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Pipeline Technology Conference 2008

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Black powder, its causes and cures


Peter van Beugen, M.Sc.
Pipesurvey International
The Netherlands

Speaker C.V.
Peter van Beugen has long experience in the field of pipeline
cleaning and inspection technologies. He got his education at
the Rotterdam College of Technology, where he obtained is
Bachelor Degree in Mechanical Engineering, and at the Delft
University of Technology, where he obtained his Masters
Degree in Applied Physics.
Starting his career with Kleiss company where he gained a lot
of experience in the design and manufacture of pipeline
cleaning tools, he now also runs the company Pipesurvey
International where several techniques for pipeline inspection
and integrity have been developed. Having worked onshore
and offshore in various parts of the world on pipeline cleaning
and inspection operations, Peter van Beugen has obtained both the theoretical as
well as the practical skills in pipeline technology and is now a frequent speaker and
lecturer on topics related to pipeline cleaning and inspection technology.
Peter van Beugen,
Managing Director of Pipesurvey International
Schrijnwerkerstraat 13
3334 KH Zwijndrecht
The Netherlands
pvanbeugen@pipesurveyinternational.com

Abstract
Black powder has now become a recognized threat to pipeline efficiency and integrity
world wide. Nevertheless still companies are still struggling with the subject and
questions such as:
- What caused the problem of black powder in our particular case?
- What procedures for construction and commissioning of pipelines should be
followed in order to prevent the occurrence of black powder?
- How can the black powder problem be recognized and what are its potential
consequences?
- What methods exist for the removal of black powder and which method is
most suitable in our particular case?
This lecture will touch on all the issues related above and it will explain in detail the
mechanisms which are active in pipelines to produce black powder, such as
reactions with free water, reactions in sour gas, reactions in Microbiologically Induced
Corrosion, the influence of mill scale and the hydrotest phase.
A root cause analysis will show how the origin of black powder can be identified.
Methods will be discussed to prevent the occurrence of black powder in pipelines.

Pipeline Technology Conference 2008

Further, much emphasis will be laid on the various methods to remove black powder
from pipelines and the cost effectiveness of these methods.
These methods include the usage of mechanical pigs, the installation of filters,
chemical solution and advanced surfactant technology

1. Introduction
Black powder is one of the common type contaminations found in gas pipelines. The
name black powder is a generic name for various types of fine particles (black dust),
although it sometimes appears in wet type (asphaltenic).
These particles are mostly related to iron oxides, iron sulphides and iron carbonates.
Although black powder has been present in gas transportation systems for longer
time, it was either considered to be a fact-of life, or there was no proper
apprehension of the extent of the problem, mainly because regular cleaning pig have
only a limited capability to remove substantial parts of black powder from pipelines.
Only in the past decade has been black powder been recognized and identified as a
problem that must be dealt with.
Black powder interferes with the pipeline in that
- ferrous particles are distributed along the pipe wall by routine pigging
operations and tend to accumulate in corrosion spots. In this way, black
powder will tend to mask metal loss from MFL intelligent tools, which results in
an underestimation of defects
- ferrous particles will collect on the magnetic system of the ILI tools and will
lead to sensor lift off, data loss or even damage of the tool
- black powder is abrasive and increases the friction of the ILI tool in the
pipeline, which results in great variations of velocity. These have an adverse
effect on the quality of the inspection data
- As black powder is abrasive, cups and discs of cleaning and inspection tools
get worn out and tools may become stuck in the pipeline
- Black powder interferes with down stream equipment such as filters, valves,
compressors and other instruments, leading to damage, cloaking
- Black powder contaminates the gas and end users of the gas may complain
about the quality of the product.

2. Sources
2.1 Iron Sulphide
Sulfur and sulphuric complexes can occur in pipelines, predominantly due to one of
two sources: hydrogensulfide or as sulphate reducing bacteria (SRB), associated
with microbiologically induced corrosion (MIC). SRB however, can only take place in
the presence of free water and will not occur in dry gas systems.
Depending on the conditions, various reactions can take place with the line steel
The most commonly formed sulphide under the influence of hydrogen sukphide is the
so-called mackinawite:

Pipeline Technology Conference 2008

9 Fe + 8 H2S  Fe9S8 + 8 H2
Other iron sulphides, such as pyrrhotite (Fe1-xS) and Troilite (FeS) are less prevalent
because they are formed at higher temperatures.
Sulphate reducing bacteria can produce corrosion products via the intermediate step
2H+ + SO4- + CH4  H2S + CO2 + 2 H2O
It should be noted that mackinawite is not stable in the presence of water and air; it
will readily oxidize as per the following reaction
2 Fe9S8 + 9 H2O + 27/2 O2  18 FeO(OH) + 2S8
In subsequent reactions, these hydroxides will be converted to oxides:
3 FeO(OH) + e  Fe3O4 + H2O + OHFe2+ + 8 FeO(OH) + 2e  3Fe3O4 + 4 H2O
Therefore, in dry pipelines, iron sulfides can be retrieved from the pig trap, where as
in pipelines with higher dew point, the sulfides will in part or completely oxidize when
exposed to the air. Change in colour of black powder has sometimes been noticed
while retrieving pigs from the pig trap.

2.2 Iron carbonate


Carbon dioxide (CO2) is to some degree a natural constituent of natural gas. In
presence of free water, it will react with the line steel and create iron carbonates:
H2O + CO2  H2CO3
H2CO3 + Fe  FeCO3 + H2
Again, absence of water will prevent this type of corrosion and iron carbonates will
not be found in dry gas systems.

2.3 Iron oxides


Water, associated with dissolved oxygen, will react with the steel and form iron
oxides:
4 Fe + 2 H2O + 3 O2  4 FeO(OH)
Again, the FeO(OH) is not stable and will react further
8 FeO(OH) + Fe  3 Fe3O4 + 4 H2O
3

Pipeline Technology Conference 2008

Alternatively, hematite will be formed in presence of abundant dissolved oxygen, as


per the following reaction:
2 FeO(OH) + O2  Fe2O3 + H2O
2.4 Mill scale
Mill scale is formed on top of the steel in the iron mill process. Mill scale is a generally
speaking a brittle and porous layer, and will often consist of multiple layers of iron
oxide complexes, which are formed in various phases of the process and at various
temperatures.
The following layers will be formed on top of the steel: Wuestite (FeO), Magnetite
(Fe3O4) and Hematite (Fe2O3).
Mill scale has a different thermal expansion coefficient than line steel, and as the
pipeline will go through various temperature cycles during its lifetime, the mill scale
will start to burst and become loosened from the pipe wall. Routine pigging enhances
the effect and will scrape off the loose parts of the mill scale.
As mill scale is porous, in the hydrotest phase water will penetrate the smallest
cavities and not easily be removed during the drying process. When drying takes
place in air, the ideal environment is created for the formation of oxides with the line
steel underneath the mill scale, under the formation of FeO(OH) and Fe2O3 and
Fe3O4.
As these oxides have different specific weight an volume compared to steel (Fe),
tensions will be created in the mill scale layer which results in the mill scale springing
off from the solid steel.
To some operators it is a known phenomenon that large amounts of black powder
show up just a few months after testing, drying and commissioning of the pipeline,
while only limited amounts of debris were recovered during the construction phase.
The above scenario gives a valid explanation for this phenomenon.
Each pipeline is different, has a different quality of steel ,mill scale, construction and
testing procedures, and transports different qualities of gas under different operating
conditions. Hence, it is clear that no one case compares to another, although
common features are easily recognized.
As a resume of the above descriptions of sources for black powder, the following
cross reference table can be made, which has no claim for being complete.

Fe9S8

FeO(OH) Fe3O4

FeCO3

Fe2O3

FeO

H2S
MIC
CO2
H2O
Mill scale

Pipeline Technology Conference 2008

3. Cures
Before going into the details of the various methods to mitigate the consequences, it
is most useful to highlight the measures which can be taken to prevent the
occurrence of black powder, as we can learn them from the origins as described
above.
First, it is clear the presence of H2O is in most cases a key factor. Therefore, proper
drying of the pipeline in the construction phase, as well as thorough gas treatment, is
essential to prevent black powder.
Second, the presence of H2S is plays an important roll, at least in a number of cases.
This again, can be combated by proper gas treatment (desulphurization) and e.g. use
of scavengers further reduce the presence of H2S to sub ppm level.
The same goes for CO2, although generally it does not play the same role as H2O
and H2S.
Finally, removal of the mill scale should be considered at installation of new pipelines.
Operators who install factory blasted and internally coated pipe are facing
considerably less problems with black powder than in other cases.
However, once the black powder is present in the pipeline system, various
technologies can be chosen to overcome the problem.

3.1 Filters
Installation of filters only offers a solution in that the black powder, or at least the bulk
of it, can be filtered out of the sales gas before it is delivered further downstream. The
filters will not remove the black powder from the pipeline, and where e.g. internal
inspection of the pipeline (ILI tools) is a problem due to black powder, filters will not
offer a timely solution.
It must be taken into consideration that parallel filters must be installed with regard to
maintenance and repair.

3.2 Gels
Water-based or hydrocarbon based gel can be created by adding a gelling agent to
the base liquid in order to achieve higher viscosity of the liquid batch. Gels are used
in pipeline cleaning operations to keep particles floating (in suspension), thus
enhancing the displacement capabilities of liquids. One of the drawbacks of gels is
that due to the high viscosity there will be a higher residue in the pipeline after
cleaning, which can only be removed by running a gel breaker. In order to clean
pipelines which are in service, handling large amounts of gel is problematic in many
cases.
Compared to other liquids, gels have lower wetting capability due to changed surface
tension properties.

Pipeline Technology Conference 2008

3.3 Chemical Dissolution


Chemical dissolution of contamination in pipelines is generally not viable, since these
reactions require long contact times, which can not be achieved while cleaning
operating pipelines.
For black powder, the so called chelant technology has proven good results on iron
suphide (FeS) in laboratory circumstances. For application in pipelines however, the
technique requires very large amounts of liquids.
Another drawback of the technology is that chelants are water-based dissolutions.
Thus, the chelants can become part of a problem in stead of the solution, even when
adding corrosion inhibitors to the batch.

3.4 Surfactant technology.


Surfactants (surface active agents) are added to a batch of liquids, which can be
hydrocarbon based or water based, and will create an efficient and time-effective
cleaning action. Rather than trying to dissolve contaminations, or just trying keep
them in suspension, surfactants will penetrate the contaminations and break them up
in pieces, with a typical reaction time of 1 minute only. By changing the surface the
surface properties, a stable dispersion is created, which can be displaced out of the
pipeline by means of mechanical pigs.
Over the past decade, surfactant technology has been introduced in various parts of
the world and has proven to be a successful solution to overcome the problem of
black powder in gas pipelines.
For the cleaning of pipelines in an on-line mode i.e. without taking the pipeline out
of operation installation of mobile equipment is required to conduct the cleaning
service. At the launcher, a pump spread is installed in order to inject a batch of liquids
into the pipeline.
At the receiving end, a mobile high pressure separator is installed together with
ambient-pressure liquid containers (frac tanks) in order to separate the liquid sludge
from the gas.
Usually, a number of 3 to 4 runs is sufficient in order to obtain excellent cleaning
results.