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ENDOTHERMIC GAS PRODUCTION OVERVIEW

Written by

Jason Jossart

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Introduction

This document is intended as an introduction to endothermic gas production with the purpose of
providing heat treatment personnel with a basic understanding of the gas generation process and
some important rules-of-thumb when trying to identify gas generation problems.

What is Endothermic Gas?

“Endothermic Gas” is a common atmosphere used in many heat-treatment furnaces for applications
that require a strong oxygen reducing atmosphere. The most common heat treatment applications
include gas carburizing and carbonitriding. It is important to understand that endothermic gas is not
actually one gas but a mixture of different gasses. To begin, let us examine what Endothermic Gas
is made of.

Endothermic Gas produced from natural gas (CH4) is primarily composed of:

Hydrogen Gas (H2).................................... 40%

Nitrogen Gas (N2)...................................... 40%
Carbon Monoxide Gas (CO) ............. 19.5 – 19.8%
Carbon Dioxide (CO2) ......................... 0.2 - 0.5%
Water Vapor (H2O) ................................ < 0.1%
Methane (CH4) ........................................ < 0.1%

Endothermic Gas produced from LPG or Propane (C3H8) is primarily composed of:

Hydrogen Gas (H2).................................... 31%

Nitrogen Gas (N2)...................................... 46%
Carbon Monoxide Gas (CO) ............. 22.5 - 22.8%
Carbon Dioxide (CO2) ......................... 0.2 - 0.5%
Water Vapor (H2O) ................................ < 0.1%
Propane (C3H8)........................................ < 0.1%

Endothermic Gas Production

The most common and economical method of producing this mixture of gasses is with the use of an
endothermic gas generator. Endothermic gas generators are comprised of an air-gas mixing system
that supplies a mixture of air and natural gas (or propane) through a heated retort that contains a
nickel coated ceramic catalyst. The retort and catalyst are heated to 1900’F where the natural gas
(or propane) does not burn but actually decomposes and reacts with oxygen in the air to create the
endothermic gas components noted above.

The final critical step in gas generation is the cooling of the gas from the reaction temperature of
1900’F to less than 300’F as quickly as possible to “freeze” the gas and prevent a reverse reaction
from occurring.

In addition, there is usually a closed loop control scheme in place that will sample the endothermic
gas water vapor or carbon dioxide content and make small mixture adjustments to create the desired
endothermic gas quality.

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Gas Reactions and Ratio Control

Inside the 1900’F retort within the endothermic gas generator there are a number of critical
reactions occurring. Once again, it is useful to recall that the mixture of air and gas being pumped
into the retort is not actually burning and there is no heat being created within the retort itself. The
heat is being provided by the combustion burners or electric heating elements surrounding the retort
assembly. This heat is being absorbed by the mixture of air and gas and provides the energy
required to make the chemical reactions shown below.

Predominant Natural Gas (CH4) Reaction

2CH4 + 4N2 + O2 + HEAT => 2CO + 4H2 + 4N2

Predominant LPG or Propane (C3H8) Reaction

2C3H8 + 12N2 + 3O2 + HEAT => 6CO + 8H2 + 12N2

The difference in %CO when endothermic gas is produced with different hydrocarbons is important
to note because carbon controllers at the furnace are preset to make certain assumptions. One of
those parameters is known as the “CO Factor”. This value should be changed to represent the
actual %CO of the endothermic gas being introduced into the furnace atmosphere since this value
will directly effect the carbon potential (%C) calculation made inside the carbon controller.

For generator operators looking at the flow meters on the gas generator, the above equations can
also be described in terms of the Air/Gas Ratio.

Proper Mixture Flow Rate with Natural Gas (Methane)

Air Flow / Gas Flow = 2.5
(Air Flow + Gas Flow) x 1.43 = Endothermic Gas Flow

Proper Mixture Flow Rate with Propane

Air Flow / Gas Flow = 7.5
(Air Flow + Propane Flow) x 1.53 = Endothermic Gas Flow

IMPORTANT NOTE FOR GENERATORS USING NATUAL GAS

While natural gas is primarily composed of methane gas (CH4), to meet peek demand times a gas
supplier will typically introduce a mixture of other hydrocarbons (i.e. propane) into the natural gas
supply. When this occurs the gas supplier will dilute the additional propane gas with an inert gas
(i.e. nitrogen) to maintain a consistent heat quantity per volume (BTU/CF) within the gas supply
line.

The result of this “peak shaving” is that the combustion systems and burners throughout the heat
treatment facility will not be greatly affected. However, as indicated above, the chemical reaction
required to produce endothermic gas and the atmosphere inside a heat treating furnace will
definitely be affected. A properly tuned fuel-injection mixing system will account for these
changes automatically on an gas generator by introducing a larger amount of air flow to maintain
the desired endothermic gas quality.

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Endothermic Gas Quality Control

While the amount of carbon dioxide and water vapor within endothermic gas is relatively small, the
concentrations of these components are critical in determining the carbon potential (%C) of the
endothermic gas being produced for a particular heat treatment application. Therefore, most
generators will use either Dew Point or CO2 as a process variable when controlling endothermic gas
production.

The ideal endothermic gas dew point or %CO2 is usually dictated by the temperature and desired
carbon potential (%C) within the heat treating furnace where the endothermic gas will be
introduced. As a guide, here a basic table that describes what carbon potential of endothermic gas
when introduced into a heat treatment furnace operating at a particular temperature.

Dew Point vs. Carbon Potential Relationship

Endothermic Gas %Carbon Potential in Furnace at Temperature

Dew Point (‘F) 1500’F 1600’F 1700’F
30 1.10 0.80 0.55
40 0.85 0.60 0.40
50 0.60 0.40 0.25

Once the desired dew point is selected, the primary means of controlling this variable is by
adjusting the air/gas ratio of the mixture being pumped into the retort(s) of the endothermic gas
generator. This is typically controlled using either a carburetor/trim valve setup or more precisely
with a fuel-injection ratio control system.

To better understand what the air/gas ratio adjustments are actually doing to the gas, we need to
review the reactions associated with the production of carbon dioxide (CO2) and water vapor inside
the generator.

Methane Combustion
CH4 + 2O2 => CO2 + 2H2O

Water Vapor Production (Dew Point Control)

2H2 + O2 => 2H2O

Carbon Dioxide Production (CO2 Analyzer Control)

2CO + O2 => 2CO2

According to these equations, the amount of CO2 and water vapor being produced in the
endothermic gas is primarily the result of additional air in the gas mixture. Therefore, more air
(higher air/gas ratio) will produce more water vapor and result in the production of endothermic gas
with a higher dew point. If there is not enough air in the mixture then carbon soot is created in the
generator. This is discussed in more detail in the next section.

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In addition to the creation of water vapor the excess oxygen will also produce carbon dioxide. There
is a direct relationship between the amount of carbon dioxide and water vapor created within
endothermic gas that is described by the following equation:

Hydrogen Water Vapor Reaction

H2 + CO2 <=> H2O + CO

However, a simple “rule-of-thumb” when trying to understand the relationship of dew point and
carbon dioxide in endothermic gas is simply:

Typical Carbon Dioxide / Dew Point Relationship “Rule-of-Thumb”

Dew Point (‘F) = %CO2 * 100
(for %CO2 values between 0.30 and 0.50)

The key point to remember is that more air (higher ratio) will produce a higher dew point and
%CO2 in the endothermic gas being produced.

SOOT and CARBON FALLOUT

Unfortunately, we have not covered the whole story for endothermic gas production. There are a
number of hidden reactions that can occur with even the best ratio control system using the best
dew point sensors.

The largest cause for problems in endothermic gas production typically revolves around the creation
of carbon (or soot) in the gas being produced. Soot is a byproduct of a number of undesirable
reactions that can take place in any endothermic gas generator. The easiest way for a generator to
produce soot is when there is not enough air in the gas mixture being pumped into the retort(s) of
the generator.

Too Much Natural Gas (CH4) Reaction

3CH4 + 4N2 + O2 + HEAT => 2CO + 5H2 + 4N2 + (%C(soot) + %CH4)

This begins to occur when the dew point falls below 20’F and will continue to occur as long as the
dew point of the gas remains low. During this time, the endothermic generator will not be very
easily controlled and will not respond to ratio adjustments. A three gas analyzer is useful when
identifying this reaction, because it will report a large amount of un-reacted methane (CH4) in the
endothermic gas.

“Leaning Out” a Generator

The easiest way to clean the catalyst of a small amount of soot build up is by manually increasing
the air/gas ratio to 3.5+ parts air. This process introduces more oxygen into the retort which will
react with the carbon on the catalyst in the following reaction. Once the carbon is gone, the normal
reactions described above will take over and the dew point will rise quickly. This process can take
anywhere between 5 to 15 minutes depending on the amount of soot resident inside the retort and
catalyst.

Carbon Burning with Lean Air/Gas Mixture

2C(soot) + O2 => 2CO + HEAT

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“Burning Out” a Generator

If after 30 minutes of “leaning the generator” the dew point has not come up, it is usually advisable
to perform a “burnout” on the generator. This is accomplished by stopping the air/gas mixture
completely, reducing the generator temperature to 1500’F, and introducing a small amount of air
flow (100 to 200CFH) into the retort.

Carbon Burnout (100% Air)

C(soot) + O2 => CO2 + <<+HEAT+>>

Since this reaction creates a large amount of heat, it is important to keep watch on the temperature
of the generator to ensure that there is no damage to the retort alloy. If the temperature rises by
more than 50’F it is typically recommended that the burnout air flow is turned off until the
temperature decreases back to the normal 1500’F. A three gas analyzer is useful when performing
this procedure as it can identify when the CO and CO2 concentrations fall to 0% which typically
indicate that the carbon burnout is complete.

Carbon Fallout

The other primary cause for soot creation in endothermic gas usually involves the cooling system of
the generator. The following reactions will occur quite quickly between the temperatures of 900
and 1300’F.

Water/Soot Precipitation
CO + H2 => C(soot) + H2O

Carbon Monoixide Decomposition (Carbon Fallout)

2CO => C(soot) + CO2

As mentioned, both of these reactions will produce a large amount of soot in the cooling system and
pipeline downstream of the endothermic gas generator. Therefore, it is critical that endothermic gas
be “frozen” as fast as possible from the reaction temperature of 1900’F to below 300’F to minimize
any potential for carbon fallout to occur. When the gas temperature is below 300’F there is not
enough energy in the gas for the above reactions to occur.

The use of a laser thermometer is useful when determining if there are any cooling problems with a
particular generator.

Summary

Endothermic gas is a major component of the atmosphere inside most heat treating furnaces.
Therefore, the precise control and documentation of the endothermic gas quality is critical in any
facility seeking to provide a quality heat treating service.

Due to the significance of the endothermic gas in the heat treating process, it is highly
recommended that any gas generator be equipped with a paperless chart recorder to document the
historical performance of the generator at all times. In addition, the use of a three gas analyzer to
regularly verify the endothermic gas quality is a good practice to identify any problems before they
occur.

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Phone: 414-331-2457 2821 N. Fourth Street Suite #514 E-Mail: [email protected]
Fax: 414-332-2457 Milwaukee, Wisconsin 53212-2364 Web: www.atmoseng.com