Forensic Engineering

Chemical Corrosion Damage in Adiabatic Expansions

Corrosion Damage in Expansions

Description

A sudden change in a fluid cross-section area provokes a dynamic condition in which water pressure drops sharply below its boiling point and produces instant vaporization.

Since this process is adiabatic, there is no exchange of heat with its surroundings, therefore, the total enthalpy remains the same. Consequently, most of the water molecules will absorb the bulk of that energy as latent heat and will make water turn into steam.

This phenomenon brings about many destructive effects related to chemical corrosion attack, which is one of the most common issues found in steam water systems. Subsequently, it can derive to accumulation of sediment in the cycle, under-deposit corrosion, overheating, caustic corrosion, control valve obstructions or spray nozzle cloggins to mention a few cases.

The problem is likely encountered in LP drain motorized valves feeding flash tanks, spray nozzles and diffusers at bypass attemperations, orifice plates, nozzle or pitot flowmeters, LP flash tank drains to condenser, blowdown systems. We have also observed the same type of corrosion patterns at the deaerator nozzles.

Image 1 represents the cross section top view of a HRSG preheater module It also shows how temperatures vary at the back-end tubes. The increase of velocity in the flue gas would produce gradients of pressure between the two opposite sides of the tube. In consequence, this would eventually create a vortex effect and turbulences in the backside of the tubes. This is shown in image 2.

Turbulence would drop velocity down to zero near the surface, which would decrease the rate of energy transfer from the flue gas to the condensate. By the same token, the lack of flue gas circulation around the tubes would bring temperatures down below the dew point and end up creating droplets of condensation. Image 3 shows areas of high probability for this phenomenon to occur. In that event, a layer of condensation would develop all along the surface of the tubes, while drastically altering the heat convection and thermal conduction rate across the wall.

Chemical Corrosion Issues

It is empirically proven that solubility of chemical species is actively dependent on pressure and temperature, among other properties. Although there is not a direct correlation to predict such dependency, it has been observed that, for most compounds, solubility falls with a decrease in those properties.

As water expands into a pressure below the boiling point, some impurities will exceed its limit of saturation and precipitate. In fact, these precipitates are deposits of salt compounds which can be very aggressive to the equipment. Depending on the nature of the accumulation, the affected zone can develop several types of corrosion patterns. Hence, sodium salts can undergo hydrolysis and produce caustic corrosion. Silica precipitates to form a very hard and impervious scale which can derivates into stress corrosion cracking. Sodium carbonate or sodium chloride can be adsorbed on the surface of the metal affecting the passivation protective layer. Under-deposit corrosion would be expected to happen in most of cases as a result of electrochemical reactions underneath deposition of salts.

I took the attached photo during a inspection to show calcium carbonate deposits (light white patterns) encountered downstream the HP spray attemperation bypass valve.

Air in-leakage in the condenser, caused high level of carbon dioxide dissolved in water, in the form of carbonic acid ions. Subsequently, the carbonic acid ions combined with impurities of calcium dissociated in water to form calcium carbonate. In the even of an abrupt expansion, which is the case of the spray attemperation, the equilibrium among the chemical species dissolved in water is broken. Some ions will vaporize and escape as carryovers into the steam flow, while other impurities will exceed its solubility under the given conditions and precipitate as insoluble salts.

Refer to the following post to find extra information about this type of failure, click here

Engineering

HRSG Preheater Simulation

HRSG Preheater Simulation

Purpose

A computational fluid dynamic simulation was carried out to study the effects of the flue gases velocity in the last stage modules of a HRSG preheater. The results allows us to visualize a map of temperature in a preheater module, hence, to better understand how energy is distributed. In addition, it provides valuable information to predict points of low efficiency and propose estrategies for optimization.

Description

Image 1 represents the cross section top view of a HRSG preheater module It also shows how temperatures vary at the back-end tubes. The increase of velocity in the flue gas would produce gradients of pressure between the two opposite sides of the tube. In consequence, this would eventually create a vortex effect and turbulences in the backside of the tubes. This is shown in image 2.

Turbulence would drop velocity down to zero near the surface, which would decrease the rate of energy transfer from the flue gas to the condensate. By the same token, the lack of flue gas circulation around the tubes would bring temperatures down below the dew point and end up creating droplets of condensation. Image 3 shows areas of high probability for this phenomenon to occur. In that event, a layer of condensation would develop all along the surface of the tubes, while drastically altering the heat convection and thermal conduction rate across the wall.

Why is that relevant?

Back-end corrosion occurs when the gas turbine’s exhaust temperature falls below the dew point of any combustion product. Subsequently, high corrosive liquid acid would form in the presence of moisture. When natural gas contains sulfur in its composition, the reaction products derived from combustion will have, in addition to carbon dioxide and water, an equivalent proportion of sulfur dioxide. This compound will oxidize to sulfur trioxide and create sulfuric gas as it combines with the humidity of the flue gas.

If the temperature of the flue gas falls below the dew point of the sulfuric gas, liquid acid will form on the surface of such regions.

The aggressiveness of this attack depends on the concentration of acid in the condensate, which depends on the equilibrium H2O – H2SO4.

This simulation allows us to predict points of high probability where condensation droplets might form in the preheater module, so satisfactory mitigation strategies can be implemented during the HRSG design.

Refer to the following post to find extra information about this type of failure, click here

Commissioning

Ineffective Cleaning?

Ineffective Chemical Cleaning?

Introduction

Ineffective chemical cleaning? Not really… we have encountered situations where engineers and operators complaint about the cleanliness of the boiler as they see a black liquid coming off the blowdown system during first fire.

It´s not difficult to get carried away by a first impression and put into question the effectiveness of the chemical cleaning.

Explanations

This dark watery constituent is in reality a very welcome natural corrosion-protection product called Magnetite and it is formed as the steel surface is exposed to water under certain conditions.

The formation of Magnetite is an electrochemical process controlled by a continuous diffusion of iron ions from the steel surface across the water boundary layer and its stability, morphology and porosity depends on the oxidation-reduction potential, pH, oxygen concentration, pressure, temperature and the influence of the make-up water chemistry (CO2, Cl, Si, Na, Ca, Mg…)

Solubility rises with temperature up to 150ºC, then decreases with a steep drop to 300°C. Pressure promotes the growth of magnetite and thickness Having said that, the reason of the dark appearance of the blowdown during a boiler ramp-up is mainly due to the deposition of low quality magnetite since steady conditions has not been reached yet.

magnetite