Iron Control

CONTENTS

1. Introduction. 1

2. Oxidation State Of Dissolved Iron. 3

3. Methods Of Iron Control. 4

3.1. Chelating Agents. 6

3.1.1. Citric Acid. 6

3.1.2. EDTA Acid. (Ethylene-Di-Amine-Tetra-Acetic Acid) 6
3.1.3. Tetra Sodium EDTA. 7
3.1.4. Di-Sodium EDTA.. 7
3.1.5. Tri-Sodium NTA.. 7
3.1.6. Nitrilo-Acetic Acid. 7

3.2. Reducing Agents. 8

3.2.1. Sodium Erythorbate. 9

3.2.2. Erythorbic Acid. 9
3.2.3. Ferrotrol 260L. 9
3.2.4. Ferrotrol 270 And Ferrotrol 271. 10

3.3. Ph Control Agents (Buffers). 10

3.3.1. Acetic Acid And Acetic Anhydride.. 11

3.3.2. Sodium Acid Pyrophosphate (SAPP). 11

3.4. Sulphide Scavengers. 11

3.4.1. Ferrotrol HS-A And Ferrotrol HS-B. 11

4. Acid Treatment Designs. 12

4.1. Pipe Pickling Treatments. 12

4.2. Sequestering Acid Systems (SA-Systems). 12
4.3. Hydrogen Sulphide Scavenger Acid (HSSA). 16

4.3.1. HSSA Corrosion Inhibition. 18

5. Non-Acid Treatments Using Chelating Agents. 19

Page i
Iron Control

TABLES

Table 1: Sources of Iron. 2

Table 2: Ferrotrol Products (Iron Control Chemicals). 5

Table 3: Conversion Factors, Ferrotrol Chelating Agent Equivalents. 7

Table 4: Ferrotrol 270 and Ferrotrol 271 Guidelines up to 20% HCl. 9

Table 5: Pounds of Iron Sequestered per 1000 gallons of SA-Acid System . 13

Table 6: Effectiveness of Various Iron Sequestering Agents in Spent Acid. 15

Table 7: Limitations of Ferrotrol Agents in Acid. 16

Table 8: HSSA System Options Based on Well Conditions. 17

Table 9: HSSA Treatment Fluids. 17

FIGURES

Figure 1: Effect of Increasing pH on Various Sequestrants. 13

Page ii
Iron Control

1. Introduction.
{ XE "Introduction" } { XE "Iron Scale:Introduction} { XE "Iron Carbonate:Introduction}{
XE "Iron Sulphide:Introduction" } { XE "Water Insoluble Scales:Introduction" } { XE
"Complexes:Introduction" } { XE "Acidizing:Introduction" } { XE "Iron
Chloride:Introduction" } { XE "Ferric Iron:Introduction" }{ XE "pH:Spent Acid" } { XE
"pH:Introduction" }{ XE "Ferric Iron:Introduction" } { XE "Ferric Iron:pH" } { XE "Ferric
Iron:Hydrolysis" }{ XE "Hydrolysis:Ferric Iron" } { XE "Ferric Iron:Spent Acid" } { XE
"Spent Acid:Hydrolysis" }{ XE "Spent Acid:Ferric Iron" } { XE "Hydrolysis:Ferric Iron" }{
XE "Precipitates:Introduction" } { XE "Precipitates:Iron Hydroxide" } { XE "Iron
Hydroxide:Introduction" } { XE "Iron Hydroxide:Precipitation" } { XE "Iron Hydroxide:pH"
}
The presence of undesirable metal ions in production or injection wells, whether in the
formation fluids, or in treating solutions, is an expensive problem. One of the most
successful answers is that offered by chelation chemistry. Specific materials are added
to treatment fluids which tie-up metal ions in a complex molecule so that their presence
is no longer harmful. Those specific materials are called "chelating" and sequestering
agents.

Iron scale deposits on tubing and casing in producing and injection wells have been a
continuous and costly problem to the petroleum industry since the earliest days. These
water-insoluble scales; iron oxides and salts such as iron carbonate and iron sulphide,
not only restrict production or injectivity directly, but can also produce undesirable
effects during acid stimulation.

When an acid treating solution is injected through tubing or casing it will dissolve part of
any existing iron scales present (rust{ XE "rust" }, iron sulphide, iron carbonate{ XE
"iron carbonate:introduction" } etc.). The acid will then carry these iron compounds, that
are put into solution as iron chlorides, deep into the formation. Additionally, iron
compounds or minerals may be present in the formation itself and will also be dissolved
by the acid (Table 1).

Various studies have shown that hydrochloric acid entering the formation during a
treatment, may contain concentrations of iron in solution as high as 10,000 parts per
million. The presence of this iron can create three types of problems.

First, interaction of the live acid containing ferric ions with reservoir hydrocarbons,
specifically asphaltenes{ XE "Asphaltenes" }{ XE "Organic Deposits" }, can cause the
deposition of organic materials (sludge{ XE "Sludge" }s) that are almost impossible to
remove

Second, as the acid becomes spent by reacting with the formation, the pH (acidity
alkalinity value), of the solution increases. As the pH rises above 2.0, the ferric iron in
solution will undergo hydrolysis and begin to re-precipitate as iron hydroxide. Formation
of insoluble iron hydroxide increases as the pH of the treating solution continues to rise
towards a neutral pH of 7.0.

Page 1
Iron Control

The insoluble iron hydroxide thus formed, is a gelatinous type precipitate that adheres
strongly to rock surfaces. Such reprecipitation can reduce formation permeability and
plug flow channels, reducing oil or gas production in producing wells or increase the
injection pressure and reduce the injection volume in water-flood wells.

The third problem is one of reprecipitation in a hydrogen sulphide (sour gas)

environment. This involves iron sulphide scale{ XE "Iron sulphide scale" } removed from
the tubulars by the acid being re-deposited in the formation due to precipitation{ XE
"Precipitates:Iron Sulphide" }{ XE "Sour Gas:Hydrogen Sulphide" }{ XE "pH:Iron
Sulphide Scales" }{ XE "Hydrogen Sulphide:Iron Sulphide Scales" } as the pH of the
spent acid rises above 1.9.

Page 2
Iron Control

Table 1: Sources of Iron.

Scale Deposit Chemical Formula Oxidation State

Casing, tubing and equipment{ XE "Casing, tubing and equipment:Sources of Iron"

}.

Iron oxide{ XE "Iron FeO +3

oxide:Sources of Iron" }
Rust{ XE "Rust:Sources of Iron" } Fe2O3 +3
Ferric oxide{ XE "Ferric Fe2O4 +2
oxide:Sources of Iron" }
Iron carbonate{ XE "Iron FeCO3 +2
carbonate:Sources of Iron" }
Iron sulphide{ XE "Iron FeS +2
sulfide:Sources of Iron" }

Formation{ XE "Formations:Sources of Iron" }.

Haemetite{ XE Fe2O3 +3
"Haemetite:Sources of Iron" }
Magnetite FeO3, Fe2O3 +2 and +3
Pyrite{ XE "Pyrite:Sources of FeS +2
Iron" }
Siderite FeCO3 +2
Chlorite{ XE "Chlorite:Sources - +2
of Iron" }
Mixed Clays{ XE "Mixed - +2
Clays:Sources of Iron" }

Page 3
Iron Control

2. Oxidation State of Dissolved Iron.

{ XE "Oxidation State of Dissolved Iron" }{ XE "Oxidation State" }{ XE "Oxidation
State:Ferric Iron" }{ XE "Oxidation State:Ferrous Iron" } { XE "Ferric Iron:Oxidation
State" } { XE "Ferrous Iron:Oxidation State" }{ XE "pH:Ferric Iron" } { XE "pH:Ferrous
Iron" }{ XE "Ferric Iron:Precipitation" }{ XE "Ferrous Iron:Precipitation" } { XE
"Precipitates:Ferric Iron" } { XE "Precipitates:Ferrous Iron" }{ XE "Oxidation
State:Precipitation" }{ XE "Precipitates:Oxidation State" }{ XE "Solubility:Iron
Compounds" }{ XE "Solubility:Oxidation State" }{ XE "Acidizing:Oxidation State" } { XE
"Oxidation State:Acidizing" }
Iron in solution is found in two oxidation states, ferric (Fe+3) and ferrous (Fe+2), which
depends upon the source of the iron compound which is dissolved by the acid (see
Table 1). The oxidation state is important to iron control because, the two states form
compounds of different solubilities, with the same anions. The oxidation state also
determines the pH at which precipitation of the compound will occur. For example; ferric
ion present in solution will precipitate as ferric hydroxide at a pH of about 2.5. However,
ferrous hydroxide from ferrous iron remains in solution up to a pH of about 7.5.

The chemistry of dissolved iron is further complicated by a changes to the oxidation

state of the iron anion that take place down hole. This change occurs by the
oxidation-reduction balance of the solution. For example; dissolved ferrous iron is
readily oxidized to ferric iron in oxygen-containing waters. Conversely, ferric iron is
reduced to ferrous iron in the presence of a reducing agent, such as hydrogen sulphide
(H2S) and can even produce elemental sulphur.

During Acidizing treatments dissolved iron will be present in both oxidation states
(ferrous and ferric). Analysis conducted on return fluids after acid treatments has shown
that the ferrous state (Fe2+) is the dominant form. The ratio of ferrous to ferric state iron
present can vary greatly depending on well conditions, but commonly fall between the
range of 5:1 and 10:1 ferrous to ferric iron.

• Ferrous iron (Fe2+).

Precipitates occurs at pH of 7.0 or greater.
• Ferric iron (Fe3+).
Precipitates occurs at pH of 2.0 to 3.0.

Understanding of the environment in which the acid is to be pumped is essential to

determining the appropriate materials and quantities of iron control (Ferrotrol) agents to
be used.

Page 4
Iron Control

3. Methods of Iron Control.

{ XE "Methods of Iron Control" }
Several chemical additives are used to inhibit the precipitation of iron from spent acid.
These comprise four main methods and are used as follows

• Chelation and Sequestration.{ XE "Chelation:Methods of Iron Control" } {

XE "Methods of Iron Control:Chelation" }{ XE "Sequestration:Methods of
Iron Control" }{ XE "Methods of Iron Control:Sequestration" }

Complexion of metal ions by organic or inorganic molecules. These

additives form stable, water soluble, metal-complexes. By complexing
with iron, its activities are reduced and it is prevented from reacting as
normally expected. Most often these additives are organic compounds.

• Reducing Agents.{ XE "Methods of Iron Control:Reducing Agents" }{ XE

"Reducing Agents:Methods of Iron Control"}

These additives function primarily by converting ferric iron present in

solution to the more soluble ferrous state.

• pH Control Agents (Buffers). { XE "Methods of Iron Control:Buffering (pH

Control)" }{ XE "Buffers:Methods of Iron Control" } { XE "pH:Methods of
Iron Control" }

Organic acids such as acetic acid are used as buffering agents to control
and maintain a low pH within the acid system. They retard the
precipitation of insoluble iron particularly after the treatment has spent.

• Sulphide Scavengers.{ XE "Methods of Iron Control:Sulphide

Scavengers)" }{ XE "Sulphide Scavengers:Methods of Iron Control" }

Chemicals that form stable complexes with sulphide ions. Used in

conjunction with ferrous iron complexing agents, prevent the formation of
iron sulphide.

The choice of iron control agent is usually determined by well conditions. The addition of
a chemical agent in acidizing should not be done without design, because the equality
of effective iron control is not the same for all chemicals. Their effectiveness is
influenced by:

• The pH{ XE "pH:fluid systems" } of the system in which they are utilized.
• Temperature{ XE "Temperature" }.
• Concentration{ XE "Additive Concentrations" } at which the additive is
used.
• Other additives present in the system.
• Presence of oxygen{ XE "Oxygen:Reservoir fluids" } in the reservoir
fluids.

Page 5
Iron Control

• Presence of hydrogen sulphide{ XE "Hydrogen sulphide:reservoir fluids"

}.

The data shown in Table 2 for the Ferrotrol agents may be used as a guide for selecting
an iron control agent. Table 3 shows conversion factors for the different Ferrotrol
chelating agents equivalents. Often these materials are used in conjunction with each
other to optimize their benefits.

Table 2: Ferrotrol Products (Iron Control Chemicals).

Ferrotrol Type Chelation Amount to Retain Product Solubility

Product Function Ratio* 1000 ppm Ferric in 15% HCl
Code Iron in Solution (lbs/1000 gal)

200 Reducing Agent 1.0 : 2.5 9.45 ppt Very Soluble

210 Reducing Agent 1.0 : 1.7 7.7 ppt Very Soluble

260L Reducing Agent 3.0 : 3.1 1.3 gpt Very Soluble

270L Reducing Agent 2.02 : 1.0 1.8 gpt Very Soluble

271L Catalyst for Very Soluble

Ferrotrol 270L
300 Chelation 3.53 : 1.0 29.45 ppt > 300

300L Chelation 3.53 : 1.0 5.89 gpt > 300 (60 gal)

700 Chelation 5.30 : 1.0 44.23 ppt 68

800 Chelation 5.19 : 1.0 43.44 ppt > 400

800L Chelation 5.19 : 1.0 8.64 gpt > 400 (85 gal)

810 Chelation 3.61 : 1.0 30.10 ppt Very Soluble

900 Chelation 8.33 : 1.0 69.95 ppt 100

900L Chelation 7.45 : 1.0 14.13 gpt 100 (22.7 gal)

1000 Chelation 6.70 : 1.0 55.91 ppt 89

HS-A Sulphide - See HSSA Very Soluble

HS-B Scavenger - Very Soluble
System
Acetic Acid pH Control - - -

Page 6
Iron Control

{ XE "Ferrotrol Products:Iron Control Chemicals" }{ XE "Ferrotrol Products:Function" }{

XE "Iron Control Chemicals:Usage" }{ XE "Ferrotrol Products:Usage" } { XE
"Usage:Ferrotrol Products" } { XE "Solubility in Acid:Iron Control Chemicals" }{ XE
"Solubility in Acid:Ferrotrol Products" }{ XE "Solubility:Iron Control Chemicals" }
Notes:

* Chelation Ratio = lbs of Ferrotrol product per 1.0 lb of Iron

1. Ratios are based on spent acid with the exception of Ferrotrol 260L,
Ferrotrol 270 and Ferrotrol 271.
2. Most Ferrotrol chelation agents are less effective in live acid.
3. Control Ratio for Reducing agents is to reduce Fe3+ to Fe 2+.
4. Ferrotrol 270L and Ferrotrol 271L must always be used together.

3.1. Chelating Agents.{ XE "Chelating Agents.:Methods of Iron Control" }{ XE

"Methods of Iron Control:Chelating Agents" }

Chelating agents{ XE "Chelating agents" }{ XE "Chelating agents:Citric Acid" }{ XE

"Chelating agents:NTA" }{ XE "Chelating agents:EDTA" } are chemicals that for stable,
water soluble complexes with ferric and ferrous iron ions. By complexing the iron, its
reactivity is reduced and its normal insoluble products are inhibited from forming.
Organic acids and their salts such as Citric Acid{ XE "Citric Acid:Chelating agents" },
NTA and EDTA{ XE "EDTA:Chelating agents" }, are the materials currently used in this
capacity.

The iron complexes{ XE "iron complexes:Chelating agents" }{ XE "iron

complexes:stability" } formed will remain in solution in the spent acid, preventing the
formation of ferric hydroxide even at pH values approaching 7.0. However, these
complexes will break down with time (see Table 6), and therefore, the chelating agent
should be selected to provide sufficient protection time to allow treatment of the well and
recovery of the fluid. Under normal circumstances fluid recovery{ XE "fluid recovery
time" } should begin within one to four hours following a treatment. If Hydrogen sulphide{
XE "Hydrogen sulphide:Chelating agents" } (H2S) is present then the use of hydrogen
sulphide scavengers{ XE "hydrogen sulphide scavengers:Chelating agents" } should be
used in conjunction with the chelating agents.

3.1.1. Citric Acid{ XE "Citric Acid:Chelating Agents" }{ XE "Chelating

Agents:Citric Acid" }.

The most commonly used chelating agent is citric acid. This is Ferrotrol 300{ XE
"Ferrotrol 300:Citric Acid" }{ XE "Citric Acid:Ferrotrol 300" }{ XE "Citric Acid:Chelating
Agents" }{ XE "Ferrotrol 300" } (powder) or Ferrotrol 300 L{ XE "Ferrotrol 300 L" }
(50% aqueous solution containing 5 pounds of citric acid per gallon). It can be used in
all acid solutions including 28% HCl and HCl:HF systems. Often combinations of citric
acid with other Ferrotrol agents (chelating and reducing types) and or buffers are used.

Page 7
Iron Control

At concentrations greater that 50 pounds per 1000 gallons the possibility exists for the
formation of calcium citrate{ XE "calcium citrate" }. This may occur when the iron
concentration is insufficient to consume all of the citric acid and sufficient calcium has
dissolved in the acid. At a pH value above 4.5 the solubility of calcium citrate is very low
in spent acid or water. Ordinarily the precipitation of calcium citrate will not occur in the
formation due to the pH effect of dissolved carbon dioxide in the treating fluid, formed
by the reaction of acid with carbonates. The calcium citrate will most likely form in areas
where the greatest pressure drop occurs, such as the perforation tunnels, the down hole
pump or at the surface.

Recommended concentrations:

Ferrotrol 300 25 to 250 pounds per 1000 gallons.

Ferrotrol 300L 5 to 50 gallons per 1000 gallons.

3.1.2. EDTA Acid{ XE "Chelating Agents:EDTA Acid" }{ XE "EDTA Acid:Chelating

Agents" } (Ethylene-Di-Amine-Tetra-Acetic Acid{ XE "Ethylene-Di-Amine-Tetra-
Acetic Acid" }).

This product (Ferrotrol{ XE "Chelating Agents:Ferrotrol 700" } 700{ XE "Ferrotrol

700:Chelating Agents" }{ XE "Ferrotrol 700:EDTA" }{ XE "EDTA:Ferrotrol 700" }) is
seldom recommended for use as an iron control agent due to its extremely low solubility
in water and very slow rate of dissolution in acid at surface conditions. Due to this
various salts of EDTA are commonly used instead and are mentioned below.

3.1.3. Tetra Sodium EDTA.{ XE "Tetra Sodium EDTA:Chelating Agents" }{ XE

"Chelating Agents:Tetra Sodium EDTA" }{ XE "Chelating Agents:Ferrotrol 900" }{ XE
"Ferrotrol 900:Tetra Sodium EDTA" }{ XE "Tetra Sodium EDTA:Ferrotrol 900" }

Ferrotrol 900 is Tertra-Sodium-Ethylene-Di-Amine-Tetra-Acetate, Tetra-Hydrate

(EDTA Na 4.4H2O) and Ferrotrol 900L{ XE "Ferrotrol 900L" } is the 42% by weight
solution (approximately 4.5 pounds of Ferrotrol 900 per gallon. These materials are
not recommended for use in acids containing hydrofluoric acid or in hydrochloric
acid that is stronger than 15% HCl. The solubility in 15% HCl is limited to
approximately 100 pounds per thousand gallons or 22.7 gallons per thousand
gallons respectively. These are the least efficient chelating agents available for
controlling iron compounds in spent acid.

3.1.4. Di-Sodium EDTA.{ XE "Chelating Agents:Di-Sodium EDTA" }{ XE "Chelating

Agents:Ferrotrol 1000" }{ XE "Di-Sodium EDTA:Ferrotrol 1000" }{ XE "Ferrotrol
1000:Di-Sodium EDTA" }{ XE "Ferrotrol 1000:Chelating Agents" }{ XE "Di-Sodium
EDTA:Chelating Agents" }

Page 8
Iron Control

Ferrotrol 1000 is Di-Sodium-Ethylene-Di-Amine-Tetra Acetate, Di-Hydrate (EDTA

Na2.2H2O). This material is not recommended for use in acids containing hydrofluoric
acid or for use in hydrochloric acid stronger than 15% HCl. Solubility in 15% HCl is
limited to approximately 89 pounds per thousand gallons. Ferrotrol 1000 is a slightly
more efficient chelating agent than Ferrotrol 900 or 900L.

3.1.5. Tri-Sodium NTA. { XE "Chelating Agents:Tri-Sodium NTA" }{ XE "Chelating

Agents:Ferrotrol 800" }{ XE "Tri-Sodium NTA:Ferrotrol 800" }{ XE "Ferrotrol 800:Tri-
Sodium NTA" }{ XE "Ferrotrol 800:Chelating Agents" }{ XE "Tri-Sodium NTA:Chelating
Agents" }

Ferrotrol 800 is Tri-Sodium-Nitrilo-Acetate, Mono-Hydrate (NTA Na 3.H2O) and Ferrotrol

800L{ XE "Ferrotrol 800L" } is a 43% by weight solution (approximately 4.7 pounds per
gallon). This product can be used in a broad range of acid strengths from 3.0% to 28%
HCl and can be placed in either the mix water or the acid. However, its solubility at
surface conditions is limited to 50 pounds per thousand gallons in 28% HCl. This
product is not recommended for use in Hydrofluoric acid systems due to the sodium
content. Tri-sodium NTA will react with calcium to form a salt that is soluble in water and
spent acid.

Recommended concentrations:

Ferrotrol 800 25 to 350 pounds per 1000 gallons (3.0% to 20% HCl).
Ferrotrol 800L 5 to 75 gallons per 1000 gallons.

3.1.6. Nitrilo-Acetic Acid{ XE "Nitrilo-Acetic Acid" \t "See NTA Acid" }.{ XE

"Chelating Agents:NTA Acid" }{ XE "Chelating Agents:Ferrotrol 810" }{ XE "NTA
Acid:Ferrotrol 810" }{ XE "Ferrotrol 810:NTA Acid" }{ XE "Ferrotrol 810:Chelating
Agents" }{ XE "NTA Acid:Chelating Agents" }

Ferrotrol 810 is NTA Acid and is the second most effective chelating agent available.
This product can be used in a broad range of acid strengths from 3.0% to 28% HCl and
most commonly used strengths of HCl:HF acid mixtures. Ferrotrol 810 is only slightly
soluble in water and should always be added to acid and not the mix water. NTA reacts
with calcium ion to form a salt that is soluble in spent acid and water.

Recommended concentrations:

Ferrotrol 810 25 to 350 pounds per 1000 gallons.

Table 3: Conversion Factors, Ferrotrol Chelating Agent Equivalents.

{ XE "Ferrotrol Products:Conversion Factors" }{ XE "Conversion Factors:Ferrotrol
Products" }

Page 9
Iron Control

To Replace Use Weight in Pounds of Ferrotrol

One Pound of
300 700 800 800L 810 900 900L 1000
Ferrotrol 300 --- 1.51 1.47 2.26 1.02 2.36 5.23 1.90
Ferrotrol 700 0.66 --- 0.93 2.15 0.65 1.58 3.40 1.26
Ferrotrol 800 0.68 1.07 --- 2.34 0.70 1.70 3.65 1.36
Ferrotrol 800L 0.44 0.46 0.43 --- 0.30 0.74 1.58 0.59
Ferrotrol 810 0.98 1.54 1.44 1.44 --- 2.44 5.24 1.96
Ferrotrol 900 0.42 0.63 0.59 0.59 0.41 --- 2.15 0.80
Ferrotrol 900L 0.19 0.29 0.27 0.27 0.19 0.47 --- 0.37
Ferrotrol 1000 0.53 0.79 0.73 0.73 0.51 1.25 2.68 ---

Note:

Density (ppg) : Ferrotrol 300L = 10.0 ppg (50% Active)

: Ferrotrol 800L = 11.0 ppg
: Ferrotrol 900L = 10.9 ppg

3.2. Reducing Agents{ XE "Reducing Agents:Methods of Iron Control" }{ XE

"Reducing Agents" }{ XE "Methods of Iron Control:Reducing Agents" }.

Reducing Agents function to convert ferric iron in solution to ferrous iron and to maintain
this oxidation state. The elimination of ferric ions prevents the precipitation of ferric
hydroxide{ XE "ferric hydroxide:Reducing Agents" } as the acid spends and the pH
rises above 2.5. In addition, removal of the ferric ions reduces the risk of asphaltene
flocculation and precipitation. Anytime asphaltenes{ XE "asphaltenes:Reducing
Agents" } are present in the crude oil, a reducing agent should be used. The presence
of dissolved oxygen{ XE "dissolved oxygen:Reducing Agents" }{ XE "Oxygen:Reducing
Agents" } ( maximum 8.0 parts per million) will react with these reducing agents and
therefore, the amount of reducing agent used in the acid should compensate for this.
Erythorbic acid{ XE "Erythorbic acid:Reducing Agents" } and its salts are commonly
used for this application.

3.2.1. Sodium Erythorbate.{ XE "Reducing Agents:Sodium Erythorbate" }{ XE

"Ferrotrol 200:Sodium Erythorbate" }.{ XE "Sodium Erythorbate.:Reducing Agents" }{
XE "Sodium Erythorbate.:Ferrotrol 200" }

Page 10
Iron Control

Ferrotrol 200{ XE "Reducing Agents:Ferrotrol 200" }{ XE "Ferrotrol 200:Reducing

Agents" } is Sodium Erythorbate (NaC6H7O6.H2O). The products of this reducing agent
are believed to be complexes with the ferrous ions. Ferrotrol 200 is very soluble in water
and 15% HCl. It is less stable as the acid strength is increased and if added to 28%
HCl, degradation will occur, producing a fine carbon like product. Stability is also
affected by temperature. Storage time in acid should be minimized to ensure the
chemical stability. Usage of this material in HCl:HF acid systems should be minimized.
This product is more effective in spent acid.

Recommended concentrations:

Ferrotrol 200 10 to 40 pounds per 1000 gallons.

3.2.2. Erythorbic Acid. { XE "Reducing Agents:Erythorbic Acid" }{ XE "Ferrotrol

210:Erythorbic Acid" }.{ XE "Erythorbic Acid.:Reducing Agents" }{ XE "Erythorbic
Acid.:Ferrotrol 210" }{ XE "Ferrotrol 210:Reducing Agents" }{ XE "Reducing
Agents:Ferrotrol 210" }

Ferrotrol 210 is Erythorbic Acid (C 6H8O6.). The products of this reducing agent are
believed to be complexes with the ferrous ions. Ferrotrol 210 is very soluble in water
and 15% HCl. It is less stable as the acid strength is increased and if added to 28%
HCl, degradation will occur, producing a fine carbon like product. Stability is also
affected by temperature. Storage time in acid should be minimized to ensure the
chemical stability. This product is more effective in spent acid.

Recommended concentrations:

Ferrotrol 210 10 to 40 pounds per 1000 gallons.

3.2.3. Ferrotrol 260L.{ XE "Ferrotrol 260L:Reducing Agents" }{ XE "Reducing

Agents:Ferrotrol 260L" }

This is a proprietary blend of chemicals in liquid form which can be readily mixed with
hydrochloric acid at concentrations ranging from 3.0% to 28% HCl and most common
HCl:HF acid mixtures. This system is quite expensive however, 1.3 gallons per
thousand gallons will reduce 1000 parts per million of ferric iron. This product works
equally well in live acid or spent acid.

Recommended Concentrations:

Ferrotrol 260L 1.5 to 15 gallons per thousand gallons.

Page 11
Iron Control

3.2.4. Ferrotrol 270 and Ferrotrol 271. { XE "Ferrotrol 270L:Reducing Agents" }{ XE

"Reducing Agents:Ferrotrol 270L" }{ XE "Ferrotrol 271L:Reducing Agent Catalyst" }{
XE "Reducing Agents:Ferrotrol 271L" }{ XE "Catalyst:Reducing Agents" }

These are proprietary blends of chemicals in liquid form which can be readily mixed
with hydrochloric acid at concentrations ranging from 3.0% to 20% HCl and most
common HCl:HF acid mixtures up to 12%:3.0% HCl:HF. The system has two
components with Ferrotrol 270 being added to the acid at the time of loading, and
Ferrotrol 271, the catalyst, being added just prior to pumping. Failure to pump the fluid
immediately after adding the catalyst may result in more material being required to
provide adequate reducing capabilities. 1.8 gallons per 1000 gallons of Ferrotrol 270
and 1.0 gallons per 1000 gallons Ferrotrol 271, together will reduce 1000 parts per
million of ferric iron. These products work equally well in spent or live acid. Table 4 lists
guideline concentrations for these products for use in hydrochloric acid up to 20%
concentration.

Recommended Concentrations:

Ferrotrol 270L 2.0 to 16 gallons per thousand gallons.

Ferrotrol 271L 1.0 to 2.0 gallons per thousand gallons.

Table 4: Ferrotrol 270 and Ferrotrol 271 Guidelines{ XE "Ferrotrol 270 and
Ferrotrol 271 Guidelines" } up to 20% HCl.

Ferric Iron (ppm) Ferrotrol 270 (gpt) Ferrotrol 271 (gpt)

1000 2 1
2500 5 1
5000 8 2
10000 16 2

3.3. pH Control Agents (Buffers).{ XE "pH Control Agents (Buffers).:Methods of

Iron Control " }{ XE "Methods of Iron Control:pH Control Agents" }{ XE "Methods of Iron
Control:Buffers" }{ XE "Buffers:Methods of Iron Control" }

These materials act as buffering agents to maintain a low pH and retard the
precipitation of insoluble iron compounds. Proper buffering agents help control the pH
of an acid treating fluid once it begins to react on the formation or other acid soluble
materials. The use of buffers without chelating agents and or reducing agents is
generally not recommended. Buffers should also not be used in well with a bottom hole
temperature greater than 160 °F (71 °C). Acetic Acid, Acetic Anhydride or Sodium Acid

Page 12
Iron Control

Pyrophosphate (SAPP) are the primary materials used as buffers in acid treating
solutions. The effect of pH on the precipitation of iron compounds with various pH
control agents is shown in Figure 1 on page 12

3.3.1. Acetic Acid{ XE "Acetic Acid:pH Control Agents" }{ XE "Acetic Acid:Buffers" }{

XE "Buffers:Acetic Acid" }{ XE "pH Control Agents:Acetic Acid" } and Acetic
Anhydride.{ XE "Acetic Anhydride:pH Control Agents" }{ XE "Acetic
Anhydride:Buffers" }{ XE "pH Control Agents:Acetic Anhydride" }{ XE "Buffers:Acetic
Anhydride" }.

These are both liquids that mix rapidly in all normal acid stimulation fluids and should be
readily available in most areas.

Recommended Concentrations:

Acetic Acid 10 to 20 gallons per thousand gallons.

3.3.2. Sodium Acid Pyrophosphate{ XE "Sodium Acid Pyrophosphate" \t "See

SAPP" } (SAPP{ XE "SAPP:Sodium Acid Pyrophosphate" }{ XE "SAPP:Buffers" }{
XE "SAPP:pH Control Agents" }{ XE "pH Control Agents:SAPP" }{ XE "Buffers:SAPP"
}).

SAPP is a white solid material which dissolves slowly in acid treating solutions, but is
not corrosive or difficult to handle.

Recommended Concentrations:

SAPP 1.0 to 10 pounds per thousand gallons.

3.4. Sulphide Scavengers{ XE "Sulphide Scavengers:Methods of Iron Control" }{

XE "Methods of Iron Control:Sulphide Scavengers" }.

Sulphide scavengers are chemicals which form stable complexes with sulphide ions.
This complexation in conjunction with the complexation of the ferrous ions{ XE "Ferrous
ions:Sulphide scavengers" } by one of the chelating agents, prevents the precipitation of
iron sulphide{ XE "Iron sulphide:Sulphide scavengers" } in a formation containing
hydrogen sulphide{ XE "hydrogen sulphide:Sulphide scavengers" }, when the acid
spends.

Iron sulphide scale dissolved by hydrochloric acid will precipitate out of spent acid as
the pH of the fluid rises above 1.9. BJ Services’ sulphide system consists of Ferrotrol
HS-A{ XE "Ferrotrol HS-A:Sulphide scavengers" } and Ferrotrol HS-B{ XE "Ferrotrol

Page 13
Iron Control

HS-B:Sulphide scavengers" } to provide control of the sulphides in solution, whilst

Ferrotrol 300{ XE "Ferrotrol 300:Sulphide scavengers" } (300L), Ferrotrol 800{ XE
"Ferrotrol 800:Sulphide scavengers" } (800L) or Ferrotrol 810{ XE "Ferrotrol
810:Sulphide scavengers" } can be used with these additives to control the ferrous ions.

3.4.1. Ferrotrol HS-A and Ferrotrol HS-B.

Ferrotrol HS-A and Ferrotrol HS-B should be added to the acid prior to pumping. The
Ferrotrol HS-A may be added as much as twenty four hours prior to pumping, however,
Ferrotrol HS-B must not be added until just prior to pumping. These two components
mixed in acid release the active ingredient which controls the sulphide. This ingredient
is very volatile and will eventually evaporate from the acid solution. Ferrotrol HS-A and
Ferrotrol HS-B concentrates should never be mixed directly together. Ferrotrol HS-A is
corrosive and Ferrotrol HS-B is flammable.

Recommended Concentrations:

Ferrotrol HS-A 5.0 to 15 gallons per thousand gallons.

Ferrotrol HS-B 3.0 to 10 gallons per thousand gallons.
4. Acid Treatment Designs.

4.1. Pipe Pickling Treatments.

The most effective means of controlling tubular iron as a source of problems is to

perform a “pipe pickling{ XE "pipe pickling treatments" }” treatment. This involves
pumping a volume of inhibited acid{ XE "inhibited acid" }, down the tubing and then
reversing it out of the well, allowing the acid to remove the majority of iron deposits. This
prevents the main acid treatment from dissolving as much iron and carrying it into the
formation.

It is generally recommended that a volume of 100 gallons per 1000 ft of tubing be used
to perform this “pickle”. The fluid should consist of at least 10% hydrochloric acid and
preferably 15%. It is further recommended that a solvent phase (xylene{ XE "xylene:pipe
pickling" }) be used either ahead of the acid or dispersed within the acid (One Shot
Acid Plus{ XE "One Shot Acid Plus:Pipe Pickling" }), to facilitate removal of organic
materials and pipe dope{ XE "pipe dope" } that may be in the tubing. If casing is to be
“pickled”, the volume to use may need to be adjusted depending on the extent of the
iron scale present.

4.2. Sequestering Acid Systems (SA-Systems).

{ XE "Sequestering Acid Systems" }{ XE "Precipitates:Sequestering Acid Systems" }{
XE "Acetic Acid:Sequestering Acid Systems" }{ XE "Citric Acid:Sequestering Acid
Systems" }{ XE "Lactic Acid:Sequestering Acid Systems" }{ XE "Organic
Acids:Sequestering Acid Systems" }{ XE "pH:Precipitation" }{ XE "pH:Sequestering
Acid Systems" }{ XE "pH:Effect on Sequestrants" }{ XE "SA-10:Sequestering Acid

Page 14
Iron Control

Systems" }{ XE "Effect of pH on Various Sequestrants" }{ XE "Iron

Hydroxide:Sequestering Acid Systems" }{ XE "Precipitates:Iron Hydroxide" }{ XE "Iron
Hydroxide:Precipitation" } { XE "Hydrochloric Acid:Sequestering Acid Systems" }{ XE
"pH:Hydrochloric Acid" }{ XE "Hydrochloric Acid:pH" }{ XE "Spent Acid:pH" }{ XE
"pH:Spent Acid" }
Chemicals called sequestering agents are used in acidizing to control the secondary
precipitation of iron deposits from spent acid solutions in non hydrogen sulphide
environments. Added to hydrochloric acid or HCl:HF systems, these sequestrants
prevent the customary, iron-spent acid reaction for extended periods of time.

Most sequestering agents are organic acids such as acetic, citric or lactic acid, or a
mixture of these acids. However, not every organic acid is equally effective for reducing
or controlling the activities of iron. The effectiveness of each acid is influenced by many
factors, such as the pH of the system in which it is used, its concentration and the
external temperature. For these reasons sequestrants should be laboratory tested at
different concentrations under simulated pH and temperature conditions of actual use.

Figure 1 shows the pH range at which iron re-precipitates in neutralized SA-10

compared to three other sequestrants in spent acid. As can be seen the alternative
sequestering systems, will retard the reprecipitation of iron hydroxide up to a pH of
about 5.0, whereas the SA-10 will prevent this up to a pH of nearly 8.0.

BJ Services Sequestering Acid systems (SA-2, SA-4, SA-6, SA-8 and SA-10), will
effectively prevent water insoluble iron hydroxides, resulting from the chemical reaction
of hydrochloric acid and iron compounds, from forming and precipitating out into the
formation or well-bore by sequestering (chemically "tying up") these hydroxides.

Figure 1: Effect of Increasing pH on Various Sequestrants{ XE "Effect of

Increasing pH on Various Sequestrants" }.

Page 15
Iron Control

SA-10

ACETIC AND CITRIC ACID *

ACETIC ACID (GLACIAL) IRON

REPRECIPITATES
LACTIC ACID (44%)

pH OF NEUTRALISED ACID
0.0 1.0 2.0 3.0 4.0 5.0 6.0 7.0 8.0 9.0 10.0
pH SCALE

* 10 gallons Acetic Acid & 50 lbs Citric Acid per 1000 gallons.

Sequestering acid systems prevent the severe plugging and permeability damage that
might otherwise result where iron scales or minerals are present. The specific SA-Acid
system selected depends upon the quantity of iron solids present that must be tied up in
solution. SA-2 can sequester 2000 ppm of ferric iron whilst SA-10 will complex about
10,000 ppm iron. Typical quantities of common iron salts that are sequestered by the
different SA-Acid systems is shown in Table 5.{ XE "Sequestering Acid Systems:Iron
Hydroxide" }{ XE "Sequestering Acid Systems:Hydrochloric Acid" }{ XE "Sequestering
Acid Systems:pH" }{ XE "pH:Hydrochloric Acid" }{ XE "Hydrochloric Acid:pH" }{ XE
"Spent Acid:pH" }{ XE "pH:Spent Acid" }{ XE "Iron Scales:Sequestering Acid
Systems" }{ XE "Iron Salts" }

Table 5: Pounds of Iron Sequestered per 1000 gallons of SA-Acid System{ XE

"Pounds of Iron Sequestered per 1000 gallons of SA-Acid System" } { XE "Ferrous Iron
Sulphide:SA Acid Systems" }{ XE "Iron Sulphide:SA Acid Systems" }{ XE "Ferrous Iron
Carbonate:SA Acid Systems" }{ XE "Iron Carbonate:SA Acid Systems" }{ XE "Ferric
Iron Oxide:SA Acid Systems" }{ XE "Ferric Oxide:SA Acid Systems" }{ XE "Iron
Oxide:SA Acid Systems" }.

SA-ACID FERROUS IRON FERROUS IRON FERRIC IRON

SYSTEM SULPHIDE CARBONATE OXIDE
FeS FeCO3 Fe2O3
SA-2 26.2 34.6 23.8

SA-4 52.5 69.2 47.6

SA-6 78.8 103.8 71.5

Page 16
Iron Control

SA-8 105.0 138.1 95.4

SA-10 131.3 172.9 119.1

Sequestering agents, such as Ferrotrol 300, control metal ions by blocking the reactive
sites of the metal ion and preventing them from entering into their normal (and in many
cases undesirable) reactions. Those sequestering agents forming the most stable
bonds with metal ions will be the most effective in preventing metal ion activity. { XE
"Ferrotrol 300:SA Acid Systems" }{ XE "Ferrotrol 300:Sequestrant" }{ XE "Ferrotrol
210:Reducing Agent" } { XE "Reducing Agents:Ferrotrol 210" }{ XE "Sequestering
Agents:Ferrotrol 300" }
Ferrotrol 210 is a reducing agent. This product works by reducing Fe3+ to Fe2+, based
on a chemical reaction where an electron is donated to the ferric iron thus reducing its
oxidation state. When mixed with hydrochloric acid, Ferrotrol 210 also exhibits weak
chelating properties that combine with its reducing properties to provide enhanced
activity.

In general, a molar ratio of 1.0 to 1.0 sequestrant is sufficient to maintain solubility of the
iron. Using this ratio, one pound of iron requires:
{ XE "Molar Ratio of Sequestrant to Iron Solubility" }{ XE "Citric Acid:Weight Ratio to
Iron" }{ XE "EDTA:Weight Ratio to Iron" }{ XE "NTA:Weight Ratio to Iron" } { XE
"Sequestrants:Molar Ratio" } { XE "Sequestrants:Performance" }{ XE "Iron Control
Chemicals:Performance" }
• 3.5 lbs Citric Acid
• 5.2 lbs EDTA (H4 EDTA)
• 7.5 lbs EDTA Tetra-Sodium Salt (Na4 EDTA)
• 17.9 lbs EDTA Na 4 solution
• 3.5 lbs NTA Na 3 (Tri-Sodium Salt)

The performance of sequestering agents is not always equal. Their effectiveness at

forming stable metal chelates can be influenced by

• The pH of the system.

• Temperature.
• Concentration at which they are used.
• Metal ion or ions that are present in the system.

The best approach in selecting a sequestering agent is to compare their performance

under simulated actual use conditions. Table 6 shows the effectiveness of various
sequestering in spent hydrochloric acid at different temperatures.

Studies to compare the performance of iron control agents under similar well conditions
have shown the relative order of stability of the soluble complexes to be; Citrate > EDTA
> NTA > Acetic.

Page 17
Iron Control

Table 6: Effectiveness of Various Iron Sequestering Agents in Spent Acid.

{ XE "Effectiveness of Various Iron Sequestering Agents in Spent Acid" }{ XE "Citric
Acid:Effectiveness" }{ XE "Acetic Acid:Effectiveness" }{ XE "Lactic
Acid:Effectiveness" }{ XE "EDTA:Effectiveness" }{ XE "NTA:Effectiveness" }{ XE
"Gluconic Acid:Effectiveness" }{ XE "Ferric Iron:Amount Stabilized by Various
Sequestrants" } { XE "Stability of sequestrants" }
{ XE "Complexes:Stability" }

Sequestering Additive Temperature Ferric Iron Time

Agent Concentration (°F) Stabilized Before
(Lbs/1000 (ppm) Reprecipitation
Gals)

Citric Acid 35 200 1,000 Over 48 Hours

(Ferrotrol 300) 75 10,000 24 Hours
Acetic Acid 174 150 5,000 2 Hours
200 10,000 10 Minutes
5,000 20 Minutes

Mixture Of 50 75 10,000 48 Hours

Citric And 87 5,000 7 Days
Acetic Acid 150 10,000 24 Hours
5,000 7 Days
200 10,000 15 Minutes
5,000 30 Minutes

Tetra-Sodium 225 All Ranges 4,300 Over 48 Hours

Salt of EDTA
(Ferrotrol 900)
Tri-Sodium 50 Up to 200 1,000 Over 48 Hours
Salt of NTA
(Ferrotrol 800)
Lactic Acid 65 75 1,700 24 Hours
150 1,700 2 Hours
200 1,700 10 Minutes

Gluconic Acid 103 150 1,500 20 Hours

Page 18
Iron Control

Table 7: Limitations of Ferrotrol Agents in Acid{ XE "Limitations of Ferrotrol

Agents in Acid" }.

Ferrotrol Agent Common Name Limitations

Ferrotrol 200{ XE Sodium Erythorbate{ XE Not recommended for acid stronger

"Ferrotrol "Sodium than 20% HCl or with HF.
200:Limtations" } Erythorbate:Limtations" }
Ferrotrol 210{ XE Erythorbic Acid{ XE Not recommended for acid stronger
"Ferrotrol "Erythorbic than 20% HCl.
210:Limtations" } Acid:Limtations" }
Ferrotrol 260L{ Proprietary Blend Expensive.
XE "Ferrotrol
260L:Limtations"
}
Ferrotrol 270L{ Proprietary Blend Must be used together and not in acid
XE "Ferrotrol
270L:Limtations"
}
Ferrotrol 271L{ Proprietary Blend stronger than 20% HCl.
XE "Ferrotrol
271L:Limtations"
}
Ferrotrol 300{ XE Citric Acid{ XE "Citric Needs sufficient iron to consume.
"Ferrotrol Acid:Limtations" }
300:Limtations" }
Ferrotrol 300L{ Citric Acid Solution Needs sufficient iron to consume.
XE "Ferrotrol
300L:Limtations"
}
Ferrotrol 700{ XE EDTA Acid{ XE "EDTA Not recommended due to low solubility.
"Ferrotrol Acid:Limtations" }
700:Limtations" }
Ferrotrol 800{ XE Tri-Sodium Salt of NTA{ Not recommended for acid stronger
"Ferrotrol XE "Tri-Sodium than 20% HCl or with HF.
800:Limtations" } NTA:Limtations" }
Ferrotrol 800L Tri-Sodium Salt of NTA Not recommended for acid stronger
Solution than 20% HCl or with HF.
Ferrotrol 810{ XE NTA Acid{ XE "NTA None
"Ferrotrol Acid:Limtations" }
810:Limtations" }
Ferrotrol 900{ XE Tetra-Sodium Salt of Solubility
"Ferrotrol EDTA{ XE "Tetra-
900:Limtations" } Sodium

Page 19
Iron Control

EDTA:Limtations" }
Ferrotrol 900L{ Tetra-Sodium Salt of Solubility
XE "Ferrotrol EDTA Solution
900L:Limtations"
}
Ferrotrol 1000{ Di-Sodium Salt of Solubility
XE "Ferrotrol EDTA{ XE "Di-Sodium
1000:Limtations" EDTA:Limtations" }
}
Ferrotrol HS-A{ Proprietary Blend Must be used together and with one of
XE "Ferrotrol HS-
A:Limtations" }
Ferrotrol HS-B{ Proprietary Blend the Chelating agents above.
XE "Ferrotrol HS-
B:Limtations" }
SAPP{ XE Sodium Acid Not recommended as a Buffer at
"SAPP:Limtation Pyrophosphate temperatures greater than 160 °F
s" }
Acetic Acid{ XE Acetic Acid Not recommended as a Buffer at
"Acetic temperatures greater than 160 °F
Acid:Limtations" }
or Acetic
Anhydride

4.3. Hydrogen Sulphide Scavenger Acid{ XE "HSSA:Hydrogen Sulphide

Scavenger Acid" }{ XE "Hydrogen Sulphide Scavenger Acid" \t "See HSSA" } (HSSA{
XE "HSSA" }).

The HSSA{ XE "HSSA:Sour Wells" }{ XE "Sour wells:HSSA" } system is a special acid

system for use in sour wells to help control the re-precipitation of iron sulphide{ XE "Iron
sulphide:HSSA" }, iron hydroxide and the formation of elemental sulphur{ XE
"Elemental sulphur:HSSA" } during acid stimulation. The system incorporates Ferrotrol
HS-A{ XE "Ferrotrol HS-A:HSSA" }, Ferrotrol HS-B{ XE "Ferrotrol HS-B:HSSA" }, and
Ferrotrol 300{ XE "Ferrotrol 300:HSSA" }, Ferrotrol 800{ XE "Ferrotrol 800:HSSA" } or
Ferrotrol 810{ XE "Ferrotrol 810:HSSA" }, which provide a synergistic effect to control
these very damaging acid reaction precipitates. The system may be prepared using
3.0% to 28% hydrochloric acid. The following tables show the conditions for usage.

Table 8: HSSA System Options Based on Well Conditions.{ XE "HSSA System

Options Based on Well Conditions." }

Severe Conditions System Options

Page 20
Iron Control

A- Iron Sulphide{ XE "Iron A- Higher Concentrations of additives in

Sulphide:HSSA" }{ XE "Pipe the spearhead fluid with reduced
Pickling:HSSA" }{ XE "Hydrogen quantity in body of treating fluid
Sulphide:HSSA" } Scale present.
B- Unable to pickle tubulars.
or

C- Moderate to high H2S B- Treat entire fluid with same high

(Greater than 5.0%). concentrations.

Moderate Conditions System Options

A- Moderate H2S
(2.0% to 3.0%)
B- Able to pickle tubulars A- Treat entire fluid with same
concentration.
C- Iron Silphide Scale may be present.

Normal Conditions System Options

A- Low to moderate H2S

(0.5% to 2.0%).
B- Able to pickle tubulars. A- Treat entire fluid with same
concentration.
C- Iron Sulphide Scale may be present

Table 9: HSSA Treatment Fluids.{ XE "HSSA Treatment Fluids." }{ XE

"HSSA:Additive quantities" }

Conditions Quantities of Additives

Severe Spearhead :

Acid + 15 gpt Ferrotrol HS-A + 10 gpt Ferrotrol HS-B

+ Ferrotrol 800 or 200 ppt Ferrotrol 300 ( 40 gpt Ferrotrol 300L)

or
Body of Treatment:

Acid + 8.0 gpt Ferrotrol HS-A + 6.0 gpt Ferrotrol HS-B

+ Ferrotrol 800 or 150 ppt Ferrotrol 300 ( 30 gpt Ferrotrol 300L)

Moderate

Page 21
Iron Control

Acid + 7.5 gpt Ferrotrol HS-A + 5.0 gpt Ferrotrol HS-B

+ 100 ppt Ferrotrol 800 or 100 ppt Ferrotrol 300
( 20 gpt Ferrotrol 300L)

Normal
Acid + 5.0 gpt Ferrotrol HS-A + 2.5 gpt Ferrotrol HS-B
+ 50 to 75 ppt Ferrotrol 800 or Ferrotrol 300
( 10 to 15 gpt Ferrotrol 300L)

4.3.1. HSSA Corrosion Inhibition{ XE "Corrosion Inhibition:HSSA" }{ XE

"HSSA:Corrosion Inhibition" }.

Use recommened inhibitor loadings based on acid strength at temperatures up to 180

°F (82.2 °C). Above this temperature 25% more corrosion inhibitor should be utilized to
provide adequate protevtion of tubulars.

Page 22
Iron Control

5. Non-Acid Treatments Using Chelating Agents.

{ XE "Non-Acid Treatments Using Chelating Agents" }{ XE "Calcium
Sulphate:Removal" } { XE "Gypsum:Removal" } { XE "Mud Damage:Removal" } { XE
"Water Based Mud Damage:Removal" }{ XE "Gypsol:Non Acid Treatments" }{ XE
"Scale:Gypsum" }{ XE "Versol:Non Acid Treatments" }{ XE "Acid Sensitive
Formations" }
Chelating agents are also used in non-acid treating solutions for the removal of damage
from water based mud and for the removal of calcium sulphate scales (gypsum).

Gypsol systems are water based systems containing chelating agents and surfactants
that chemically disperse the scale into more simple acid soluble constituents by a
dissociation process, or dissolve the scale by complexing the calcium ion and retaining
it in solution in its ionic state. Both these systems are applied by using soaking of up to
24 hours and then swabbing the treatment back.

These systems are useful where it is undesirable to perform an acid job. Gypsol 1 for
example, can be used when there is the risk that an acid treatment might stimulate
water production. Gypsol 1 dissolves the calcium sulphate scale by complexing the
calcium ion and retaining it in its ionic state. This removal of the calcium provides the
mechanism by which the scale material dissolves, usually requiring the solution to be left
in contact for between 16 and 24 hours.

Gypsol 2 is a "converter type" solvent, that converts calcium sulphate from an acid
insoluble scale to one that can be easily dissolved with acid. Normally this solution is
spotted across the scale deposit and left to soak for up to 24 hours, and is then
swabbed or pumped out of the well. This treatment is then followed with a conventional
hydrochloric acid soak to remove the converted scale.

Versol 1 and Versol 2 are non acid reactive solvents which consist of a mixture of
chelating agents and surfactants. They are used in the removal of formation damage
caused by drilling muds, to break emulsions and water blocks, and to lower the viscosity
of drilling fluids. Versol solvents are particularly useful in place of acid when treating,
acid sensitive formations or wells with deep high temperature formations where
excessive corrosion of tubular goods may be a problem.

Versol treatments range from 100 to 200 gallons per foot of formation, with a
recommended radial penetration of 4.0 to 6.0 feet from the well-bore. For best results
these solvents should be allowed to soak for between four and six hours.

Page 23