. . . . . . . . ....

^ K

Gas Analysis

33.1 I GENERAL CONSIDERATIONS

Anaerobic decomposition of sludges and of some liquid wastes, particularly those
with BOD values exceeding 1500 mg/L, is considered the most economical method
of treatment when the organic materials involved are amenable to methane fermen-
tation. Anaerobic processes are popular because operating costs are low and energy
is produced rather than consumed by the process.
Anaerobic digestion; The gas produced in anaerobic digestion of sludges usually contains 33 to 38
percent carbon dioxide, 55 to 65 percent methane, small amounts of hydrogen,
CO2 some nitrogen, and traces of hydrogen sulfide; and it has a heating value in the
CH4 neighborhood of 22,000 kJ/m3 (600 Btu/ft3 or 5,300 kcal/m3). The caloric value of
H2 the gas produced is normally in excess of the heat requirements for maintaining
N2 proper temperatures in municipal sludge digestion units. It may be in excess for
H2S industrial wastewaters as well, depending upon waste strength and the heating
needs for treatment. The excess gas has value for producing energy for heating or
for useful work.
The composition of gas produced during anaerobic treatment varies some-
what with the environmental conditions in the reactor. It changes rapidly during
the period that anaerobic treatment is being initiated, such as when reactors are
first started, and when normal treatment is inhibited. For anaerobic reactors oper-
ating in a routine manner and being fed a given substrate regularly, the composi-
tion of the gas produced is fairly uniform; however, the ratio of carbon dioxide to
methane varies radically with the character of the substrate undergoing decompo-
sition. Buswell and Boruff' showed that methane fermentation of the three com-

'A. M. Buswell and C. S. Boruff, The Relation between the Chemical Composition of Organic Matter
and the Quality and Quantity of Gas Produced during Sludge Digestion, Sewage Works J., 4: 454
(1932).
 700
Gas analysis;
*determine their fuel value
*detect the treatment unit conditions
Gas analysis;
1. Volumetric methods
2. Gas Chromatography
P A R T 2 Water and Wastewater Analysis
mon classes of organic materials produces carbon dioxide and methane in the fol-
lowing ratios:
Carbon dioxide Methane
Carbohydrates 50. 50
Low-MW fatty acids 38 62
High-MW fatty acids 28 72
Proteins JJ4 76
131 69
Because of the wide variety of organic substances (usually of unknown compo-
sition) that are subjected to methane fermentation, it has become common practice
to analyze the gases produced to determine their fuel value and, in some cases, to
maintain a check on the behavior of the treatment units. The idea has been advanced
that the onset of anaerobic treatment troubles is accompanied by an increase in the
carbon dioxide content of the gas produced and that this test can be used in place of
the volatile-acids determination to detect such conditions. Experience will demon-
strate whether carbon dioxide measurements can substitute for volatile-acids deter-
minations in this capacity. Because of the influence of the substrate on the ratio of
carbon dioxide to methane in the gas produced, it is reasonable to assume that inter-
pretations based upon carbon dioxide content alone may lead to faulty conclusions.
Interest has been shown in recent years in the use of hydrogen concentration as
an additional indicator of the performance of anaerobic treatment. Hydrogen plays a
key role in anaerobic treatment as discussed in Sec. 32.2. In order for the anaerobic
process to operate properly, the hydrogen concentration must be maintained quite
low by the hydrogen-using methanogens, such that the concentration in the gas pro-
duced is normally below 0.01 percent. During digester upset or unbalance, the hy-
drogen concentration may exceed this value by one to two orders of magnitude, an
increase that could signal the need for closer observation and control. Unfortu-
nately, the standard methods for gas analysis given in the following will not mea-
sure hydrogen at such low values, and a different instrumental approach is required,
such as use of a reduction gas detector.2
33.2 I METHODS OF ANALYSIS
Gas analysis can usually be accomplished either by the volumetric procedure or by
gas chromatography, except for the measurement of hydrogen sulfide, which usu-
ally occurs in amounts too small to be measured by either of these procedures. In
general, volumetric analyses are quite accurate and are suitable for the determina-
tion of oxygen, methane, hydrogen, and carbon dioxide. Nitrogen is usually deter-
mined in such analyses by an indirect procedure. Volumetric analyses are quite
time-consuming. However, the equipment required is relatively simple, needs no
2
D. P. Smith and P. L. McCarty, Energetic and Rate Effects on Methanogenesis of Ethanol and
Propionate in Perturbed CSTRs. Biotechnology and Bioengineering, 34: 39 (1989).
 C H A P T E R 33 Gas Analysis 701

calibration before use, and therefore is particularly suitable when analyses are con-
ducted on an infrequent basis.
Gas chromatographic analysis has the distinct advantage of speed; a gas analy-
sis can be completed in only a few minutes. For this advantage to be utilized, how-
ever, the instrument must have been previously calibrated for each gas of interest,
the oven must have reached a constant temperature, and the detector must be giving
a stable response. Because of these requirements, this method of analysis is more
suited to routine work where gas analyses are conducted several times each week,
making it permissible to keep the instrument always in operating condition. This
method is sufficiently accurate for most practical purposes, although not quite as
good as volumetric analysis. Although it is possible to separate hydrogen, oxygen,
nitrogen, methane, carbon dioxide, and hydrogen sulfide by gas chromatography,
this is not presently practical on a routine basis, using one instrument witii a single
column and detector. In addition, the quantities of hydrogen or hydrogen sulfide oc-
curring in digester gas are usually too small in concentration to be measured with
any accuracy. Gas chromatography is mainly suited to routine analysis to determine
the relative proportions of methane, carbon dioxide, and "air" (nitrogen plus oxy-
gen) occurring in a sample of anaerobic reactor gas. Normally, these are the main
gaseous components of interest.

33.3 I VOLUMETRIC ANALYSIS

Early methods of volumetric analysis employed separate measurement of carbon
dioxide and oxygen, followed by a slow simultaneous combustion of hydrogen and
methane. The analysis was completed by measuring the amount of carbon dioxide
produced during the combustion of the methane and then employing a knowledge
P1/T1=P2/T2=k of Gay-Lussac's law of combining volumes (Sec. 2.9) to determine the amounts of
methane and hydrogen present in the mixture.
In the past an apparatus was sometimes used that employed a slow-combustion
unit in which hydrogen and methane were burned together in the same unit. How-
ever, its operation in the determination of hydrogen and methane was somewhat
hazardous because of the possibility of explosions; and it is therefore not recom-
mended. A preferred device, such as illustrated in Fig. 33.1, provides for separate
oxidation of hydrogen and methane. Hydrogen is oxidized by passing the gas
through a heated unit charged with cupric oxide, and methane is oxidized in a sepa-
rate unit by bringing a mixture of it and oxygen in contact with a catalyst at rela-
tively low temperatures. Explosion hazards are completely eliminated.

Carbon Dioxide
Carbon dioxide is measured by bringing a sample of known volume, usually 100
mL, into contact with a solution of potassium hydroxide. The carbon dioxide reacts
with the hydroxide to form potassium carbonate, as shown in the following equation:
C0 2 + 2KOH -» K2C03 + H 2 0 (33.1)
I vol. 0 vol.

KOH is used instead of sodium NaOH to

absorb CO2 because of the greater
solubility of K2CO3.
In the rxn;
1. CO2 disappears from the gaseous phase,
2. K2CO3 formed remains in the liquid phase,
3. CO2 amount = the loss in the volume.
P A R T 2 Water and Wastewater Analysis

-ill
mL
;-»4-íi.íi l . ^ - f S i f t
, six, •. ,.;' ¡ASMS
# Hi ill
":•••::?•• W l l
:i:,xx

Al :
>f;
j- - j . ~ ! - £ f , > •:¿
^ « ' ^ « »
î • ;_£ -•; i .'•--) l';
• I'M
.s ' -f.
í,\; :sJ¡

P mm

^¿-^G^KA¿-:_^

Figure 33.1
Gas-analysis apparatus equipped for separate low-
temperature oxidation of hydrogen and catalytic oxidation
of methane. (Courtesy of Burrell Scientific, Inc.)

In the reaction, the carbon dioxide disappears from the gaseous phase, and the
potassium carbonate formed remains in the liquid phase; therefore, the loss in vol-
ume of the gas is equal to the carbon dioxide content. Additionally, any hydrogen
sulfide present in the gas also combines with the potassium hydroxide,
H2S + 2KOH -» K2S + 2H 2 0 (33.2)
1 vol. 0 vol.

but the volume of hydrogen sulfide is usually so small that its effect may be ignored.
Potassium hydroxide is used instead of sodium hydroxide to absorb carbon
dioxide because of the greater solubility of potassium carbonate. If sodium hydrox-
ide is used, sodium carbonate tends to precipitate. Some of it usually floats and
clogs the capillary passages.
 CHAPTER 33 Gas Analysis 703

Oxygen
Theoretically, there is very little possibility of oxygen being present in the gas pro-
duced by anaerobic treatment. However, small amounts may gain entrance to the
sample during the sampling procedure and during charging of the gas-analysis ap-
paratus. It is therefore good practice to analyze for oxygen. The presence of more
than 0.1 to 0.2 percent usually indicates poor technique in sampling and in transfer-
ring the sample to the gas-analysis apparatus.
Oxygen in gas from anaerobic treatment is generally measured by the use of alka-
line pyrogallol. Under alkaline conditions, pyrogallol (1,2,3-trihydroxybenzene) is ox-
idized by oxygen. The end products of the reactions, such as carbon dioxide and or-
ganic acids, are held as potassium salts in the absorbing solution. If all carbon dioxide
has been removed from the sample before bringing it into contact with the alkaline
pyrogallol, any decrease in sample volume will be due to removal of oxygen.

Hydrogen
Hydrogen may be determined separately in the presence of methane by passing the
gas mixture over cupric oxide maintained at a temperature in the range of 290 to
300°C. Under such conditions hydrogen is oxidized to water, but methane is not ox-
idized. The water vapor formed condenses at the temperatures to which the sample
must be reduced for subsequent volume measurements, and therefore loss in vol-
ume after contact with heated cupric oxide is a measure of the hydrogen present.

Methane
After removal of hydrogen, methane may be determined in the residual gas by slow
combustion or by catalytic oxidation. In either case oxygen is required, but the tech-
nique for each is very different,
Catalytic Oxidation A mixture of the gas containing methane and oxygen is used
in this method, and the oxidation is performed catalytically attemperaturesbelow
the kindling point; consequently, an explosion does not occur. The volume of oxy-
gen required is determined from the equation
CH, + 20 2 -» C0 2 + 2H20 (I) (33.3)
I vol. 2 vol. 1 vo!. 0 vol.
(excess)
It will be noted that 2 volumes of oxygen are required to oxidize 1 volume of
methane and that 1 volume of carbon dioxide is produced. The 2 volumes of water
vapor produced are reduced to zero volume at the temperature at which final gas
volumes are measured. Since 2 volumes of oxygen are required for each volume of
methane, at least 2 \ volumes should be used to provide a sufficient excess to carry
the reaction to completion.
After the analyses for carbon dioxide, oxygen, and hydrogen arefinished,the
volume of residual gas containing methane is about 60 to 70 mL if a 100-mL sam-
ple is used initially. It is impossible to mix 60 to 70 mL of gas with 21timesits vol-
ume of oxygen in the equipment provided. The maximum-size sample of methane
ro4 P A R T 2 Water and Wastewater Analysis

that may be used in a 100-mL buret and be mixed with 21timesits volume of oxy-
gen is about 28 mL. The usual procedure is to waste sufficient residual gas to leave
a sample ranging in size from 20 to 25 mL. Some analysts prefer not to waste the
gas but store the excess in the oxygen absorption pipet as a reserve supply in case it
is needed. Oxygen is next admitted to the sample in proper amount, and then the
mixture is brought into contact with the catalyst.
The methane content of the gas used for the combustion may be determined in
two ways. Inspection of Eq. (33.3) will show that 2 volumes of oxygen are used for
each volume of methane oxidized and 1 volume of carbon dioxide results. A con-
traction in gas volume occurs that is equal to the amount of oxygen used. Since this
is equal to two times the methane.
Volume of methane = £ total contraction
The residual gas, after measurement to determine total contraction, still contains
carbon dioxide in a volume equal to the methane originally present. It may be mea-
sured by bringing it into contact with potassium hydroxide and measuring the resid-
ual gas to get the volume absorbed.
Final calculations of methane content must be based upon an adjustment of the
values obtained on the test portion of the methane-bearing sample to the total vol-
ume. For example, if 65 mL remained after carbon dioxide, oxygen, and hydrogen
were removed and 25 mL was used for the methane determination, the values
should be multiplied by a factor of 65/25 to obtain the percentage of methane.
Slow Combustion The separate determination of methane by the slow-combustion
method is not common. The procedure is essentially the same as for a combina-
tion of hydrogen and methane. Analysis of the data is exactly as described under
catalytic oxidation.

Nitrogen
Nitrogen is a relatively inert gas and remains unchanged at the end of the usual gas-
analysis procedure. It is assumed that it is the only component of any significance
that behaves in this manner. It is customary to total the carbon dioxide, oxygen, hy-
drogen, and methane percentages and subtract them from 100. The difference repre-
sents inert gases and is reported as nitrogen.

Sources of Error
There are four major sources of error in gas analysis, as follows:
Collection, Storage, and Handling of Samples Unless special care is taken in
the collection of samples, contamination by air occurs. Samples should always be
collected in glass or metal tubes, particularly if an appreciable time elapses before
analysis can be made. Gum-rubber balloons are not suitable because they are per-
meable to hydrogen and methane. Transfer of gas from the sample tube to the gas-
analysis apparatus requires the use of a displacing fluid, and some modification of
the sample is apt to occur. Also, some air may gain entrance.
 C H A P T E R 33 Gas Analysis 70S

Confining Fluid Mercury is the ideal confining fluid because of the insolubility
of all gases in it but, because of its great density, cost, and potential for human
health hazard, it is not usedtoday.For ordinary purposes, a high degree of accuracy
is not needed and less ideal confiningfluidscan be used. Water has much too great a
solvent power for all the gases involved to serve satisfactorily. However, it has been
found that an aqueous solution containing 20 percent sodium sulfate and 5 percent
sulfuric acid has markedly reduced solvent powers. This is the mixture normally
used in portable equipment but does introduce some error in analysis.
Incomplete Combustion of Methane During the combustion of methane, a high
concentration of oxygen is present at the start of the combustion, but as the combus-
tion proceeds, the oxygen concentration decreases markedly, owing to use and to
dilution by the carbon dioxide formed. Unless a volume of oxygen at least 2 \ times
the size of the gas sample is used, an oxygen deficiency may occur. Incomplete
combustion is a common cause of high nitrogen values and of low methane values.
Temperature Changes In gas analysis, small changes intemperaturecan cause
serious errors. This is a special problem during the measurement of hydrogen and
methane, where the reactions are conducted at high temperatures. There is always a
tendency to measure the volume remaining after combustion before the temperature
of the gas has returned to the original value. This may lead to positive errors in
some instances and negative errors in others.

33.4 I GAS CHROMATOGRAPHIC ANALYSIS

Gas chromatography affords a rapid and simple method of gas analysis when used
on a routine basis. The principles of this method were outlined in Sec. 12.4. An in-
strument equipped with a thermal conductivity detector is usually used for analysis
of gas from anaerobic treatment, and helium is normally used as a carrier gas to
sweep the gas sample through the instrument. Only about 1 or 2 mL of a gas sample
are required for the analysis, and this is usually introduced into the instrument with
a syringe, although some instruments are equipped with a gas sampling port, which
simplifies sample measurement and introduction.
One of the most important items in the gas Chromatograph is the packing mate-
rial used in the column for separation of the gaseous components. Several commer-
cially available column packings are listed in "Standard Methods," together with
the gases for which they are particularly suitable for separating. Columns that sepa-
rate air (oxygen plus nitrogen), methane, and carbon dioxide are necessary for rou-
tine analysis of gas from anaerobic treatment. Columns that also give separation be-
tween the two components of air are more desirable, however. The ability to
determine the presence of oxygen is desirable since this is a good check on the ade-
quacy of sampling technique as discussed under the volumetric method.
Most instruments have a sufficiently stable operation, so at a given temperature
of operation and gasflowrate a linear relationship will exist between the height of a
peak on the gas chromatogram and the concentration of a gaseous component.
Thus, by using a pure gas standard and injecting different volumes into the gas
roe P A R T 2 Water and Wastewater Analysis

Chromatograph, a curve of peak height versus gas volume may be prepared. The
percentage by volume of a given gas in a sample is then equal to its measured vol-
ume divided by the total of the sample injected. Peak area is also widely used and
can be determined automatically with an integrater.
Thermal-conductivity detectors tend to lose sensitivity with time, with the re-
sult that the peak height for a given volume of gas tends to decrease. This can be
corrected by frequent standardization. However, it has been found that the decrease
in peak height is proportionally the same for methane, carbon dioxide, and air.
Since gas from anaerobic treatment is composed almost entirely of these gases, the
summation of their respective concentrations should total almost 100 percent. Any
significant decrease below this total will indicate a decrease in detector sensitivity,
provided that other analytical errors have not been made. If this is true, then the cor-
rect percentage for each component can be determined by proportioning each up to
give a total of 100 percent. For example, if the measured percentages of the three
components total 90 and the measured methane percentage is 54 percent, its actual
percentage would be 54(100/90) or 60 percent.

Sources of Error
Errors in collection, storage, and handling of samples will be the same as with the
volumetric analysis method. In addition, changes in instrument temperature or car-
rier gas flow rate, changes in detector sensitivity, degeneration of column packing,
and inaccuracies in measurement of volume of injected gas samples will all result in
errors. With gas from anaerobic treatment the summation of the methane, carbon
dioxide, and air percentages should total close to 100 percent. If it does not, then
one of the discussed sources of en-ors might be the cause.

33.5 I HYDROGEN SULFIDE

The measurement of hydrogen sulfide is particularly important where gas is to be
used for fuel in gas engines. Most engine manufacturers specify that the gas used
should not have more than 50 grains of H2S/100 ft3 (1.14 mg/L), in order to prevent
harm from corrosion.
Hydrogen sulfide is commonly measured in gas by means of the Tutweiler ap-
paratus shown in Fig. 33.2. The procedure is essentially as follows: A sample of gas
is introduced into the apparatus, which contains a small amount of starch indicator.
Small amounts of a standard iodine solution are added intermittently, with vigorous
shaking between additions of iodine. The iodine reacts with hydrogen sulfide as
shown in the following equation:
H2S + I2 -* 2HI + S (33.4)
When sufficient iodine has been added to oxidize all the hydrogen sulfide, excess
iodine is indicated by the typical blue color produced by starch indicator. The
strength of the iodine solution is selected to facilitate calculation of hydrogen sul-
fide in the particular units desired.
 CHAPTER 33 Gas Analysis 707

I ! -

•
•r
¡y
: \ ' .
•
-
:
'•¿•m
• •ir_
y i
Xyl Ï
•í .
• -ï-
.?/ -ym : :•
:
ft I
•
< , ;

€• •'.
-£-«.-•
:
.i
.-,• Í? T S
Í
-¿"

II •

Figure 33.2
Tutweiler apparatus used to determine hydrogen sulfide in sludge
gas. (Courtesy of Burretl Scientific, Inc.)

33.6 I APPLICATIONS OF GAS-ANALYSIS DATA

Gas analyses are used largely at wastewater treatment plants where information on
the fuel value of gas is important. In addition, a knowledge of gas composition can
be of considerable help in the control of digestion units as a supplement to informa-
tion provided by volatile-acids, pH, and other determinations or as a replacement
for some of them. Under normal conditions of operation, the percentages of
methane and carbon dioxide do not vary greatly. Sudden changes in gas composi-
tion can signai a change either in the operation of the treatment unit or in the
amount or composition of incoming wastewater or sludge. Such changes can thus
be used as a warning sign to suggest the need for closer observation and control of
the treatment unit.
PART 2 Water and Wastewater Analysis

The determination of hydrogen sulfide will continue to be an important consid-

eration wherever gas is used for fuel in gas engines, particularly in areas where the
sulfate content of wastewater is high.

PROBLEMS
33.1 How is gas analysis used in the control of the anaerobic waste treatment process?
33.2 What principle is involved in the separation of gases by chromatography?
33.3 (a) How is the fraction of nitrogen determined in a gas sample using volumetric
analysis?
(b) What sources of error would be of particular concern in determining nitrogen by
this method?

REFERENCE
Clesceri, L. S., A. E. Greenberg, and A. D. Eaton (eds.): "Standard Methods for the
Examination of Water and Wastewater," 20th ed., American Public Health Association,
Washington, DC, 1998.