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Black Powder

Black Powder

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Published by Pervaiz Rizvi
BLACK POWDER IN GAS PIPELINE
BLACK POWDER IN GAS PIPELINE

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Categories:Types, Research
Published by: Pervaiz Rizvi on Jan 17, 2011
Copyright:Attribution Non-commercial

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07/01/2013

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ABSTRACT
Despite its common occurrence in the gas industry, blackpowder is a problem that is not well understood across theindustry, in terms of its chemical and physical properties,sources, formation mechanisms, prevention or management of its impacts. To prevent or effectively manage the impacts of black powder, it is essential to have knowledge of its chemicaland physical properties, formation mechanisms and sources.This article is a follow-up to an earlier article published inthe
Saudi Aramco Journal of Technology
Fall 2007 issue. Inthat issue, it was shown that black powder is regenerative,and is formed inside natural gas pipelines as a result of corrosion of the internal walls of the pipeline. Morespecifically, black powder forms through reactions of thepipeline steel with condensed water containing oxygen (O
2
),hydrogen sulfide (H
2
S), and carbon dioxide (CO
2
).This article is divided into three parts. The first part of thisarticle is a synopsis of published literature including ourearlier findings. New field evidence showing the presence of excess moisture in the lines will be presented and discussed.The second part is a summary and short discussion of variousblack powder management philosophies and methods. Finally,the ongoing black powder research activities at the SaudiAramco Research and Development Center (R&DC) arebriefly presented.
INTRODUCTION
Black powder is a worldwide phenomenon experienced bymost, if not all, Sales Gas pipeline operators
1-6
. In the gasindustry, the term “black powder” is a color-descriptive termloosely used to describe a grayish material that is generatedinside the gas pipelines. Black powder can be found in severalforms, such as wet with a tar-like appearance, Fig. 1, or dry inthe form of a very fine powder, Fig. 2. Black powder wasreported in recently commissioned as well as older Sales Gastransmission pipelines
1-6
. Black powder could have majoradverse effects on customers by contaminating the customerSales Gas supply leading to an interruption of the customer’soperations and/or poor quality of products in which the SalesGas is used as feedstock. It could also negatively affect gaspipeline operations. For example, it can lead to instrumentscraping delays, reduced inline inspection accuracy, controlvalve erosion as well as flow reduction. Finally, black powdercould present a major health and environmental hazard. Thisis because some black powder is contaminated with mercuryand naturally occurring radioactive materials, such asradioactive Lead-210 (Pb-210). Iron sulfides are alsopotentially pyrophoric. These hazardous substances requirespecial procedures for handling and disposal of the removedblack powder.
42
FALL 2008 SAUDI ARAMCO JOURNAL OF TECHNOLOGY
Managing Black Powder in SalesGas Transmission Pipelines
Authors: Dr. Abdelmounam M. Sherik, Dr. Arnold L. Lewis and Dr. Sebastien Duval 
Fig. 1. Shows wet tar-like black powder collected at the scraper doorreceiver of a Sales Gas pipeline.Fig. 2. Dry fine black powder collected at the scraper door receiver of a Sales Gas pipeline.
 
COMPOSITION AND SOURCES
As used in the surveyed literature, “black powder” meansvarious forms of iron sulfide (FeS), iron oxide (Fe
3
O
4
, FeOOH)and iron carbonate (FeCO
3
), mechanically mixed orchemically combined with any number of contaminants, suchas salts, sand, liquid hydrocarbons and metal debris. Differentgas pipeline operators report different compositions for theblack powder removed from their pipelines. For example,whereas some literature reports black powder as beingpredominantly iron sulfides
1-3
, others report the completeabsence of iron sulfides, but the presence of iron oxides andhydroxides such as Fe
3
O
4
and FeOOH
4, 6
, while others reporta combination of all of these products (iron sulfides, ironcarbonates and iron oxides)
5
. These products have onecommon source, which is that they are formed inside naturalgas pipelines as a result of corrosion of the internal walls of the pipeline
1-6
. More specifically, they are formed by reactionsof iron (Fe) present in ferrous pipeline steel with condensedmoisture containing oxygen (O
2
), hydrogen sulfide (H
2
S) andcarbon dioxide (CO
2
). Internal corrosion in “dry” gaspipelines is often overlooked due to an underestimation of thecorrosion risk due to the perceived absence of condensedwater in the line
1, 7
. Under normal conditions, gas pipelinesare under minimal corrosion risk; however, it is generally notfeasible to completely eliminate water from pipelines
7
. Watervapor can potentially condense on the inner walls of thepipeline due to high dew points. It can also enter the pipelinethrough periodic upsets that cause moisture carry-over intothe line. This water, coupled with corrosive species such asCO
2
, H
2
S and O
2
, even in small amounts, as low as ppmlevels, can result in unexpected internal corrosion with theformation of corrosion products, namely FeCO
3
, FeS and ironoxides, respectively
1, 5
. It should be noted that CO
2
, H
2
S andO
2
are benign in dry gas, but become corrosive in the presenceof condensed water
1
.
FORMATION MECHANISMS
Internal corrosion of Sales Gas pipelines is the main cause forthe formation of black powder. Corrosion due to H
2
S, CO
2
and O
2
in Sales Gas pipelines has well establishedmechanisms. Following are simplified electrochemicalreactions that describe these corrosion processes and theirrespective corrosion products. It is important to note that inall of these electrochemical reactions, condensed water is anecessary condition for these reactions to proceed.
Iron Carbonate Formation due to CO
2
Corrosion
Iron carbonate corrosion product found in black powder isformed by the chemical reaction of CO
2
, a naturally occurringconstituent of natural gas, with condensed water producingcarbonic acid (H
2
CO
3
), which in turn reacts directly with steelto produce FeCO
3
, in accordance with these reactions
8
:H
2
O (condensed water) + CO
2
(in gas)
H
2
CO
3
(1)H
2
CO
3
+ Fe (pipeline steel)
FeCO
3
+ H
2
(2)
Iron Sulfides Formation due to H
2
S Corrosion
Hydrogen sulfide can be a naturally occurring constituent of natural gas, or alternatively, produced by sulfate reducingbacteria (SRBs)
1
. These anaerobic bacteria use the reductionof sulfate as a source of energy and oxygen, in accordancewith reaction such as
1, 2
:2H
+
+ SO
4-2
+ CH
4
H
2
S + CO
2
+ 2H
2
O (3)Iron sulfide corrosion products are usually formed from H
2
Sdissolved in condensed moisture reacting directly with thesteel wall of the pipeline shown in the following reactions
1, 2
:H
2
O (condensed water) + H
2
S (in gas)
H
3
O
+
+ HS
-
(4)HS
-
+ Fe (pipeline steel)
FeS + H
2
(5)
Iron Oxides Formation due to Oxidation
The source of oxygen in gas pipelines is oxygen ingressthrough leaks at low-pressure points throughout the systems
1
.Oxygen ingress in gas lines can cause significant corrosion insmall concentrations and even combustion, if present, in largeramounts
9, 10
. A 1988 survey of 44 natural gas transmissionpipeline companies in North America indicated that their gasquality specifications allowed maximum O
2
concentrationsranging from 0.01 mol% to 0.1 mol% with a typical value of 0.02 mol%
9, 10
. It has been shown that oxygen content of approximately 0.01 mol% has little effect on steel corrosionin the presence of stagnant water inside Sales Gastransmission pipelines, while 0.1 mol% produces fairly highcorrosion rates. As a general rule of thumb, it is recommendedthat transmission pipelines should consider limiting maximumoxygen concentrations to 10 parts per million by volume(ppmv) (0.001 mol %)
9, 10
.In cyclical wet-dry environments with low dissolvedoxygen, such as those experienced in gas pipelines, iron oxidesare usually formed by the direct oxidation of pipeline steelwalls, in accordance with the following reactions
8
:2Fe + H
2
O (condensed water) + 3/2 O
2
2 FeO(OH) (6)The FeO(OH) can be in
α
,
β
or
γ
form. In these type of environments,
γ
FeO(OH) is unstable and will quicklytransform to magnetite (Fe
3
O
4
) and water by the followingreaction
8
:8
γ
-FeO(OH) + Fe
3Fe
3
O
4
+ 4H
2
O (7)But if the water is nearly saturated with dissolved oxygen,then hematite (Fe
2
O
3
) is often present
8
.
SAUDI ARAMCO JOURNAL OF TECHNOLOGY FALL 2008
43
 
44
FALL 2008 SAUDI ARAMCO JOURNAL OF TECHNOLOGY
result of internal corrosion of the pipeline, (2) black powderparticles are jagged in shape and exhibit a high hardness,which makes it highly erosive to the currently used pipelinecontrol valves, and (3) is mainly composed of the corrosionproducts Fe
3
O
4
and FeO(OH), with fewer samples showingsmall amounts of FeCO
3
in addition to the iron oxides. Table 1summarizes black powder compounds and their potentialsources. In addition, we found that some black powdersamples contained mercury.Further, the reason for the internal corrosion was determinedto be condensed water containing H
2
S, CO
2
and O
2
, withoxygen being the most critical element. The source of thecondensed moisture is the inefficient gas dehydration processes insome of the gas treating plants. Inefficient dehydration causes theSales Gas to contain high levels of moisture in excess of themaximum allowable level of 7 lb/mmscf (7 pounds of water in amillion standard cubic feet of gas) as per Saudi Aramco Sales GasProduct Specification (SA-120). Figure 3 shows levels of moisturein the Sales Gas from one gas treating plant. It is clear from thisFigure that two deviations (upsets) from the 7 lb/mmscf standardlevel have occurred for extended periods of time. Figure 4
14
shows dew point variations vs. moisture content in the gas at aline pressure of 900 psig. It can be seen from this Figure thatstrict adherence to the Saudi Aramco specification of 7 lb/mmscf (with a dew point of 5 °C) is sufficient, under typical ambienttemperatures in Saudi Arabia, to ensure no water condensation.This Figure also shows that if excess moisture enters the gas gridAlternatively, iron oxides may be formed due to microbio-logically induced corrosion (MIC) resulting from acidproducing bacteria (APB) or iron oxidizing bacteria (IOB)
11
.Once again, condensed water is a prerequisite for thesebacteria to thrive and multiply, and as such, MIC cannotoccur in the absence of water.Magnetite found in black powder can also come from othersources, namely, (1) mill scale, which is expected to be a minorand short-term (in new pipelines) black powder
4
contributor,and (2) conversion, by oxidation inside the pipeline, of FeCO
3
and FeS corrosion products. The conversion of FeCO
3
toFe
3
O
4
is sluggish and takes place during the dry cycles inaccordance with the following reaction
12
:3 FeCO
3
+ 1/2 O
2
Fe
3
O
4
+ 3CO
2
(8)The conversion of FeS is rapid and can occur during thewet cycles according to the following reaction
7
:2Fe
9
S
8
+ 9H
2
O + 27/2 O
2
18
γ
-FeO(OH) + 2S
8
(9)The produced
γ
-FeO(OH) will quickly transform to Fe
3
O
4
in accordance with reaction (7)
8
.
SAUDI ARAMCO BLACK POWDER
Our recent findings
13
have shown that black powder: (1) isregenerative and is formed inside Sales Gas pipelines as a
Table 1. Compounds in black powder and their respective potential sources
Compound Main Source Minor Source
Fe
3
O
4
Low dissolved oxygen-induced 1. Bacterial-induced corrosion (APB, IOB).corrosion (reactions 6 and 7). 2. Conversion of FeCO
3
and FeS (in-situ) dueto oxygen ingress (reactions 8 and 9).3. Mill scale (minor and short-term).
α
-FeOOH Low dissolved oxygen-inducedcorrosion (reaction 6).FeCO
3
CO
2
corrosion (reactions 1 and 2).
Fig. 3. Actual reading of moisture content in the Sales Gas in plant A. Twoextended upsets can also be seen. An average value of moisture content experienced during the latter upset is indicated.
0.006/12 8/11 10/10 12/9 2/7 4/8 6/75.0010.0015.0020.0025.0030.0035.0040.0045.00
Time (July 2006-June2007)
     M    o     i    s    t    u    r    e     i    n     G    a    s ,     l     b     /    m    m    s    c     f
Average of MoistureContents during Upset Period
Fig. 4. A variation of the dew point with moisture in the gas. The water content value experienced during process upset shown in Fig. 3 and corresponding dew point are indicated 
14
.
0.00-15 -10 -5 0 5 10 15 20 25 30 35 405.0010.0015.0020.0025.0030.0035.0040.0045.0050.00
Dew Point, °C
     M    o     i    s    t    u    r    e     i    n     G    a    s ,     l     b     /    m    m    s    c     f
7 lb/mmscf25 lb/mmscf5.0 °C25 °C

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