SCAVENGERS

H2S AND OXYGEN SCAVENGERS

BRUCE ADAMS JR
REGIONAL TECHNICAL MANAGER
12/6/2017

1
9th Annual NACE INTERNATIONAL,
New Orleans Section
Oilfield Operator’s Chemical School

Scavengers
Presented by
Bruce Adams Jr, Technical Services, Nalco Champion
225-802-6717
Bruce.Adams@Ecolab.com
 Scavengers Outline
H2S Scavengers

H2S Solubility and Testing

H2S Scavengers and Applications

Direct Injection Flow Line Applications

Contact Tower Applications

H2S Survey and Monitoring

Oxygen Scavengers

Oxygen Solubility and Sources

Oxygen Scavengers and Application

H2S Scavengers
Sources of Hydrogen Sulfide

Natural gas (varies from a few ppm to 100%)

Gas associated with crude oil

Reservoir souring due to water injection or drilling programs
(sulphate reducing bacteria)

Thermal cracking of organic sulfur compounds (asphalt
plants)

Hydro-treating to reduce sulfur content of a refinery stream
Types of Sulfur Compounds

Hydrogen Sulfide
Sulfides

H2S
R-S-R

Carbonyl Sulfide
Disulfides

COS
R-S-S-R

Carbon Disulfide
Polysulfides

CS2
R-Sx-R

Mercaptans
Thiophenes

R-S-H
C4H8S

R denotes any organic group

Why Scavenge H2S?

4 ppmv sales gas pipeline specification widely adopted

10 ppmv maximum headspace limit for crude imported into the US

Improved safety by reducing toxic gas risk

Crude oil and water storage tank emissions

Produced gas

Refinery streams

Reduction in corrosion risk associated with sour production

Generalized pitting corrosion

Catastrophic hydrogen embrittlement failure

Meet sour service specifications for metallurgy
H2S Properties

Specific Gravity = 1.189 @ 25 C (Air =1)

Molecular Weight = 34.08

Vapor Pressure = 17.9 Bar @ 20 C

Freeze Point = -85.5 C

Boiling Point = -60.31 C

Ignition Temperature = 260 C

Lower Explosive Limit = 4.3 %

Solubility in Water

6725 ppm @ 0 C

2862 ppm @ 40 C

pH of Saturated Water = 3

Soluble in Polar Solvents Such as Glycols = 60,000 mg/L @ 20C

Less Soluble in Nonpolar Solvents Such as Hexane 13,000 mg/L @ 20 C
H2S Properties (cont.)

Odor of rotten eggs

Threshold Odor Limit

0.13 ppm

Maximum Exposure Limits

8 Hour = 10 ppm

15 Minute = 15 ppm

Ceiling = 20 ppm

Hazardous Limits

Immediately dangerous to life = 300 ppm

Lethal concentration = 700 ppm

Corrosive in aqueous solutions

Localized attack through cathodic nature of iron sulphide by-product

Embrittlement through atomic hydrogen diffusion
 Partitioning (Solubility) of H2S
(H2S Distribution in Produced Fluids)

H2S is Soluble in oil & water

Present in the liquid and vapor space according to Henry’s
Law

PH2S = k [CH2S]
 Factors Affecting Partitioning

Headspace concentration influenced by:

Liquid composition (i.e., water, oil)

Temperature

Viscosity of liquid

Headspace volume

Agitation

Concentration in Liquid
 H2S Concentration: Relative Amounts

Very difficult to predict in three phase
systems

Use GPSA tables to determine
gas/condensate partitioning (k factors)

Mole fraction in oil/mole fraction in water

Vapor

18 to 19.5 (Shell Research) 2500 ppm

1 ppm in oil can yield 100 ppm in

headspace vapor Oil
25 ppm

Distribution can be predicted using
computer models
Water

Most accurate way to determine distribution
5 ppm
is physical measurement
 Hydrogen Sulfide: Testing

Pipelines

Separators

Storage Tank Hatch & Vents

Lab/Field Testing Gas Stain Tube Measurement

Vapor Phase Test
Stain Tube

Liquid Phase Test
Stain Tube Pump
Gas Accumulator

Pipeline
 Vapor Phase Test: ASTM D-5705

Quick, Easy Field Test

Can Measure H2S
Drager Stain Tube Pump
to 80,000 PPM

At least 100 ml of
headspace Aluminum foil
Is required to avoid
stripping ..
H2S from the liquid
Drager Stain Tube
phase
Sample can 1/2 full

Container Oil Sample

 Liquid Phase Test: Sparge Method

Drager Tube Reading X 1.42

ppm H2S =
Sample Weight

Nitrogen @ 15psig Tygon tubing

and 100 ml./min.

250 ml. fritted gas ..

H2S Drager tube
washing bottle
H2S
H2S
50 ml. toluene
H2S H2S
5 ml. oil sample

H2S
Water bath
H2S @ 140oF
H2S Removal Techniques

Greater than 20 Tones/Day

Regenerable Systems (Re-circulated)

Amine treating followed by sulfur recovery or acid gas injection

Highest Capital Cost

150 kg to 20 Tones/Day

Oxidative Processes
- Catalytic Oxidation
- Zinc Oxide
- Nitrite Solution

Up to 300 kg/Day

Non-Regenerable Scavengers

Low Capital Cost

All process are able to meet the 4 ppmv pipeline specification
H2S Scavengers

Inexpensive equipment requirements

Contact towers

Direct injection

Ease of operation

Do not require dedicate operators

Flexible

Can be applied almost anywhere

Best choice for short term needs

NALCO Champion H2S Scavengers

Extensive product line

Water Soluble based products

Nitrite, Zinc

Oil soluble

Products are selected based on application type
 H2S Scavengers

Oil Soluble Scavengers

for high temperature
applications

reaction products remain
with treated stream

non-reversible

Dry oil pipelines

Water sensitive applications

Water Soluble Scavengers

reaction products removed
with water

“knock-out” pot required to
remove with water phase

fast reaction

compatible with a variety of
products

non-reversible
Scavenging Process

H2S scavengers work by a two step process.

Step 1

H2S dissolves into the scavenger solution (mass transfer)

Step 2

H2S reacts with the scavenger molecule

Reaction rate above 45 F is extremely fast

Mass transfer is the limiting step

Efficiency is the % of scavenger consumed

 Scavenger Selection

H2S Concentration

Treating Gas, Oil, or Water Phase

Water Content of Gas

System Mass Transfer and Contact Time

Scaling Potential of System

Temperature
Application Options

Contactors (including bubble towers)

Direct injection into flowlines

typically, atomizer is needed

Downhole treatments

Continuous down annulus or cap string

With lift gas

Hydrocarbon Treating
Gas Treating with Water Soluble H2S Scavengers

Application Techniques

Flow line injection
- Additive is injected directly into the line and dispersed through
gas flow, pulsation dampeners, atomizers, etc
- Little capital expense, but less efficient

Contact (bubble) tower

- Greater contact is obtained by percolating the gas stream
upward through a scrubber tower containing the scavenger
- More capital expense and maintenance, but more efficient
 Water Soluble H2S Scavengers

Generate Water-Soluble Products Under Normal Operating

Conditions
Over Spent
H2S
Water Soluble H2S Soluble H2S Soluble H2S Insoluble
Scavenger Liquid Liquid Solid
Very Fast Fast Very Slow

Flow line applications typically do not see solid reaction products

Look for dead zones where the scavenger can settle and form over
spent product
Direct Injection Applications
 Factors Affecting Scavenging

Volume of H2S Scavenger Required depends on:

Stoichiometry → Amount of H2S to be removed

Statistics → Initial and final concentration of H2S

System Conditions → Production flow rates, T, and P

System Constraints → Contact time (Pipe diameter and distance)

Scavenger application design → Injection location & efficiency
Stoichiometry - Amount H2S Removed

Stoichioic Reaction

2 H2S + 1 Scavenger → Reaction Product

More Mass of H2S to Remove = More Scavenger Required

Mass of H2S Depends on Volume of Gas and Concentration

of H2S

Vol. of gas = 1 MMscfd

H2S to be Removed

H2Sinitial = 100 ppm = (MMscfd) x (∆ppm) x (lb/ft3)

H2Sfinal = 4 ppm = (1 MMscfd) x (100-4 ppm) x (0.0909 lb/ft3)

Density of H2S = 0.0909 lb/ft3 = 8.7 lb H2S / day

 Statistics - Concentration of H2S
Initial and Final (Target)

Easy
Increasing Scavenger Required

H2S initial = 30 PPM Optimum utilization of scavenger

H2S sales = 15 PPM possible

• Achievable
Optimum utilization of scavenger
H2S initial = 30 PPM probable
H2S sales = 5 PPM

Difficult
H2S initial = 30 PPM Optimum utilization of
H2S sales = 1 PPM scavenger unlikely
System Conditions and Constraints –
Effects of Flow
The contact behavior and transport of the scavenger with the H2S is
controlled by flow.

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 System Conditions and Constraints
In-Line Injection

Temperature

Greater than 15oC (60oF)

Less than 80oC (140oF)

Contact Time

Variable

10 seconds to 10 minutes

Water Content

Gas must be saturated with water at operating pressure
and temperature
Scavenger Application Design –
Injection Location

Into straight segments of the pipe

Maximize transport of injected liquid chemical as droplets before falling to the pipe
walls

After the primary separators

Presence of free liquids reduces mass transfer efficiency as the injected scavenger
partitions into the liquid phase

H2S soluble in water and condensate can exert additional scavenger demand

Before the final separator

To remove water soluble reaction products from the gas

Minimize impact on downstream units such as glycol dehydration and or amine units
- A coalescer filter type separator should be used

At multiple injection points

To increase scavenger efficiency

When initial concentration is greater than 30 PPM

When target concentration is less than 4 PPM
 Scavenger application design –
Injection Efficiency

Improve Flow Line Injection Efficiency

High pressure injection pump
Pulsation Damper
Atomizer
o Pre-filter
o Pressure Regulator to detect back pressure and
plugging
 Impact of Scavenger on
Glycol Systems

Ensure effective separation of produced liquids from the gas at

the inlet separator upstream of the glycol tower

Carryover of unspent scavenger can raise the glycol pH

Increase in pH increases foaming & glycol loss

Breakdown of spent scavenger can generate H2S in the reboiler

Presence of produced brine can lead to fouling of tower internals,
reboilers and heat exchangers
Scavenger Efficiency
Scavenger Efficiency

Scavenger performance is a combination of TWO factors:

Contact between H2S in the gas phase and the liquid

scavenger. Function of:
- gas flow,
- chemical injection method,
- mass transfer.

Reaction between the H2S and the scavenger.
- Function of chemistry of the product
- Not impacted by how the chemical is injected
- Reaction rate strongly depends on temperature
H2S Removal Rate

Rate of H2S removal from gas phase = KL,H2S x a x ∆C

KL,H2S = Mass transfer coefficient in the Liquid Phase, (LT-1)

a = Interfacial area (L2/L3)

∆C = Concentration gradient

Mass Transfer Coefficient KL,H2S

Size of Droplets  a

Driving Potential  ∆C
Contact Between H2S and Scavenger

Low H2S Concentration

(Low Driving Potential)
High H2S Concentration
(High Driving Potential)

Scavenger
Droplets
H2S
Molecules
Interfacial Behavior for Liquid Scavenger –
H2S Gas Phase Reaction

Gas Phase Liquid Phase

CH2S Liquid Film

Gas Film Diffusion Rxn Zone CScavenger

Bulk

Bulk
Resistance to H2S Removal Lies in the
Liquid Film at the Gas- Liquid Interface

Liquid
Phase H2S in
Gas phase
Lower Resistance to H2S Removal
Reaction (Lower Gas-Liquid Interface)
Occurs here Gas Phase

Liquid Phase
Higher Resistance to H2S Removal
(Higher Gas-Liquid Interface)
Gas Phase

Interface
Scavenging Application Design – Improving
Scavenging Efficiency

For gas treatments or using insoluble scavengers maximize

contact

Atomizers for gas treating

Nalguard quill for liquid treatments

Maximize contact time

Properly sized equipment for contactors

For soluble liquid treatments

Nalguard quill for improved mixing

Maximize contact time
Atomization Can Increase Ratio of Surface
Area to Volume by >100 Fold

Liquid Volume = 0.13 ml Liquid Volume = 0.13ml

Droplet Diameter = 0.5 cm Droplet Diameter = 50µµm
No. of Droplets = 2 No. of Droplets = 2 x 106

12 cm2/cm3 1200 cm2/cm3

 Application Aids

Scavenger Filter

Pump Pulsation
Damper

Spray Nozzle
Gas Flow
 Application Guidelines

Atomizers and spray nozzles

should be:

Properly sized
- Increases dispersion
- Avoid contamination of injection
system as small solids plug the
openings in spray nozzles

Install a filter at the outlet of
the storage tank

Install a pressure relief valve
downstream of the pump
PULSATION DAMPENER
Reduced Pulsation to Improve Liquid
Delivery
Without Pulsation Dampener

With Pulsation Dampener

Contact Tower Applications
CONTACTORS

Contactors include the following

Bubble towers
- Conventional
- Flooded

Trayed towers
- Old dehydrators
- Old absorbers

Packed towers
- Minimize footprint
- Decrease tower diameter

Circulating towers
- Both trayed and packed
 Typical Contact Tower

Safety Relief Valve

Tower Internals
Gas Outlet
• Gas distributor:
Vane Demister
•Determines the
bubble pattern
Downcomer
• Mist extractor
Sparger
Manway •Removes Liquid

Gas Inlet
droplets from Gas

Spent Scavenger
Bubble Tower Design Tips

Always add some water. The standard is 20 %. For
concentrated products add 50 %.

Reduces solids formation

Reduces impact of solvent stripping

Do not exceed 80 % efficiency. Above this solid deposition

becomes a concern.

Do not exceed 6 months run time. Add more water to reduce run
time.

Ideally measure differential pressure across the tower.

For EC9102A (nitrite)

Add antifoam (foaming system)

Add surfactant (keeps elemental sulfur dispersed)

Include a day pot to slug water through sparger if it plugs
Flooded Bubble Towers

Use two vessels in series.

First vessel contactor

Second vessel separator

Contactor allowed to fill and spill over to the separator

Inject H2S scavenger into gas line feeding contactor

Scavenger injection rate based on predicted demand (80 %

efficiency).

Advantage – Continuous process
Other Contactors

Any vessel used for gas processing can be used as a

contactor

Glycol dehydrators

Lean oil absorbers

Amine contactors

Contactors can process the amount of gas they were

designed for.

Can be used for

Batch processing (scrubber)

Continuous (gas processing)

Gas production rate
Monitoring Gas Applications

Amount of H2S and scavenger demand

Contact time

Pressure in flow line

Contact time

H2S partial pressure

Temperature

Higher temperature = faster reaction

Thermal stability of additive at temperatures > 200 °F

H2S content of feed gas

Scavenger demand

H2S content of gas after treatment

Scavenger performance

Content of sulfur species other than H2S (Carbonyl sulfide, mercaptans)

Can exert demand on scavenger

Rate of scavenger injection

Scavenging efficiency
 Data Analysis

Scavenger Performance

Calculate the net H2S loading in the system
- Gas
- Water
- Condensate

Estimate the Total Pounds of H2S removed based on Inlet and

treated gas

Calculate the apparent scavenger efficiency

(gal of scavenger) / (PPM of H2S Removed x MMscf)
H2S Solutions
Triazine Chemistry
Together We Are Stronger
Oxygen Scavengers
 Oxygen Scavengers
Effects of Dissolved O2

Why is Oxygen Content important?

Dramatically increase corrosion

Acts in 2 ways:

As a cathodic depolarizer

As an oxidizer

Greatest potential of acid gasses for corrosion; ppb levels

result in corrosion

In combination with H2S / CO2 dramatic increase in corrosion

Solubility of Oxygen in Oilfield Brine
 Typical Locations for Oxygen
Corrosion

Production wells

Top 25 – 50 feet of well

Around the pump

Upper section of fluid level over the pump

Tanks

Vented to atmosphere

Leaking VRU (Vapor Recovery Units)

Gas flotation cells

Opened for routine maintenance

Leaking Pumps

Oxygen can migrate in while fluid is leaking out
 Steps to Control Oxygen Corrosion

Eliminate the source of oxygen

Mechanically fix the leak
- Leaking pump seals
- Install gas blanking on vented tanks

Oxygen Scavenger

Typically used on incoming fluid with a constant concentration of
oxygen. (Example sea water floods)

Corrosion inhibitor

Standard oil field inhibitor 40 ppb oxygen

Pyridines 200 ppb oxygen

Inhibitors formulated for oxygen 2000 ppb oxygen
Oxygen Scavengers

2(R)HSO3 + O2 2 SO4 + R + H+
Factors affecting rate of scavenging

pH

Temperature

Fresh Water/TDS

Catalyst

Calcium

Other Chemicals

Overtreat
Application Requirements

• Injection should be into a fast flowing

stream that will provide rapid mixing. An
injection quill may be used to facilitate
mixing.

Maximum residence time

Higher temperatures

Excess scavenger
Surveillance Plan

Bisulfite residual should be measured at a sample point

close to the final oxygen probe location mentioned
above.(target 1-2ppm)

Solids monitoring points should be before and after any
filter medium (this not only tracks water quality but also
filter efficiency – along with pressure measurement that
may be used as an aid to setting back wash frequency).
 Data Collection for KPI’s

Oxygen Oxygen Continuous Less than

Reduction Probes 5ppb

Solids removal Filtration Weekly Less than

sample 1micron

Bisulfite sample Daily 1 to 2ppm.

residual Contingent on
oxygen
remaining in
spec.
 66

Chemical Equation

Overall Chemical Equation

2NaHSO3+O2  2NaHSO4

Net Ionic Chemical Equation

2HSO31- + O2  2H+ + 2SO4 2-

HSO31- likes to hold onto its proton ( HSO31- pKa = 7.17)

Once the sulfur atom grabs hold of the additional oxygen
(AKA scavenges it), the sulfur, now with an additional
oxygen atom, will want to kick off its proton
( HSO41- pKa = 1.99)

Hence, the solution becomes more acidic.
THANK YOU