A Two-Phase Thermal Oxidation Process For The Disposal Of Odorant Materials

Damian M. Rodriguez, BSc.

President
Material Resource Recovery Inc.
Cornwall, Ontario. Canada

Abstract
Liability, as it pertains to the disposal of odorant wastes, has only in recent years become an
issue for much of the gas industry. This paper is intended to provide information on an
alternative treatment and handling process developed to satisfy the strict requirements of
the Ontario Gas Industry.
Capable of treating wastes such as soils, drums, debris, rags and equipment contaminated
with odorant, this system has the added ability to treat odorant tanks up to a length of 26
feet.
Thermal oxidation, combined with a two-phase treatment process, ensures the safe and
efficient destruction of odorant wastes. Phase I involves evaporation of odorant at low
temperature (< 150 C) and subsequent incineration of vapors in the primary and
afterburner units. Phase II involves the incremental elevation of temperature to 800 C for
the complete destruction of all remaining residues. In both Phase I and II, all gases are
treated through a quenching tower and wet scrubber for SOx removal. Measurement of SO2
concentrations entering and exiting the wet scrubber are used to measure the continuous
efficiency of the scrubber, as well as, determine the completion of Phase I and the start of
Phase II. A two phase treatment process ensures that the risk of explosions and uncontrolled
exothermic reactions are eliminated. An after-burner unit with a retention time of 2.7
seconds and a minimum operating temperature of 1300 C allows for the complete
destruction of all organics. An Anderson 2000 wet scrubber with a minimum operating
efficiency of 95% ensures effective removal of S02.

Introduction
It is a late Friday morning when a call comes in urgently requesting assistance for the
containment and removal of a container described as a type of tank containing mercaptan.
This device, thrown into a scrap metal recycling bin has been picked up and delivered to a
recycling facility located in a small suburb just east of a large metropolitan city. Upon
dumping this bin, an odor is immediately detected and quickly spreads involving five
square blocks of businesses. The odor, smelling similar to natural gas, causes the local fire
departments to close and evacuate all businesses and residences within a five block radius.
As it happens, many of the affected businesses are suppliers to a major auto manufacturer
and soon, their closure causes a loss of two production shifts. As the financial loss to all
involved becomes substantial, accusations as to whom was responsible immediately come

into play. Since the material involved smells much like mercaptan and is contained in a tank
like vessel, the scrap metal recycler immediately seeks to find the natural gas companies
responsible. Private investigators are hired, samples of paint coatings from the exterior of
the vessel are taken, as well as the contents of the vessel, both being sent for analysis to
assist in the determination of the user and owner.
An Ontario drum recycler obtains a permit for the treatment and recycling of mercaptan
tanks from the Ministry of Environment. A large number of odorant tanks are shipped to
this recycler who in the end, simply places them in storage and eventually abandons the
site. The result is confusion and debate over whom is ultimately responsible for the cleanup
and removal of these tanks. Is it the generator who shipped the material, or is it the Ministry
who approved the recycler? Meanwhile, public relations becomes an ever increasing
problem to both as constant odors are emitted from the site, located in the center of a small
community.
The selection of a treatment and disposal facility for mercaptan wastes is one which should
not be decided lightly. The consequences of a poor choice can lead to public relations
problems, costs related to leak calls and potential litigation. Up until just recently, this
problem was exacerbated by the fact that the number and choice of adequate and
experienced treatment facilities was limited if not non-existent.
This paper discusses the specific program initiated by Consumers Gas and Union Gas of
Ontario to provide a treatment program for mercaptan wastes ensuring their complete
destruction of such wastes, as well as elimination of all associated liabilities.

Project Background
With specific programs already in place for the replacement of outdated odorization
equipment, it was recognized by Consumers and Union Gas that the problem of disposal
was going to be an issue and a future source of potential liability.
In 1996, both Consumers and Union Gas approached Material Resource Recovery
("MRR") to review, select and install a treatment technology suitable for the complete
destruction of mercaptan wastes, while integrating specific operating principles that would
ensure long term environmental objectives.
In the preliminary stages of this cooperative effort, a significant portion of time was spent
establishing specifications and criteria from which selection of technology and facility
design would be based. These specifications are as follows:
1. The technology must not only be proven and not of an experimental nature, but must
have the ability to treat all potential forms of mercaptan contaminated waste. This would
include soils, piping, pumps, water, equipment and tanks of assorted shapes and sizes.
Specifically for odorant tanks, the technology must be capable of accommodating tanks up
to twenty-six feet in length as well as any attached piping configurations.

2. Since the composition of odorant used by each gas distributor can vary, the technology
must be 100% effective in the complete destruction of all mercaptans and other sulfur
bearing compounds that may be present. In addition, the technology must be able to treat
pyrophoric sediments that may have formed or dropped out and accumulated over time on
the tank bottoms.
3. The technology must support long term viability.
4. Ensure that the selected treatment process minimizes all environmental exposures. This
means that the specific treatment process does not generate other by-products that are
hazardous, that require further treatment or disposal and may pose further exposure to
liability. This also includes air emissions.
5. Recovery and recycling must be a major component of the treatment system
6. The implementation of a recognized environmental management system. Such a system
must have both internal and external auditing mechanisms.
7. Verification of treatment success (no detectable odor - < 1 ppb) as well as verification of
final destination of all treated components.
8. Facility design must incorporate controls for air handling in the event of internal air spill.
A zero tolerance for odor release to the environment and surrounding communities.
9. Clear guidelines and protocols for on site preparation and transport of all mercaptan
wastes. Zero tolerance for air spills.

Technology Selection
Over a period of six months, a number of treatment technologies were reviewed and
assessed based on the aforementioned specifications. All processes showed varying degrees
of effectiveness, however, many were not able to meet many of the specifications
demanded by Consumers and Union Gas.
Chemical Oxidation Processes
Chemical treatment of mercaptan wastes is widely used by the industry today, however,
their effectiveness on all forms of mercaptan wastes is reported to vary widely. The ability
to reduce odors noticeably is proven with treatment times that are quite fast. However, in
many cases, the materials after treatment, such as soils and debris must be considered and
disposed of as a hazardous material. In addition, the volume of oxidative chemical used
must also be disposed, and in some instances, a distinct smell of mercaptan remains
detectable, generating further disposal problems.
Biological Processes
Biological treatment of mercaptan wastes is very effective, but is dependent on specific
conditions including temperature, pH, mixing and time. To reduce mercaptan
concentrations below 2 ppb, the amount of treatment time can be quite substantial. In the

case of odorant tanks, rotation or agitation is required on a daily if not continuous basis.
This may present significant problems with large tanks or pieces of equipment that are not
easily moveable or require use of aeration systems that generate their own problems in
terms of odor loss through leaks. Biological treatments for mercaptans are very specific and
do not assist in the removal of pyrophoric or other sediment materials that may have
collected over time.
Thermal Oxidation
Thermal destruction of mercaptan wastes is 100% effective with its ability to treat not only
mercaptans and other sulfur bearing compounds, but also any pyrophoric and other
sediment materials. This makes it a preferred treatment choice. However, specific concerns
with respect to sulphur dioxide emissions resulting from incineration and safety must be
considered specifically when dealing with tanks, or large volumes of odorant.
After careful consideration, it was decided that the technology most suitable and capable of
meeting the specifications demanded by Consumers and Union Gas was that of Thermal
Oxidation.

Design Of The Thermal Treatment System

Upon selecting a reputable furnace manufacturer, MRR proceeded to design and engineer a
thermal process that would not only accommodate the largest of mercaptan tanks, but
provide the highest degree of safety. This was accomplished through the design of a twophase thermal oxidative process utilizing a car-bottom furnace, primary and after-burner
units, a quenching tower and an acid gas scrubber.
Process
In the case of large odorization tanks, the units are placed into a car-bottom furnace and
connected by a manifold to a separate primary furnace. With the primary and after-burner
units operating at 800 and 1300 degrees Celsius respectively, and after pressure tests of the
manifold and connections, the temperature in the car-bottom furnace is raised. This initial
phase involves the incremental raising of temperature to no greater than 150 degrees
Celsius. The result of this phase is the slow evaporation or boiling off of mercaptans which
are transferred through the manifold and directed to the primary furnace. Here the gases are
incinerated in an oxygen deficient atmosphere and then passed on to the after-burner for
complete and efficient combustion. The second phase of the process again involves the
incremental elevation of temperature from 150 C to 800 C. As the auto-ignition
temperature of most mercaptans is no greater than 400 C, this high temperature phase
guarantees the complete destruction of all mercaptan residues and other sediments. Like the
first phase, all gases are transferred through the manifold and directed to the primary
furnace and after-burner units for complete and efficient combustion. Total treatment times
range from three to five hours depending on percentage residue of mercaptan.
In both phases, all combustion gases exiting the after-burner unit are passed through a
quenching tower resulting in the cooling of gases to a temperature less than 500 C . These

gases are then directed to an acid gas scrubber and neutralizer effectively removing 95% of
all sulphur dioxide emissions.

Table 1
Emission Rates
Contaminant

Unit

Emission Rate for

Large
Mercaptan
Tank Processing

Carbon monoxide

g/sec

0.006

Nitrogen oxides

g/sec

0.12

Particulate matter

g/sec

Trace

Mercaptans

g/sec

0.00001*

Sulphur dioxide

g/sec

0.69

* based on the worst case scenario of a minimum 99.9999% destruction efficiency Source :
Envirometrex Corporation

Table 2
Maximum Ground Level Concentrations
Contaminant

Unit

Large
Mercaptan
Tank
Processing

Ontario Point of
Impingement
Standard

Carbon monoxide ug/m3

0.08

6000

Nitrogen oxides

16.2

500

Particulate matter ug/m3

Trace

100

Mercaptans

ug/m3

0.001

20
(total
mercaptans)

Sulphur dioxide

ug/m3

93.2

830

ug/m3

Source : Envirometrex Corporation

After all tanks or equipment have cooled, the units are cut into quarter sections. Verification
that no odor is present is carried out at this stage and only upon such verification are the
components then placed into various recycling containers.
Control Systems
In order to effectively determine the end point of Phase I and the start of Phase II of the
process, SO2 monitors were placed on the inlet and outlet stacks of the wet scrubber unit.

As the concentration of sulphur dioxide entering the scrubber decreases to background

levels , Phase II of the process is initiated. The SO2 monitor on the outlet stack of the
scrubber is used in conjunction with the SO2 monitor on the inlet stack to provide
continuous data on scrubber operating efficiency.
To ensure compliance with all emission standards, a Continuous Emission Monitoring
system (CEM) for temperature, carbon monoxide, oxygen and sulphur dioxide levels in the
flue gas was incorporated. These indicators of combustion efficiency are monitored during
all furnace operations with all data collected and stored on a PC for future reference and
reporting. A Relative Accuracy Testing Audit (RATA test) is performed every six months on
the CEM system by an independent analytical firm to confirm calibration and emissions.
Source Testing on stack emissions is conducted by an independent analytical firm every
twelve months to ensure compliance of emission rates. This testing involves the following
test contaminants:
Total Suspended Particulate Arsenic
Matter
Cadmium

Chromium

Lead

Sulphur Dioxide

Oxides of Nitrogen

Total Hydrocarbons

Total Mercaptans

Odor

Both toxicology and air dispersion modeling was conducted to ensure compliance with all
regulations, as well as provide to the public a level of confidence that such a facility would
have no impact on their environment or community. These reports are available to anyone
upon request.
As natural gas is used as the fuel for the furnace burners, a concentration of SO2 is always
present. This concentration is used as a baseline.
A Public Liaison Committee was also incorporated to enable community participation in
the development and expansion of any operations. This committee will also act as an
independent monitoring body to ensure compliance with all municipal, provincial and
federal environmental regulations. The formation of this committee also maintains a public
relations component necessary for any waste management operation.
Facility
Just as important as the design of the technology was that of the design and construction of
the building. With specific areas for reception, storage and treatment, and a containment
wall surrounding the entire perimeter of the facility, containment of all liquids within the
building is guaranteed. No floor drains are present in any of the reception, storage and
treatment areas of the facility. All handling and storage of mercaptan materials is conducted
within the facility, with no outdoor storage tolerated.

In the case of air spills, the design of the building allows the draft of the furnace system to
generate a sufficient negative pressure, drawing all air from the facility into the combustion
chambers.
Tracking and Reporting
A material tracking system, specifically designed for MRR provides fully integrated
inspection and maintenance control systems, as well as on line protocols and accountability.
As material moves through the plant, all verification and treatment steps are recorded, as
well as placement and final shipping of all recyclable components. Each client is provided
with a detailed report as to when their wastes were treated, verification of treatment success
and final destination of all recyclable components, including dates, times, container ID and
transporters. In addition, the client can receive a copy of the air emissions during the
treatment of his particular material. This provides the assurance and evidence to the client
that all liabilities attached to the waste is now eliminated.
Environmental Management System
To comply with the specifications established, MRR has incorporated ISO14001 as its
EMS. With both internal and external verification audits performed on a regular basis, this
system provides additional assurance that compliance with all environmental standards and
regulations are complied with.

Summary
By using a two-phase thermal oxidation process, the requirements of the Ontario
Gas Industry were not only met, but surpassed.
Proven technology was utilized, providing complete destruction of all mercaptan wastes
and other associated residues;
The development of a two-phase treatment process assures a high degree of safety and
efficiency;
Thermal oxidation provides the ability to treat other hazardous materials, making it
viable in the long term;
The process does not generate any other hazardous wastes that require additional offsite treatment;
All components are recycled and reused;
ISO 14001 implemented as an EMS;
Independent verifications of treatment success;
Detailed reporting and accountability;
Incorporation of air control systems meeting zero tolerance for odor emission;

A complete and detailed waste management program for mercaptan wastes has been
developed through the cooperative effort of Consumers Gas, Union Gas and Material
Resource Recovery Inc. This program provides a responsible and efficient solution to
mercaptan waste disposal, as well as ensuring compliance with the environmental goals of
these companies.