PDVSA – CRP – Cardón, Venezuela

UOP Service Visit

September 28-30, 2011

Contacts:

Juan Bohorquez Deep Conversion Area Superintendent (CRP)

Gelimarth Colina CCR Platforming Senior Engineer (Cardon)
Jhorman Martinez CCR Platforming Process Engineer (Cardon)
Marcos Valero CCR Platforming Process Engineer (Cardon)
Yanelys Medina Butamer/Alky/Merox Senior Engineer (Amuay)
Raisel Andrade Butamer/Alky/Merox Process Engineer (Amuay)
Yuriana Carmona Butamer/Alky/Merox Senior Engineer (Cardon)
Laremz Ramonez Butamer/Alky/Merox Process Engineer (Cardon)

General

This service visit followed a slightly revised format. We met with all of the Butamer/Alky process engineers
for both Cardon and Amuay at the Amuay offices, and the second day met with the CCR Platforming
engineers in Cardon. I will include all of the discussions in one report, as follows.

CCR Platforming

PDVSA is still looking for some clarity on the replacement membrane cartridges. We agreed to set up a
teleconference as a starting point to explain the change from six membrane cartridges to three membrane
cartridges and three “dummy” cartridges, including discussion on how the cartridges will be installed, and
confirming the impact, if any, on delta P across the cartridges. PDVSA would also like to have a better idea
of the “normal” life of the membrane cartridges – assuming no damage from liquid hydrocarbon entrainment
(and maybe an overall average) for planning on replacements.

We reviewed earlier discussions regarding addressing the ongoing problems with condensation in the gas
lines going to the recycle gas and net gas compressors. Eric has separately initiated discussions with
engineering to develop an appropriate study proposal. The scope would include potentially adding cooling
to products condenser (no existing trim condenser); looking at the net gas treater design and the stabilizer
feed treater design.

The unit is currently struggling with fouling of the stabilizer feed exchanger (on the feed side). PDVSA have
sampled deposits from cleaning, and found primarily corrosion products – FeCl. The problem started after
PDVSA switched to metal oxide adsorbent in 2004. Do we know if the metal oxide adsorbent would
generate water, or promote corrosion in any way? The treater is currently bypassed, but PDVSA is
considering putting it back in line as they are concerned about downstream salting problems. Even with
the exchanger bypassed they are seeing an increase in fouling.
Butamer

We started a discussion on corrosion problems in the gas scrubber of the Butamer Unit in Amuay. After
some discussion on caustic strength control it was mentioned that in both units there is no caustic
circulation, and most of the corrosion problems are in the caustic circulation piping. There have been
problems maintaining the circulating caustic pumps.

Both units have also been operating for significant periods over the last 2 months in H.O.T. mode due to
problems with the recycle gas compressors. The compressors are now back in service. With the extended
operation in H.O.T. mode, we again discussed the recommendation to complete the revamp work to
upgrade the units to allow for operation in H.O.T. mode without risk of uncontrolled temperature excursions.

Amuay

Amuay are fairly happy with current catalyst stability. The lead reactor was loaded in December of 2008,
and was moved from the lag to lead position in November of 2010. Current delta T across the lead reactor
is 37°C, with 16°C across the lag reactor. iC4 ratio in the Isomerate is typically 60%.

Cardon

We reviewed Kurt’s recommendation for controlling the hot oil supply to the charge heater to control the
heat up rate prior to putting feed into the unit. The last startup PDVSA put feed in at a low temperature –
they did not see any temperature excursions, but it took some time to get the conversion up to normal. In
previous startups they have tried controlling the heat by opening the heater bypass – I explained the
suggestion that they install a small bypass of hot oil to the heater so they can directly control the amount of
hot oil to the heater. Opening the bypass appears to have little impact on the amount of hot oil going to the
exchanger.

The catalyst in the lead reactor was replaced in August with I-12. The reactor positions were switched with
the new catalyst now in the lag position. The current lead reactor is already significantly deactivated – the
lead reactor delta T is 6°C; and the lag reactor delta T is 20°C. Current operation is without recycle gas.

HF Alkylation

Amuay

The Alkylation Unit turnaround has been further delayed until mid-January, 2012. PDVSA is still interested
in having a UOP inspector during the turnaround, but we haven’t seen an ODT as yet.

Amuay uses a local company for cleanout prior to opening. They do not acidize – they use a detergent
solution from “MTech(?)”. A local company, “Field Service” conducts the cleaning operation. One issue
with the process is disposal of the cleaning solution – the contractor leaves the solution for PDVSA to
dispose of. The contractor has suggested to PDVSA that they will use a “water cannon” to help with
cleaning of the larger vessels – have we seen devices like this used for cleaning?
PDVSA asked what the minimum/normal level should be in the acid settlers – they are currently operating
at 6-7% in the settler. It wasn’t clear if this is 6-7% of the total height of the settler or some other range.
They asked that we confirm the target and minimum levels.

Amuay also has an ongoing problem with plugging of the drain of the KOH treater – are there options to
help keep this line clear?

As part of the overall plan to install emergency shutoff valves on all large liquid containing equipment in the
refinery, PVDSA is planning to install emergency shutoff valves on the depropanizer bottoms. The concern
is what to do with pump flush in this case – switch to alkylate?

Cardon Alky I

Recent problems have risen with corrosion/leaks in the iC4 stripping vapors heater. PDVSA thinks the
problem starts on the process side. However, there are similar problems with the butane alumina treater
feed heater, which is heated with the same high P steam supply. It seems likely that the problem could
also be on the steam side of both exchangers. PDVSA would like suggestions for early detection of leaks
in this/these exchangers.

Cardon Alky II

The CRP complex had a refinery wide power failure in May of this year. Cardon took advantage of the
shutdown to address some specific operating issues. First was to clean the reactor feed nozzles. Both
sets of reactor feed nozzles were severely plugged with fluoride salts. The water side of the reactors were
chemically cleaned during the shutdown as well. With the current high ambient temperatures, the reactor
temperature is 35-36°C. Most of the time since the cleaning the reactors have operated at 30°C. There is
still some imbalance, as reactor B outlet temperature is higher than reactor A.

They had been having problems with high water content. The acid regenerator was opened for inspection
– all of the trays were gone. PDVSA would like to consider alternate tray metallurgy. They have used
monel in the past and consider Hastelloy options – 276(?) and/or C200(?). What has UOP’s experience
been?

Based on previous discussion, the isostripper feed heater has been bypassed for repairs. Once complete,
PDVSA will take a shutdown to put it back in service.

ORU

PDVSA would like to have UOP guidelines for handling/unloading of the ORU adsorbent. In their
experience they have had significant problems getting oxygen and hydrocarbon levels down to permissible
limits for unloading.
Merox

FCC Gasoline Merox (Cardon)

Since the last visit operations have re-adjusted caustic strength, and have seen a significant drop in caustic
entrainment into the product. We discussed this issue with Amuay engineers – PDVSA will push to make
the same change in the Amuay unit.

LPG Merox (Cardon)

Generally the Merox product is on specification (20 ppm). However, if/when they stop the alkylate wash,
the LPG product S goes well off specification to as high as 150 ppm total S. The engineers were not
familiar with actual operating conditions – we provided a copy of operating guidelines for LPG operation.
The LPG units in Amuay have more problems with meeting sulfur specifications – we repeated our
recommendation to have a UOP Merox Audit, including the presentation of our proposal for a site visit to do
an operations audit, and to prepare the basis for preparing a proposal for a revamp engineering study for
Amuay’s future operation once the gasoline Merox Units are taken out of service.

FCC Naphtha Merox (Amuay)

The process engineers were curious what the normal frequency for maintain the “special” air check valve.
They recently had a failure of the valve.
Action Items

1. Schedule teleconference soon with Gas Processing specialist to review the membrane questions.

We completed the teleconference discussion on October 7th of last year. Out of the discussion
came the request to confirm operational estimates with the new membranes and the current
feed gas definition. UOP’s membrane technology group is working on the estimates for the
actual feed gas composition. We expect to be able to send the final results by the end of
January.

2. Knowledge of metal oxide (Zn) adsorbents in stabilizer feed service – corrosion?

I reviewed our discussion on the stabilizer feed treater with our adsorbents specialist. We do
not have knowledge of the metal oxide adsorbents in this service with relation to corrosion
issues. After further discussion, it still seems unlikely that the fouling seen on the stabilizer
feed exchanger would be related to deposit of corrosion products. The conditions at the inlet
to the stabilizer do not lend themselves to corrosion – there should not be enough water
present to create a liquid water phase, which is required to generate corrosion.

We would also not expect to see ammonium chloride deposits in this location – generally the
salt deposits will form in colder sections of the stabilizer (overhead system). The feed
exchanger is actually increasing temperature of the process stream which reduces the
likelihood of salt deposit/sublimation.

There still exists the more likely possibility that there are polymers/gums being formed across
the adsorbent bed (especially when the adsorbent nears saturation with chlorides) which will
deposit in the stabilizer feed exchangers. The replacement of the adsorbent should be
scheduled based on a calculated life. One option to confirm whether or not the treater is
saturated is to test the stabilizer overhead off gas for HCl content.

3. Acid Settler normal/minimum operating acid levels.

Our typical recommendation for horizontal settlers with boots is a minimum level of 6” (150 mm)
above the bottom of the vessel, and a maximum of about 24 “ (600 mm). For settlers without
boots, we recommend a minimum level of 12” (300 mm) above the bottom of the vessel, and a
maximum of 30 “ (750 mm).

4. KOH treater drain plugging solution.

The slides from the training course on the KOH Treater design are attached. To minimize
plugging problems it is important to keep the brine lines as short as possible. It is also
important to heat trace the lines from the KOH Treater to the Blow Pot. Notes on operation of
the blow pot are included in the UOP General Operating Manual. We can set up a telecom to
discuss further if PDVSA would like.

5. Depropanizer bottoms shutoff valve – issue with loss of pump flush media.
 We don’t know the details of the emergency shutoff system, or what conditions might exist
when it trips, but aligning the alkylate flush to the iC4 flush header is probably a good choice in
this situation.

6. Send procedures/recommendations for purging and unloading of ORU adsorbent.

Attached are the standard recommendations for adsorbent handling for UOP adsorbents.

7. Acid regenerator tray material selection – options vs. benefits.

Our current specification is still Monel trays in the regenerator. There have been one or two
refiners use Hastelloy C-276 trays in the regenerator. So far, it appears that the life of
Hastelloy trays in the regenerator is as good or better than Monel. Hastelloy is expected to be
more expensive.

8. Juan Bohorquez would like to have an updated list of recommended suppliers for equipment in the
Butamer/Alkylation Units.

We do not keep a list of recommended suppliers or vendors for equipment in the Butamer or
Alkylation area – except for valves in HF Alky service. Attached is an updated copy of our
current HF Alky piping specifications.

9. Recent problems with corrosion/leaks in the iC4 stripping vapors heater (Alky 1)

Most units do not have corrosion problems with these exchangers. PDVSA should definitely
investigate the possibility of corrosion on the steam side. In these exchangers, the tubes
should be strength welded to the tubesheet. If the steam pressure is higher than the process
pressure, I don’t know a good way to detect a small leak in these exchangers.

10. Turnaround cleaning of acid circuit

I believe the company cleaning solution they are probably referring to is EnvTech – this is a
cleaning solution used by many HF Alky units. Attached is a presentation on cleaning the unit
using EnvTech from the HF Alky symposium in June 2011. Also attached is a presentation
used in the past to discuss general Turnaround and cleaning issues.