LA RD&E Center

Asset Integrity Division

H2S Scavenger and

Corrosion Overview

Rafaela Passos

NOV 2015
Mission Statement
 Provide safe and professional work environment
 Nalco Champion follows a total system approach
 Meet and exceed operational expectations
 Design best-in-class chemical programs

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Agenda
 Our purpose is to present an Overview of LA R&D Center
focused on Asset Integrity Division: H2S Scavengers and
Corrosion
 Outline
 LA R&D Center: People and Capabilities
 Corrosion Overview
 H2S Scavenging Overview

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LA R&D Center: People

David Horsup André Krell

Jeffery Caleb Clark

Asset Integrity
 Rafaela Passos
 Simael Rodrigues
 Patrícia Severino
 Naylil Capreti
 Barbara Melanda

 Fernanda Lima

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LA R&D Center: Capabilities
Corrosion
 Nationalization of new technologies and new formulations
to attend LA requirements;
 Physical properties determination:
 Viscosity;  Boiling and flash point;
 Density;  Vapor pressure;
 Solubility;
 Secondary properties qualification:
 Emulsion tendency tests;
 Compatibility with packer fluid;
 Foam tendency tests;  Thermal stability;
 Gunk test;  Brine compatibility;

 Qualification for chemical injection:

 Surflo Plus® Certification;
 Injection through gas-lift system.

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LA R&D Center: Capabilities
Corrosion
 Qualification for chemical injection:
 SurFlo Plus™ (SFP) Product Suitability Standard;

 Corrosion Modeling:
 Nalco Champion’s Pitting Corrosion Model
- Phase I –Qualitative estimate of corrosion rates; 
- Phase II - Model will report an expected range of
corrosion rates.

 Nalco Champion’s Treat Rate Model.

- Batch Treatment;
- Film Intregrity;
- Film Maintenance.

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LA R&D Center: Capabilities
Corrosion
 Nalco Champion’s Pitting Corrosion Model
– Corrosivity Model that considers: Phase
Behavior, Fluid Dynamics, pH Changes
and Pitting Factor;
 General and pitting rates addressed
- Pitting Corrosion = Pitting Factor x General corrosion
rate. Pitting Factor ranges aprox. from 20 to 100;

 Non-ideality issues addressed

 Operational parameter sensitive
 Flow regimes/patterns sensitive
 Corrosion thermodynamics/kinetics addressed
 High correlation to field failure;

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 Oil Field

Injection Well Production Well

Oil
water bank

8 8
 Production Well

P2, T2, [CO2]2

Oil
water
bank

P1, T1, [CO2]1

9 9
 Impact of Water Chemistry Changes
3E+07
Henry's Solubility Cons
-
tant for CO2 in H2O

2E+07

1E+07

1E+05
0 50 100 150 200 250 300 350

Temperature, oF 10 10
Impact of Water Chemistry Changes
10
Corrosion Rate, mm/yr

0.1

0.01
0 50 100 150 200
Bicarbonate Concentration, mg/L
11 11
 Example: Wells of CDE Trunkline

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Corrosion Inhibitor Treat Rate Model
• Dosage for batch film formation
• Dosage for Film Integrity
• Dosage for Film Maintenance
CI adsorbed onto solid particles

CI Film Maintenance by continuous

injection – lower dosage concentration

CI film formation via batch

Fulfillment of CI protective film via

continuous injection of CI during Film
Integrity phase
Metal 13 13
 Input Data
Well conditions simulation
Gas Specific Gravity (Air = 1) 0,62
CI dosage recommendation Mole Fraction N2 0,0001
Pipeline Length, miles 20,03 Mole Fraction CO2 0,04
Pipeline ID, inches 6,42 Mole Fraction H2S 2E-07
Corrosion Inhibitor Activity, % 25 Oil API Gravity 38
Targeted Film Thickness, mils 3 Water TDS, mg/L 145051
Volume of Oil, bbls/d 4.200 (Cl), mg/L 0
Volume of Water, bbls/d 100    
Gas Volume, MMscfd 0,01 Inlet Temperature, oF 125
Corrosion Inhibitor S.G. (Water = 1) 0,975 Inlet Pressure, psi 1043
INITIAL FILMING   Outlet Temperature, oF 80
Pig Speed, ft/sec 4 Outlet Pressure, psi 850
Inhibitor Coverage Initial Filming - Batch, % 100 Angle, degrees 3
Corrosion Inhibitor Loss, % 0 Flow - V =1, H =2 2
FILM INTEGRITY   Select Pit Geometric Shape - Conical [C] or  
ID Inhibitor Coverage Film Integrity, % 30 Hemispherical [H] H
Corrosion Inhibitor Loss, % 0    
FILM MAINTENANCE   Solid/Sand Particle Major Diameter "a", microns 125
ID Inhibitor Coverage Film Maintenance, % 15 Solid/Sand Particle Minor Diameter "b", microns 80
Fraction Film Replenishment 0,06 Solid/Sand Particle Minor Diameter "c", microns 80
Corrosion Inhibitor Loss, % 0 Solid/Sand Concentration, lbs/1000 bbl 35
       
Inhibitor Adsorption Driver Concentration, ppm 10 Current Batch Inhibitor Volume, gals 2.500
    Current Continuous Inhibitor Injection Rate, gals/d 141,00
   
Pit Depth, in 0,0030
Percent of Pipe Surface Pitted 15 14
CDE Trunkline
CI Dosages

Multiple
injections

15 15
 LA R&D Center: Capabilities
Corrosion
 Performance Evaluation:
 Low Pressure Tests
- Bubble Cell Test
 Electrochemical report or/and weight loss measurement;
 Check the partition of corrosion inhibitor between two
phases;
 Evaluate the corrosion protection in dead legs;
 Water soluble corrosion inhibitors;

- RCE – Rotating Cylinder Electrode Test

 Electrochemical report ;
 Corrosion protection under hydrodynamic conditions –
Re (similar Reynolds number of the field);
 Film persistency test;
 Water soluble and oil soluble corrosion inhibitors;

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 LA R&D Center: Capabilities
Corrosion
 Performance Evaluation:
 High Pressure Tests
- RCA – Rotating Cage Autoclave Test
 Weight loss measurement;
 Micrographs of the coupon surface – pit depth and
statistic evaluation of pit distribuition ;
 Evaluate corrosion under hydrodynamic conditions – high
Reynolds number;
 Water soluble and oil soluble corrosion inhibitors;
 Prange: 0 – 350 bar and Trange : 25 to 250 ºC)

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LA R&D Center: Capabilities
H2S Scavengers
 Synthesis of H2S Scavenger Molecules and
characterization;
 Physical properties determination:
 Boiling and flash point;
 Viscosity;
 Vapor pressure;
 Density;
 Solubility;

 Secondary properties qualification:

 Emulsion tendency tests;  Compatibility with packer fluid;
 Foam tendency tests;  Thermal stability;
 Gunk test;  Brine compatibility;

 Qualification for chemical injection:

 Surflo Plus® Certification;
 Injection through gas-lift system.

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 LA R&D Center: Capabilities
H2S Scavengers
 Performance Evaluation:
 Dynamic H2S Scavenger Analyser, DHSA
- Product qualification for field recommendation;
- Scavenging capacity determination under a kinetic
perspective;
- Testing in multiphase fluid and at preferred temperature and
pressure (Prange: 10 -150 psi and Trange : 25 to 200 ºC);
Scrubber GT-157

 Rapid screening Techniques

- H2S Scavenger Development – new molecules and 
To

formulas;
N2

- Total scavenging capacity determination;

- Testing is performed,preferentially, in single phase fluid and Sparger 1 Sparger 2 Sparger 3

under atmospheric pressure and temperature;

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Dynamic H2S Scavenger Analyser (DHSA) – Example 1

Monitoramento do Teor de H2S na fase Gasosa após injeção de 1000 ppm v

de sequestrantes de H2S de diferentes matérias ativas.
Fonte: Tese de Mestrado – Avaliação de Desempenho de Sequestrantes de H 2S em Petróleo – André L. C. Bonfim

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Dynamic H2S Scavenger Analyser (DHSA) – Example 2

Test - 10 bar, 70C and BSW 80%

2000
1800
1600
1400
1200
H2S (ppm)

1000
800
600
400
200
0
0:00 1:12 2:24 3:36 4:48 6:00 7:12

Time (h)

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Rapid Screening Tecniques – Gas Breakthrough
Example 3

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Research and Evaluation Capabilities
 Sour facility located in Fresno, TX
 Testing procedures
 Dynamic testing
 Partitioning behavior
 Simulated contact towers
 Vapor phase reductions
 Liquid phase reductions

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Research & Evaluation Capabilities
Partitioning Behavior

 Chemical placed in production fluids

 Mixtures are placed under dynamic state
 Pressures and Temperatures can be applied
 Samples analyzed through Gas Chromatography
 Mass Balance performed of chemical partition

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 H2S in Multi-phase Systems
Vapor
The removal from a multi-phase system is more 2500 ppm
complex – Depends on the Partitioning of H2S
between the oil, water and gas;
• Partitioning of H2S is a thermodynamic process that is a Oil
function of :
25 ppm
• Temperature
• Pressure,
• fluid composition,
• water pH and Water
• ionic strength;
5 ppm
• Changes in gas-oil ratio might mask or accentuate
changes in gas concentration levels;

• When pH > 6 for high water cut systems - high H2S

Ionization in water and will not partition into oil and
gas”

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H2S Scavengers

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 H2S Scavenging Overview
 The H2S removal may involve:
 Regenerable Systems (Re-circulated);
 Oxidative processes;
 Non-regenerable scavengers;

Oil soluble H2S Try to have a

Scavengers partitioning behavior
that of H2S in the
Water soluble H2S system under
Scavengers treatment;

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 28

How do scavengers work?

 All liquid scavengers work through a two step
process:
 Step 1: H2S dissolves into the scavenger solution (mass
transfer);
 Step 2: The dissolved H2S reacts with the scavenger.

 Mass transfer is the rate limiting step in the

reaction
 Reactions with H2S are stoichiometric:
 For Hexahydrotriazines the ratio is 1:2 (Scavenger:H2S);
 Problems if ratio of 1:4 ( Scavenger:H2S) is used!
R
R R
S N
N N
2 H2S 2 NH2R Reacts with CO2
S
N

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Chemistry of the scavenging process:

OH

HO
N
N

OH

• 1,3,5-Tris(2-hydroxyethyl)-hexahydro-s-triazine is the most common

triazine;

• After 70% spent – two phases occur followed by solids. • Crystalline

then amorphous solids are deposited
• Disposal of spent fluid containing solids problematic;
• Amorphous solids very hard to inhibit, avoidance is the best
policy.

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Solid Deposition from Spent Triazine*
 Lab Sample – Heavily  Field Sample
Spent Triazine

* 1,3,5-Tris(2-hydroxyethyl)-hexahydro-s-triazine

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 Theoretical Capacity
 Based on Stoichiometrics
 Mole Reaction Ratio with H2S
 Actual Capacity
 Based on Lab Performance Data
 Based on System Performance Data
Capacities are further defined as
Volume of Chemical required to
remove weight of H2S:
• Liters of Chemical / Kg
Hydrogen Sulfide
• Gallons of Chemical / Lb
Hydrogen Sulfide

 Extent of Reaction
 Comparison of Theoretical Capacity vs. Actual Capacity
 Provides direction for efficiency and the amount of reaction product

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Hydrogen Sulfide Scavengers
 Amine-Based Chemistries
 Triazines
- Monoethanol Amine (MEA)
- Monomethyl Amine (MMA)
 Non-amine Based Chemistries
 Glyoxal
 Proprietary Chemistries
 Oil Soluble Chemistries

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H2S Scavengers – Triazines
Amine based chemistry
 Most commonly used chemistry for H2S removal in multi-
phase systems OH

 Water soluble amine based chemistry

 Kinetically very fast reaction rate N

 pH >10 HO
N
N
 Thermally stable up to 257 F
o

OH
 Formulations can contain various solvent packages

33
H2S Scavengers – Triazines
Amine based chemistry

Materials Compatibility
 Less Than 10%
Change = A
 10 to 20% Change = B
 Greater than 20% = C

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H2S Scavengers – Triazines
Amine based chemistry
 Corrosion of Metals

35
H2S Scavengers
Glyoxal
 Glyoxal can be efficiently used at acidic pH
 Stable and effective across all pH
 Will not contribute to CaCO3 scale

 Good thermal stability

 Thermally stable up to 302oF

 Potentially corrosive
 Must consider flow regime/dead legs in system
 Concentration in water HO OH
O O

O O
HO OH

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H2S Scavengers
Non-amine based Proprietary Chemistry
 Non-amine based chemical formulations
 Non-scaling chemistry
 Neutral pH
 Higher Capacity than Triazines
 H2S removed per gallon
 Kinetically slower than Triazines
 Longer retention times

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H2S Scavengers
Oil Soluble Scavengers
 Aldehyde Condensates
 Liquid product
 pH: 11.9
 Density: 0.82g/mL
 Viscosity: 5-15cPs @75ºF
 Metal Carboxylates
 Liquid product
 Flash Point: 172ºF
 Density: 1.0g/mL
 Viscosity: 13.3cPs @100ºF
 Primarily for downstream application

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Technical Applications Overview

Reference Equation
 Scavenger Kinetics + System Mass Transfer = System
Reaction Rate

 Mass transfer is the limiting step

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Technical Applications Overview
 Direct-Continuous Injection
 Flowlines
- Multi-phase
- Single-phase
 Gas lift
 Contact Towers
 Traditional
 Flooded

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Technical Application
Direct Injection
 Most common application found in upstream productions
 Requires minimum CAPEX investment by operator
 Can be installed in multiple locations
 Less efficient then contactors
 Typical 10-40%
 Efficiency is based on
 Flow velocity (annular vs. stratified)
 Contact time
 Liquid Composition (Partitioning)

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Chemical Applications
Efficiency Overview

Theoretical Injection Gas H2S

Location Product H2S Inlet H2S Outlet System Efficiency
Capacity Rate Production Removed

Name Name Gallon/Lb H2S Gallon/Day ppmv ppmv MMSCFD Lbs/Day %

Direct Injection Formula A 1.0980 297.94 30.00 0.00 10.00 27.13 10.00
Enhanced Direct Injection Formula A 1.0980 74.48 30.00 0.00 10.00 27.13 40.00
Tradtional Contact Tower Formula A 1.0980 42.56 30.00 0.00 10.00 27.13 70.00
Submersible Contact Tower Formula A 1.0980 33.10 30.00 0.00 10.00 27.13 90.00

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Application Criteria & Strategy
 Design parameters to consider for chemical
recommendation
 Gas Flow Rate
 Water flow rate
 Hydrocarbon flow rate
 Pressure
 Temperature
 Pipeline ID
 Pipeline Distance
 Hydrogen Sulfide Concentration
 Downstream Processes
 Desired outcome

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Application Criteria & Strategy
 Mass balance approach for chemical management:
 Gas flow rates
 H2S removed
 Chemical injection rates
 Optimize chemical program based on:
 Mass balance
 Calculated system efficiencies

44
Qualification Process
 No way to exactly simulate system
 Used to determine dosage ratio
 ppm scavenger to remove ppm H2S
 3 laboratory techniques to determine “dosage ratio”
 Bubble Tower Capacity
 Dynamic Liquid Phase Reduction
 Vapor Phase Reduction (ASTM-D5705)
 Subsea Qualification
 Surflo Plus® - Same process as all other subsea chemicals
 Mitigate scale risk

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Application Criteria & Strategy
Risk Assessment
 H2S Scavengers can promote scale due to high pH
 Dynamic Scale Loop testing allows for the study of scale with
production brines
 H2S Scavengers can generate solid reaction product
 Observe the Dynamics of the System
- Static Areas of Liquid Load Up can allow reaction product to aggregate

 Understanding the Extent of Reaction

- Each chemistry can generate solids due to high extents of reaction
- Extent of reaction limitation for solids generation is both system and chemical
dependent

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Future Technologies & Direction

 Development of Non-Amine based chemistries for H2S

Scavengers
 Advances of new Non-Scaling H2S Scavengers
 Research of HT/HP H2S Scavengers
 Research of Oil Soluble H2S Scavengers
 Investigation of Multifunctional H2S Scavengers for
downhole application
 Development of an Atomizer Technologies specific to H2S
Scavenging

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Summary

 Nalco Champion has an extensive H2S scavenger product

line
 Products are selected based on application type
 The capacity of a scavenger to remove H2S is based on
stoichiometry
 Dosage rates are based on application type, amount of H2S
and gas flow rate
 Application is the key to a successful scavenger program

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