R)
ates a 100% counter current flow
configuration between the flue gas during operation. The bundles can down through the acid dew point.
and air streams. This configuration be washed with water. The chemical Sulphuric acid condenses on the
improves the heat transfer by up to properties of the polymer allow for tube wall in the polymer heat
20% compared to cross flow type even more aggressive cleaning with exchanger. The highly hygroscopic
exchangers. Flue gas flows from top detergents, acids or caustic if the acid absorbs water as it moves
to bottom through the tubes (see duty requires this. down the tube and drops into the
Figure 3, red arrow) and combustion The low weight of the polymer bottom basin. It is worth noting that
air flows in the opposite direction bundles allows flexible installa- the temperatures remain above the
around the tubes (see Figure 3, blue tion of the heat exchanger, even water dew point.
arrow). Inside the polymer tubes, at height, when plot space is lim-
the flue gas will go through its acid ited. The lightweight bundles Research
dew point and acid condenses on are retractable from the top and The condensation of sulphuric
the tube wall. At the ADP, the con- can be cleaned or replaced with- acid means that SO3 is selectively
centration of sulphuric acid is high. out demounting the complete removed from the flue gas. Hence
As the acid travels down the tube, exchanger. the acid dew point of the exit flue
it will absorb water and the result- gas is reduced accordingly. To con-
ing condensate is collected in and What about downstream? firm that SO3 is indeed removed
drained from the bottom section Acid removal and to what extent, a research pro-
of the air preheater. This bottom The HeatMatrix exchanger has ject was set up in conjunction with
section has been designed to dis- been designed to cool the flue gas the TNO research institute in the
engage condensate from the flue
gas. Whereas the top three sections 130
of the exchanger are carbon steel
based, the bottom section is spe- 120
cifically designed to withstand the Okkes
110
diluted acidic condensate (approxi- ZareNezhad
mately 1% H2SO4 content).
Acid dew point, ºC

100
In addition to corrosion resist-
ance, the application of polymer 90
offers benefits in fouling conditions.
80
Polymers have very smooth surfaces
and have low affinity for binding 70
with dust, soot, salts and particu- H2O =15 vol %
lates. The positioning of the tubes in 60
0 0.4 0.7 1.1 1.4
a vertical flow direction means that
SO3, ppmv
there are no dead zones inside the Inlet HeatMatrix exchanger

tubes where fouling can accumu-

SOx 200 mg/Nm3
SO2 70 ppm v
late. As a result, fouling build-up is Outlet HeatMatrix exchanger
SO3 1.4 ppm v
reduced. In cases of extremely foul-
SO3 0.18 to 0.28 ppm v
ADP Okkes 108 to 112ºC ADP Okkes 123ºC
ing flue gases, each bundle can be ADP ZareNezhad 121ºC
ADP ZareNezhad 98 to 105ºC
equipped with an in-line spraying
nozzle, which cleans each bundle
in an alternating cleaning sequence Figure 5 ADP reduction in a Polymer Honeycomb

www.eptq.com PTQ Q2 2019 95

 responding to a SO3 level of 3.5
3.0
ppmv, which means an ADP
(Okkes, ZareNezhad) of 130°C.
2.5 With 80-90% of the SO3 con-
densing out, the SO3 level in the
Corrosion rate CS, mpy

2.0 cooled gas is in the range 0.35-0.7

ppmv, which equates to an ADP
1.5 of 113-118°C (Okkes) or 107-114°C
(ZareNezhad). In line with Figure
1.0 6, a corrosion rate of 0.1-0.3 mm/
year would be expected. Over the
0.5 period of a year, the corrosion cou-
pon was monitored for any signs
0
80 90 100 110 120 130 140 150 160 of corrosion or weight change. No
Acid dew point, ºC significant impact was discerni-
ble. In Figure 7, development of the
plate thickness and material loss is
Figure 6 Relationship between rate of corrosion and the acid dew point shown for the carbon steel coupon.
Source: HeatMatrix Group B.V.: No rights can be derived from this graph The analysis confirms that down-
stream of the HeatMatrix air pre-
Netherlands. In the test programme, to a lower corrosivity of the flue gas. heater, the resulting acid dew point
gas with SO3 was passed through Figure 6 shows the corrosion rate of of the flue gas has been lowered to
the polymer tubes at typical gas carbon steel as a function of the acid such an extent by the condensa-
velocities. The inlet and exit SO3 dew point. The graph shows that as tion of sulphuric acid in the heat
levels were measured. The testing soon as the acid dew point drops exchanger that the corrosion rate
showed that 80 to 90% of the SO3 below 105°C, the corrosion rate has dropped to levels well below
will be removed in HeatMatrix reduces to less than 0.1 mm/year, the design corrosion rate of 0.1
Polymer Honeycomb technology. which is a typical design corrosion mm/year.
As SO3 is removed, the acid dew rate. This shows that cooled flue gas
point is lowered accordingly. Taking is significantly less corrosive and Case study: CDU furnace
for example the Okkes equation that the corresponding corrosion HeatMatrix technology has been
and starting with a SOx level of 200 rates are within the design param- proven in a wide range of appli-
mg/Nm3, an SO3 level of 1.4 ppmv eters for the materials of construc- cations, including methane steam
(assuming 2 vol% SO3) gives an ADP tion used downstream of the air reformer and oil refinery furnaces.
of 123°C. After 80-90% has condensed preheater. Here is a case study in a refinery.
out, the SO3 level in the cooled gas On a CDU furnace, an existing
drops to 0.14-0.28 ppmv, which Proof from the field metal air preheater (APH) recov-
equates to an ADP of 108-112°C, so a At an operating unit, a carbon steel ered part of the heat in the flue gas.
drop of 11-15°C (see Figure 5). material coupon was installed in The acid dew point of the flue gas
the exit of the HeatMatrix poly- was 129°C (Okkes, ZareNezhad).
Impact on corrosion rate mer APH. The flue gas SOx level To protect the existing metal APH
A lower acid dew point corresponds in this unit is 500 mg/Nm3, cor- against cold spot corrosion and to
improve the refinery’s energy per-
formance, an additional metal APH
in combination with a HeatMatrix
polymer APH was installed. The
3.1 0.2

polymer APH protects the metal

3.0
APH from cold spot corrosion.
0.1
2.9
The combined additional recovery
Plate thickness, mm

amounted to an energy saving of 9

2.8 0 MW, of which about 30% is recov-
ered in the polymer APH.
The overall pay-back time for this
Weight loss

2.7
−0.1 project is less than five years.
2.6
Conclusion
2.5 −0.2 Crude oil refineries are large con-
0 50 100 150 200 250 300 350 400
sumers of energy in their ther-
Time, days
mal processes. Of the energy used
in combustion, about 10% is lost
Figure 7 Carbon steel coupon in flue gas below the acid dew point through the stack. Concerns about

96 PTQ Q2 2019 www.eptq.com

acid dew point corrosion have held showstopper for this kind of energy
refiners back in recovering more saving.
waste heat from the flue gases. Flue gas flow: 103 000kg/h

Traditional solutions like glass tubes

Air flow: 98 000 kg/h
Duty: 9MW References
or enamel coated tubes have caused 1 Okkes A G, Get acid dewpoint of flue gas,
reliability issues and are therefore
Flue gas Hydrocarbon Processing 7, 1987, S. 53–55.
94ºC
375ºC
less frequently applied. Operators HeatMatrix
2 Verhoff F H, Banchero J T, Predicting dew
points of flue gases, Chem. Eng. Prog. 70 (8),
tend to stay well above the acid Metal Polymer
APH APH 1974, 71–72.
dew point after their air preheaters. 180ºC
3 ZareNezhad B, New correlation predicts
However, variations in fuel sulphur flue gas acid dewpoints, O&G Journal 107, 35,
341ºC
content and low ambient air temper- Furnace 2009.
atures in winter can still lead to cold
New Metal 115ºC
15ºC
APH
spot corrosion in the existing metal Ambient
air
air preheaters. To mitigate against Pim van Keep is Director of Technical Sales
this cold spot corrosion, some oper- Figure 8 Refinery CDU furnace: revamp case at HeatMatrix Group BV. He has an extensive
ators choose to preheat the combus- background in catalytic processes in oil
tion air with steam, which implies ment downstream from the poly- refining and the chemical industry. He holds
costs for steam and reduces the over- mer APH. an MSc in Chemical Engineering from Delft
all heat recovery. The extra heat recovered from the University of Technology, The Netherlands
Polymer based heat exchange flue gas can be used to preheat the and an MSc in Business Management.
technology allows operators to combustion air which in turn leads Email: [email protected]
Robert Sakko is Director of Technology with
recover more heat from the flue to a reduction in the consumption
HeatMatrix Group BV. A co-founder of the
gas by addressing acid corro- of combustion fuel. Overall, this
company, he has worked for many years
sion concerns. Moreover, in the solution allows refiners to improve in the process industries, before taking on
HeatMatrix polymer honeycomb their sites’ energy efficiency by the new adventure of helping industry to
heat exchanger, most of the sulphu- up to 4%. The many references of become more sustainable. He holds an MSc in
ric acid is removed from the flue the HeatMatrix technology have chemical engineering from the University of
gas, which makes the cooled flue proven that concerns around acid Delft, the Netherlands.
gas much more benign to equip- dew point should no longer be a Email: [email protected]

www.eptq.com PTQ Q2 2019 97