Corrosion Issues and Prevention in Oil Industry

INTRODUCTION

The humans have most likely been trying to control corrosion for as long as they have been using the metals because whatever are the results of the corrosion, remedial measures are always costly in terms of manpower, finance and time. In case of US only, the annual cost incurred because of corrosion and its protection is

approximately 70 billion dollars & of that, 30% was defined as avoidable.

DEFINITION OF CORROSION

Corrosion is generally defined as the deterioration or destruction of the metals usually caused because of chemical reaction or oxidation with its environment. It is usually an insidious process and it can be identified by merely the visual observation, which means that merely the naked eyes are sufficient to recognize corrosion.

Corrosion is irreversible reaction of a material whether it is a metal, ceramic or a polymer with its environment which results in the dissolution into material of a component of environment or in the consumption of the material.
FORMS OF CORROSION IN OIL INDUSTRY

The most common forms of corrosion in Oil Industry are as follows: 1.High-Temperature Gaseous Corrosion 2.Crevice Corrosion 3.Pitting Corrosion
HIGH-TEMPERATURE GASEOUS CORROSION

When at an elevated temperature, a metal is exposed to an oxidizing gas, the corrosion occurs only through direct reaction with the gas even without the presence of the liquid electrolyte. The corrosion in such cases is generally referred to as tarnishing, scaling, gaseous corrosion or high-temperature oxidation. The rate of corrosion attack generally increases with the increase in the temperature. The surface film thickens due to the transport of the cat-ion as well as an-ion through the scale, which plays the role of a solid electrolyte in this whole process. Usually, the growth rate of the film is very rapid in the initial stages. If the scale is solid as well as non-porous and it completely covers the surface of the metal, then the pace of the reaction will be decreased with the further increase in thickness of scale because the ionic

transport through the scale becomes the rate controlling. The following figures illustrate the formation of protective as well as non-protective scales on Alloy800.
(a) Cr-203 base-protective oxide-scale formed in sulfur-free oxidizing agent. (b) Sulfide-oxide scale formed in reducing conditions containing hydrogen sulfide.

CREVICE CORROSION

Crevice corrosion is a confined form of the corrosion attack. This type of corrosion occurs basically at the spaces or the narrow openings between two metallic surfaces or between metallic and non-metallic surfaces. These spaces or the narrow openings are basically known as crevices. The most common forms of crevices are gaps, holes, lap joints, seals, inside cracks and seams etc. The following pictures very clearly illustrate the various stages of crevice corrosion.

MECHANISM OF CREVICE CORROSION

If a gasket is present on the metallic surface (e.g. metal Fe), then it will definitely experience heavy corrosion. Normal corrosion which is generally known as oxidation corrosion will occur through the metallic surface, inside as well outside the crevice. The surface of metal Fe which is exposed to the external environment, will act as a cathode as it is rich in oxygen, whereas the gasket contacted area inside the crevice, will become anode because of low level of oxygen. This situation will form a complete circuit where the following reactions will occur:

Fe Fe2+ + electron (e) Fe2+

+ H2O Fe2O3 + H+

2H2O + O2 4OHFe2+ + 4OH Fe2O3

The migration of Fe ions from the anode to the cathode can be explained with the help of the following diagram:

PREVENTION OF CREVICE CORROSION

The crevice corrosion can be controlled and prevented in following ways: Continuous welding, soldering and caulking of the existing lap joints Using welded butt joints instead of bolted or the riveted ones. Avoiding sharp corners and stagnant areas while designing the vessels. Proper and regular inspection of the equipment so as to remove the deposits. Use of high PRE or high resistance material. Minimize the crevices while designing the equipment as well as in the fabrication process.

Use of solid non-absorbent gaskets, for e.g. Teflon

 Coating of external surface

Pitting corrosion is one of the most confined as well as the most destructive forms of corrosion. It causes equipment failure due to perforation or penetration and basically occurs on the surfaces of the metals protected by oxides covering or films such as stainless steel and aluminum etc. this type of corrosion leads to formation of holes or pits on the metallic surfaces which lead to their failure and deterioration. It is also difficult to predict the extent of corrosion because of varying number of pits and depths under the same identical conditions.

Pitting corrosion on outer surface of pipeline.

CO2 pitting corrosion on the inner surface of pipeline.

H2S pitting on the inner surface of pipeline.

Pitting corrosion is an autocatalytic process and a unique type of anodic reaction in which the pit is provided with the reactions and the conditions which are helpful as well as necessary for the continuous activities of corrosion.
The following diagram describes the pitting process in which the metal M is being pitted by the NaCl solution.

CORROSION IN PETROLEUM REFINERY

Corrosion has always been a serious, unavoidable and a hazardous problem for the petroleum refinery as well as petro-chemical operations. There is no doubt that there are several other material issues which cause major problems for the industry, but predominant number of problems are caused due to various aspects of the corrosion. Corrosion prevention and control increase the overall maintenance, handling and the operations cost. To control the corrosion, the industry has to sometimes face the situation of scheduled or the unscheduled shutdowns, for the repair of damaged pipelines and equipment, which is also quite expensive. Anything that can be done to increase the life period of the equipment and pipelines will be of great benefit to the industry and to the economy as a whole.

Majority of the corrosion problems are caused due to shutdowns when the equipments and the pipelines are exposed to the external environment for inspection and repairs, the metals surfaces covered with corrosive products and materials are exposed to air and moisture.

High temperature sulfuric corrosion of 6 inches (150mm) carbon steel tube from radiant section of crude preheated furnace at crude distillation unit.

Naphthenic acid corrosion on top of 6 inches bubble caps made of stainless steel {type 317 (S31700)} containing 2.95% Mo.

CORROSION MONITORING

The most commonly and reliable method of corrosion monitoring in these days is FSM-IT which stands for Field Signature Method-Inspection Tool. It is a latest NDT technology used for the inspection of metallic pipes and structures. FSM-IT is helpful in monitoring of internal metal loss due to pitting corrosion or erosion corrosion. In addition, it can also be used to detect cracking and other wall changes. In FSM-IT technology, the area which is meant to be monitored is brought under the contact of electric field. In this process, metal loss is caused by the weld corrosion. It causes increase in the resistance across the weld at that specific point whereas the current is disturbed by the crack along the weld.

After the completion of the process, the resultant changes in the electric field are noticed and are then converted back into the metal loss figures.

CORROSION MINIMIZATION IN PETROLEUM REFINERY DESIGNS

The following are the main factors which should be kept in mind while implementing the equipment designs:
MATERIAL SELECTION

While selecting the material, the environmental conditions in which the equipment is meant to be

operated as well as the corrosive behavior of the environment and metal, must be thoroughly reviewed. The expert and knowledgeable engineers must thoroughly review the chemical behavior of the environment as well as the particles present the atmosphere which can stimulate corrosion. For in-depth evaluation of the materials, it is a must that their list should be minimized as it helps in thorough observation as well in saving time, energy and cost of research. The aspects of design detail can be illustrated with the help of following factors: SHAPE The basic design is geometrical form and steps must be taken to avoid the shapes that will cause corrosion. The general problems in design implementation include general corrosion followed by crevice corrosion and deposit corrosion etc.

DESIGN DETAILS

The following figure shows that how a design and its assembly can lead to formation of crevices and traps for the accumulation of the corrosive liquids and can ultimately stimulate corrosion.

The following figure illustrates the effects of the design features on the flow.

MECHANICAL FACTORS

If stresses are involved in the environment, then it can be regarded as more damaging for the design

and helpful for corrosion. Under such conditions the safety as well as the health is at high risk as the metals may fail unexpectedly and catastrophically. There is no doubt that the perfect design is quite impossible in general practice and one has to compromise with the limitations of the design whether these are mechanical or chemical. The problem is that the mechanical faults in the material can cause mechanical failure by contributing to corrosion. The mechanical faults can be avoided and eliminated only with the help of quality assurance and control. Following figure helps in demonstration of the design detail which can be helpful for reduction of stress.