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1 Permasense Ltd, Alexandra House, Newton Road, Manor Royal, Crawley, RH10 9TT, UK
www.permasense.com permasense.sales@emerson.com +44 20 3002 3672
with an acid/water mix, an unstable and non-protective hydrate scale is formed, which swells and can
become detached from the equipment.
Figure 1: HF alkylation process flow diagram showing high risk corrosion areas
Corrosion in HF alkylation units depends strongly on a complex and sensitive system of operational
parameters to handle the hydrofluoric acid catalyst safely and cost-effectively. The combination of
temperature, phase change, HF concentration and locations with low- or no-flow conditions makes
some equipment and pipework particularly vulnerable to attack. Corrosion is often aggressive,
short-term and transient, driven by process upsets, like excursions of temperature or water content,
or changes in feedstock quality - this makes corrosion difficult to track using traditional methods
such as manual ultrasound that are carried out periodically.
Key corrosion drivers within the HF alkylation unit include:
a. Water content in circulating acid – although both the iso-butane and the butane olefin feeds
are dried, water content in the circulating acid can build up. Figure 2 shows the detrimental effect of
increased water content in the HF acid on the corrosion rate of carbon steel. The water content in
the circulating acid is normally kept below 2%, which results in generally low corrosion rates in the
main reactor/settler circuit operating in liquid phase. But more diluted acid can be formed under the
following conditions:
Upon phase change: if a 98% HF / 2% water vapour mixture is condensed, the first droplet will
contain about 30% water. An example of these conditions is condensation of warm acid vapour in a
cool dead-leg. Figure 2 below shows that this concentration corresponds to the maximum
corrosion rate.
By extraction: for example, in entrained acid droplets from the settler. If free acid (containing 2%
water) is contacted with HF sub-saturated hydrocarbons, the HF will be extracted into the
hydrocarbon phase. Hence, the water content of the remaining free acid phase will increase.
2 Permasense Ltd, Alexandra House, Newton Road, Manor Royal, Crawley, RH10 9TT, UK
www.permasense.com permasense.sales@emerson.com +44 20 3002 3672
By formation of liquid water: a free water phase is formed in the product defluorinators when
exceeding the water solubility concentration in the propane or n-butane product. Traces of HF
result in a low pH and a corrosive water phase in the product rundowns.
3 Permasense Ltd, Alexandra House, Newton Road, Manor Royal, Crawley, RH10 9TT, UK
www.permasense.com permasense.sales@emerson.com +44 20 3002 3672
Figure 3: Internal corrosion and fouling of a relief valve inlet line
v. High level of residual elements in carbon steel piping – the content of key residual
elements (Cu, Ni, Cr) in carbon steel has an upper limit for HF alkylation units service. When
carbon steel pipe components with high and low content of residual elements are welded together,
severe corrosion can occur. Figure 4 shows an example of severe corrosion from this mechanism.
Figure 4: CS pipe showing preferential corrosion of the section with a high residual element content
4 Permasense Ltd, Alexandra House, Newton Road, Manor Royal, Crawley, RH10 9TT, UK
www.permasense.com permasense.sales@emerson.com +44 20 3002 3672
A greater risk, however, would result from an accidental leak of light hydrocarbons or of
hydrofluoric acid to atmosphere, resulting in:
Potential health and safety impact of HF release on the refinery staff and on the local
community;
Potential for explosion from light hydrocarbon leakage;
Damage to the corporate brand image within the local/national market.
5 Permasense Ltd, Alexandra House, Newton Road, Manor Royal, Crawley, RH10 9TT, UK
www.permasense.com permasense.sales@emerson.com +44 20 3002 3672
5. Permasense solution for high-risk locations for HF alkylation
units
The flow diagram below shows an outline of a Permasense corrosion monitoring system for a HF
alkylation unit:
6 Permasense Ltd, Alexandra House, Newton Road, Manor Royal, Crawley, RH10 9TT, UK
www.permasense.com permasense.sales@emerson.com +44 20 3002 3672
Figure 6: ET210 sensor. Non-intrusive, no paint Figure 7: circumferential array of ET210
removal required, magnetic mounting with sensors.
lightweight securing strap.
For higher temperature locations, Permasense supplies the WT sensor range which utilise our
patented waveguide design enabling continuous operation on metalwork operating up to 600˚C
(1100˚F)). For temperatures up to 200 °C (400 °F), WT sensors can be mounted onto clamps, as
shown in figure 8.
Metallurgies - Sensors can be mounted on a full range of materials including carbon and cast
carbon steel, chrome steels (1% Cr (5130), P5, P9), Duplex, P265GH (430-161), 1.4571 (316Ti),
P295GH (17Mn4), Monel, HR120, Inconel, Incoloy and Hastelloy.
Figure 8: WT sensors mounted using clamps for equipment operating under 200 °C (400 °F)
6. Case studies
Case study #1
A US refiner was concerned by the variation of wall thickness measurements on the bottom of the
Monel acid re-run tower, from manual ultrasound, which suggested very high corrosion rates were
occurring. The tower base was inside a concrete skirt, with a temperature of 200˚F inside the
enclosure and 5' clearance height. Inspectors were making manual measurements very regularly
inside this confined and difficult space in full chemical suits, with a significant inventory of HF acid
overhead. The customer was planning to shutdown the unit to make a complete inspection of the
7 Permasense Ltd, Alexandra House, Newton Road, Manor Royal, Crawley, RH10 9TT, UK
www.permasense.com permasense.sales@emerson.com +44 20 3002 3672
tower. However, Permasense manufactured two custom-built saddles to fit the geometry of the
tower base, which were fixed to the tower using epoxy adhesive, as the customer was
uncomfortable to weld studs. After curing, the sensors were fitted and the sensor data showed that,
although there was some corrosion activity at the location, it was much less than was indicated by
the earlier manual measurements. On the basis of this data, the customer built confidence to keep
the unit on-stream, avoiding a very costly 10 day unplanned shutdown.
Case study #2
A European refiner was concerned about corrosion at two key locations within the alkylation unit.
This required very regular weekly manual ultrasound measurements by inspectors inside the unit
battery limits. However, significant amounts of time were lost every time due to the need to put on,
remove and decontaminate their protective chemical suits to enter the unit. Permasense sensors
were installed at these locations to enable close monitoring from the engineer's office, enabling a
less frequent manual inspection regime within the unit.
Contact:
For more information about Permasense continuous corrosion and erosion monitoring solutions,
please contact us:
permasense.info@emerson.com
Call us on:
+44 (0) 20 3002 3672 (Europe and MENA)
+1 281 724 3774 (Americas)
+60 3 6200 0788 (Asia Pacific)
8 Permasense Ltd, Alexandra House, Newton Road, Manor Royal, Crawley, RH10 9TT, UK
www.permasense.com permasense.sales@emerson.com +44 20 3002 3672