Much information has beeb generated about the way to control crude unit overhead condenser

corrosion. Form both the efficiency and economy viewpoints, one the best schemes is to elevate
the pH of the overherad accumulator wáter ti roughly 5 to 7 and then complete the program with
a filming inhibitor.

At present, ammonia ( or ammonium hydroxide) is the agent most commonly used to neutralize
acid present in overhead condensate. Ammonia is easy to feed and has a relatively low cost per
unit of acid neutralized. Usually, condensers, into the column reflux, or directly into the top of the
column. Ammonia is rarely introduced below the top tray in a crude distillation unit because of the
danger of plugging trays, downcomers and product draws wuth ammonium chloride.

Using ammonia for neutralization has several major disadvantages. As can be see by figure 1,
ammonia possesses a very steep titration curve betweeen Ph 4 and 8. This makes it difficult to
control pH within the desired limits.

Optimum process condensate Ph for mild Steel systems contaminated by both HCL and H2O is
usually between 5 and 6, as suggeested by Hutchinson and Hughes and later Gutzeit. Below pH 4.5
the corrosion rate increanses dramatically due ti the increase in hydrogen ion concentration.
Above pH 6, an increanse in bisulfide corrosion reaches a máximum between pH 7 and 8.

´paton and Littecoltt 3 pointed out that close control of pH is more important that the selection of
any specific operation pH value. Actual plant experience corroborates this. The best operating pH
range for many plants is 5.5 to 6.5. And, the smaller the average deviation from the selected

AMMONIA FOR NEUTRALIZATION

Ammonium chloride salt is insoluble in hydrocarbons, but very soluble in wáter. Carleton 4, and
later Hausler and cable 5, have shoe that ammonium chloride crystals can form at temperaturas
above the wáter dewpoint of overhead streams, thus contributing to fouling deposits. The
presence of ammonium chloride, as shown by Backensto and Yurick, can result in severe corrosion
beneath the deposits. Ammonium chloride hydrolyzes, forming ammonia and HCl. HCl reacts with
iron to form soluble ferrous chloride. This reacts with H2S to form insoluble iron sulfide and
liberates additional HCl. Thus, acid concentration cells are formed, causing pitting and eventual
equipment failure.

Ammonium chloride can be flushed from the system by continuous or intermittent wáter
injection. However, this is not always desirable. Water wash injetion systems can sometimes be
quite expesive. And in those plants that Exchange raw crude with overhead vapors, the wáter
injection lowers the raw crude preheat temperatura. This increases the prehead furnace fuel
usage.

For plants with admiralty or other copper-bearing alloys in the overhead system, the use of
ammonia carries with it the danger of complexing the copper. The higher the pH (ammonia
concetration) the more severe this attack.

Another disadvantage with ammonia is the fact that the Environmental Protection Agency now
restricts the amount of ammonia allowed in a plants´s outfall.
CAUSTIC FOR NEUTRALIZATION

An alternate neutralization scheme is to supplemente ammonia injection with the addition of

sodium hydroxide to the crude charge. Sodium hydroxide, wich is added downstream of the crude
desalter, has been shown by Samuelson to reduce the hydrolysis of calcium and magnesium
chlirides, thus decreasing the amount of HCL formed and the demand for the neutralizer in the
overhead.

Care must be taken to prevent overfeed of sodium hydroxide, as this can cause complications such
as preheat exchanger scaling, increased crude and coker unit furnace coking, embrittlement of
furnace tubes and coke drum foaming. Use of caustic increases the sodium content of residual fuel
which can lead to boiler fireside corrosion. Also, the higher the sodium level in coker feed, the
poorer the quelity of the cke product. In addition, it is desirable to minimize the sodium content of
residual streams fed to fuid catalytic crakers, because sodium is a catalyst poison.

Generally, caustic concetration should be maintained below 14.3 g/m3 (5 pounds per 1000
barrels) of crude charge. Although caustic is used at the rate of 2.9 to 8.6 g/m3 ( I to 3 pounds per
1000 barrels) of crude in many plants without undersirable side effects,some plants are
experiencing problems even at these loe levels of caustic addition.

Humphreys and sorel 8 pointed out that the injections of caustic to control chloride corrosion in
the overhead system can bring its own problems if thesystem is improperly designed and
operated. Caustic solutions normally range in concetrations from 3 to 12 percent by weight.lower
concetrations may give rise to deposition and plugging of the injection nozzle. Por mixing of the
caustic can cause sludgeaccumulation in dowatream equipment. Caustic should always be injected
to the succion of the desalted crude booster pump to promote the máximum degree of miximum.