DrägerReview89 06.01.

2003 12:09 Uhr Seite 24

Gas detection technology

Detecting combustible gases and vapours - catalytic bead or infrared?

hot catalyst water carbon dioxide

saturated
with oxygen methane

water
platinum coil
heat

signal

GAS
0

AIR

AIR
resistance (hot) resistance (hot)
appr. 3 Ohms e.g. 3.05 Ohms

CH4 + 2 O2 ➜ CO2 + 2 H2O + heat of reaction

Detection using a catalytic bead: This change in resistance is a measure catalytic surface of the detecting
Inside a catalytic bead sensor, combus- of the gas concentration (Figure 1). element (pellistor) and may, in some
tible gases and vapours are oxidized by circumstances, deactivate it.
catalysis on a small heated bead (known Three important points: – The sensor may, depending on the
as a pellistor). The heat of the reaction – The sensor needs at least 12 % by operating and ambient conditions,
causes the pellistor temperature to rise volume oxygen for the chemical reac- decrease in sensitivity. It is not pos-
which, in turn, slightly increases the re- tion (oxidation) to take place. sible to detect electrically if the sen-
sistance of the embedded platinum wire. – The gas is in direct contact with the sor has become insensitive to gas.

ST-599-2002
Figure 1: Simplified diagram of the catalytic bead measurement method

Anyone wishing to detect combustible Is it true that a catalytic bead sensor absorption spectrum. For instance,
gases and vapours is generally faced can detect all combustible gases although cyclohexane absorbs a lot of
with the following important ques- and vapours, while the infrared infrared radiation at 3.4 µm, it hard-
tions: sensor is extremely selective and is ly absorbs any at all at 3.3 µm. Ben-
– Is it better to use the more econo- even “blind” to certain substances? zene, by contrast, does just the oppo-
mical catalytic bead sensors or the “Blind” is certainly something of an site. Depending on which gas is to be
longer life infrared sensors? exaggeration. It is correct, however, detected, therefore, instruments with
– What are the advantages and dis- that combustible gases do exist, e.g. different IR detectors should be used:
advantages of each? hydrogen, which do not absorb in- in the former case the Polytron IR Ex
– What points are important to note? frared at all or do so only at wave- (3.4 µm), and in the latter the Poly-
– Are there certain applications lengths which are not accessible to tron IR Ex ES (3.3 µm) or Polytron 2
which are better suited to one or conventional IR detectors. In other IR (3.34 µm).
the other method? words, gases such as acetylene, am- So much for the theory: as a user of
This article aims to provide answers monia, carbon monoxide and hydro- the instruments, it is not necessary to
to the questions most frequently asked gen sulphide cannot be detected by IR know the spectral characteristics of
in this context. detectors. the gases. It is important to ensure,
In addition, there are gases and however, that the gases and vapours
vapours which only slightly absorb to be detected can indeed be detected
infrared at the specified wavelengths, in the specified concentrations (e.g.
e.g. vinyl chloride, acetonitrile and 0 ... 100 % of the lower explosive limit,
acrylonitrile. LEL). In short, studies into measure-
Certain vapours are worthy of parti- ment properties and advice for the
cular mention on account of their user are extremely important – this is
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non-excited
methane
molecule
infrared
filter, trans- detector
IR-radiation source lucent at e.g.
3.4 µm

signal

radiated attenuated
infrared intensity infrared intensity

GAS
excited vibrating

AIR
methane molecule
signal

CH4 + energy (IR) ➜ CH4 (excited)

Detection by infrared measurement: therefore, the intensity of infrared radia- – The measured gas is not in direct
With just a few exceptions, the principle tion drops - the extent of the decrease contact with the infrared detectors
ones being H2, NH3, N2H4, CO, CS2, being dependent on the gas type. The which are separated by optical
HCN, H2S and (CN)2 and the hydrides reduction in intensity can be measured windows.
(PH3, AsH3 etc.), combustible gases and using infrared detectors and is a mea- – The sensor does not decrease in
vapours are organic in origin. Such sure of the gas concentration (Figure 2). sensitivity. Any insensitivity to gas,
molecules contain C-H compounds e.g. due to failure of the radiation
which absorb, in particular, infrared Three important points: source or contamination of the optical
radiation at wavelengths of between – The physical IR measurement process system, is detected and the operator
3.3 to 3.5 micrometres. When passing can be conducted independently of alerted.
through a volume filled with such gas, the atmospheric oxygen content.

ST-600-2002
Figure 2: Simplified diagram of the infrared measurement method

equally true of catalytic bead sensors. tivity. For the same reason, the follow- infrared sensors. The sensors then
The increase in pellistor temperature ing applies to liquids: the higher the have to be calibrated to the substance
which occurs when a catalytic bead flash point, the lower the sensitivity. to which the sensor reacts least sensi-
sensor is exposed to a gas is caused Vapours with a high flash point (for tively, as this is the only way to ensure
by the output heat. This is dependent example diesel or fuel oil) and – in that the sensor will detect all other
on how many molecules per unit more general terms – combustible occurring substances more sensitively
time are converted by oxygen at what fluids classified by the VbF (Regula- (i.e. with a stronger output signal),
degree of heat of combustion. As one tion concerning the storage, transport and that a reliable warning will be
would expect, sensitivity to heavy and decanting of flammable liquids) given in all cases.
vapours (high molecular weight, low as AIII substances (with a flash point
speed of diffusion, i.e. fewer mole- > 55 °C), cannot be detected using Which measurement ranges can be
cules are converted per unit time) is catalytic bead sensors. On account of covered by the different methods?
low. As EN 50 073 succinctly puts it: their low vapour pressure, such fluids Because the catalytic bead sensor
“Non-detectable combustible gases: also tend not to generate potentially is designed for detecting explosion
large molecules”. explosive atmospheres (provided they hazards, the measurement range
are not sprayed). In this sense, it can 0 ... 100 % of the LEL has, by neces-
Since sensitivity depends on the type indeed be claimed that the catalytic sity, become established as the norm.
of combustible gas (or vapour), a wide bead sensor is suitable for detecting Lower measurement ranges such as
variety of, even if not all, combustible explosion hazards. 0...50 % of the LEL are also possible,
gases can, according to EN 50 073, be If reliable detection of several diffe- provided the output signal is high
detected. As a guideline, there is a rent gases is necessary, their respec- enough (e.g. for methane or ethy-
helpful rule of thumb: the higher the tive sensitivities must be known – this lene). For the purposes of a leak
molecular weight, the lower the sensi- is the case for both catalytic bead and search, there are also attempts to
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Gas detection technology / Detecting combustible gases and vapours - catalytic bead or infrared?

achieve lower measurement range

end values. The DrägerSensor Ex LC,
for example, which is to be launched
before year's end, will be equipped
with special electronics and temp-
erature compensation to achieve a
measurement range end value of
just 10% of the LEL – for ethylene or
propylene this equates to a measure-
ment range of roughly 0 ... 2000 ppm.
Incidentally, such measurement
ranges cannot be achieved merely by
amplifying the signal – other measu-
res must be taken to also improve con-
siderably the quality of measurement.
Far above the LEL, at concentrations
for which the catalytic bead sensor is
not designed, the sensor “drowns” in
gas – i.e. the bonded reactive oxygen
for oxidation inside the pellistor is
then displaced and expelled and is no
longer available for the catalytic reac-
tion. The outcome of this is a reduced
heat output and, therefore, a lower
output signal.
The physical IR method of measure-
ment, on the other hand, can in prin-
ciple be used at up to 100 % by vol-
ume (provided it has been approved
for this type of measurement). In
general, however, IR detectors are
also designed for measurement
range end values of 100 % of the LEL
and lower. Gases and vapours which
demonstrate a particularly high
degree of IR absorption (e.g. dimethyl
ether, propane, alcohols and Otto
fuels) can be detected using the Poly-
tron IR Ex at 0...5 % of the LEL and
1-378-93

even at 0...1000 ppm. Indeed, the

Polytron IR Ex is particularly well
suited to detecting the heavy alcanes.
This is not all that surprising con-
sidering that a correspondingly high
number of CH compounds in such
Large numbers of the
molecules contribute to the IR is true of the catalytic bead sensor: Polytron IR Ex infrared
absorption process. A catalytic bead although the pellistors tend to be of transmitter are sold due
sensor, in contrast, is completely the “PR” type, i.e. “poison resistant” – to the instrument's ver-
insensitive (for the purposes of which basically means that they will satility, particularly as
measurement) to, for example, last longer than standard pellistors regards detection of
very low concentrations.
undecane. when exposed to sensor poisons – The Polytron IR Ex is
even a PR pellistor can be poisoned. approved in accordance
What needs to be remembered Statements such as “reduced reaction with Directive 94/9/EC:
when using catalytic bead sensors sensitivity caused by sensor poisons II 2G (DMT 02 ATEX
and infrared sensors? E178X)
such as silicones and silicon com-
The lifetime of a catalytic bead sensor pounds” do not sufficiently describe
may be cut drastically short if the this situation. Even in the presence
catalytic surface of the pellistor is not of many other gases and vapours,
given the proper care and attention. the catalytic bead sensor can quickly
As any car driver knows, leaded petrol decrease in sensitivity. Such sub-
would soon destroy a car's exhaust gas stances include, for example, volatile
catalytic converter. Exactly the same sulphur and phosphorous compounds
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(especially H2S and SO2), corrosive RL, new: BGR 104), this regulation, place such products on the market
substances (HCl, NO2, Cl2), polymeriz- issued by the professional associa- from 30 June 2003. Like most manu-
ing substances, organometallic com- tions, requires that aptitude-tested facturers of explosion-proof equip-
pounds (e.g. tetraethyl lead) and also gas warning equipment, i.e. instru- ment, Dräger has taken advantage of
some halogenated hydrocarbons (ref- ments tested for their suitability for the six-year transitional period before
rigerants, CFCs). The poisoning pro- the intended purpose, be maintained the ATEX Directive comes into force
cess destroys and inhibits the catalytic in accordance with the instructions to redesign all older products and
centres in the pellistor material with contained in the BG [Professional As- adapt them to the new harmonized
the result that fewer molecules per sociations'] Information Sheet T 023 CENELEC standards and/or the now
unit time are oxidized, the heat out- (new: BGI 518), which specifies the fairly tough EMC requirements con-
put drops and the output signal is re- maintenance intervals on the basis tained in EN 50 270. This ensures
duced. of the current test results. For gas that, even after 30 June 2003, all pro-
In addition, there is the problem of warning instruments with (certified) ducts will still be available – essential
contamination. Because the pellis- self-diagnostic capability (e.g. infra- for the future success of the company.
tors, which reach temperatures of red detectors), the calibration inter-
approx. 450 °C, must not be allowed val may be as long as 12 months, How can system response times be
to become a source of ignition, the while other sensors (e.g. catalytic optimized such that sufficient time
catalytic bead sensors, for the sake bead sensors) are subject to a maxi- remains to initiate automatic and
of explosion protection, are equipped mum interval of just 4 months. organizational countermeasures?
with flame arrestors in the form of It goes without saying that equipment
porous sintered metal disks. Corro- Can catalytic bead sensors with pro- operators have an interest in being
sion, small drops of oil or fine dust tection technique (Ex) es 3n G5 or warned of leaks as early as possible.
particles in the pores of the sintered (Ex) sd 3n G5 still be placed on the However, because the response time
metal can hinder the gas flow, mean- market after the ATEX Directive has of (diffusion) sensors cannot be influ-
ing once again that fewer molecules come into force? enced, being a gas- and instrument-
are oxidized per unit time, heat out- In a word: no. European Directive specific variable, operators often
put drops and the output signal is 94/9/EC, usually known as ATEX for choose to set the alarm limits at an
reduced. short, prohibits manufacturers from unreasonably low level. This can lead
In both cases the fact that a catalytic placing explosion-protected equip- to more false alarms being given and,
bead sensor quits its service without ment on the market unless it bears in the longer term, may reduce the
notice is a disadvantage from a safety the CE mark, identifying it as com- operator's acceptance of the entire
point of view. The only way to confirm pliant with the Directive. Compliance gas warning system. Operators would
that the catalytic bead sensor is func- in this case refers not only to proven do far better to locate the sensors
tioning properly is to expose it to the electromagnetic compatibility (in in the places where leaks are most
appropriate gas. accordance with EMC Directive likely to occur or to switch to using
Under these conditions the advantage 89/336/EEC, or EN 50 270 in the measurement systems which actually
of an IR sensor becomes evident. Al- case of testing of gas warning instru- permit such low alarm limit settings –
though contamination of the optical ments), but also (in accordance with apart from infrared sensors, catalytic
system also causes problems in IR 94/9/EC) to proven product compli- bead sensors could be used, offering
sensors, the system does not fail with- ance with the harmonized European as they do a measurement range end
out notifying the user: a reference standards with respect to explosion value of 10 % of the LEL. Bearing
system recognizes that the sensor is protection. To this end, an EC type- in mind the varying sensitivity to the
contaminated and signals a main- examination certificate must be target gases, however, EN 50 073
tenance request or, in serious cases, obtained from a notified body (e.g. recommends that, when using cata-
a fault (“beam block”). As cleaning DMT); the same body must also con- lytic bead sensors, alarm limits for
of the optical system is generally a duct regular quality audits. methane should not be set below 5 %
fairly straightforward process, preven- The aforementioned protection tech- of the LEL, for propane and butane
tive action can be taken to avoid niques include a Germany-specific not below 10 % of the LEL and for
downtime. protection technique conforming to petrol vapours not below 20 % of the
If the reflectors are electrically the German VDE [Association of Ger- LEL.
heated, as in the Polytron IR Ex and man Engineers] regulation 0171 / 01. Another theoretical method of accel-
Polytron 2 IR, the chances of water 69 from 1969. The old Exytron and erating the warning response is based
vapour condensation are more or Polytron measuring heads were on using models to forecast the alarm
less excluded from the outset. also certified in this way because process. However, whether a so-called
Neither infrared nor catalytic bead the CENELEC standard EN 50 018 Delta alarm would give an earlier
sensors are maintenance-free, how- “Flameproof enclosure” did not per- warning – without triggering false
ever. The German Accident Preven- mit sintered elements as “breathing alarms – is doubtful, at least as far as
tion Regulations: Gases (VBG 61, elements” until its second edition heavy vapours are concerned.
new: BGV B 6, § 56 “Testing of Gas was issued in 1994. After all, Delta alarms are based on
Warning Devices”) stipulates regular The Germany-specific protection the calculation of an expected gas
functional testing. Like the German technique is not ATEX-compliant and concentration, using a comparative
Explosion Prevention Regulations (Ex- it will no longer be permissible to model (known as a predictive alarm).
89 Dräger Review 1/03 27
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Gas detection technology / Detecting combustible gases and vapours - catalytic bead or infrared?

To rule out false alarms, a precise

knowledge of the signal rise response
(which can vary considerably for diffe-
rent gases and vapours, depending on
ambient conditions and sensor oper-
ating time) is necessary – this infor-
mation would have to be recorded in
a data log and continuously compared
with the actual measured signal.
Although Delta alarms can detect very
quick changes in gas concentration
before the alarm concentration is
reached, such rapid gas concentra-
tion changes are mainly caused by
small-molecular gases such as hydro-
gen, methane and ammonia which
the catalytic bead sensor reacts to very

ST-43-2002
quickly anyway. If exposed to 50 % of
the LEL of these gases, the 10 % LEL
alarm limit will be reached within
just 2 to 4 seconds (this is the t20
time, i.e. the time taken for the out- Polytron SE Ex PR M
put signal to reach 20 % of the actual measuring head with
concentration). If a sensor is located catalytic bead sensor.
Incidentally, the sensor
correctly, meeting the requirements was the first piece of elec-
given in Section E1.4 of the German trical equipment for which
Explosion Protection Regulations, the DMT issued an EC
there seems to be little advantage in type-examination certifi-
cate in accordance with
using a Delta alarm. Directive 94/9/EC:
DMT 97 ATEX E001X
Conclusion
Both methods of measurement have
a justified place. its sensitivity determined. If the inter- T 023 (August 1999):
Even though the infrared sensor is vals between the adjustments become BGI 518: Safe Technology: Gas Warn-
considerably more expensive to buy unreasonably short it should be con- ing Devices for Explosion Protection,
than the catalytic bead sensor, the lat- sidered whether a more suitable Use and Operation. Information
ter does have the somewhat worrying method of measurement could be Sheet of the Professional Association
disadvantage, from the point of view chosen.” [Unofficial translation] of the Chemicals Industry Available
of safety, that it can rapidly decrease Expert advice is necessary in all cases only in German from: Jedermann-
in sensitivity in the presence of sensor – the EN 50 073 standard is worthy of Verlag, 69 021 Heidelberg, Germany
poisons, without the user being mention here, as it gives an unbiased
alerted to this condition. Poisoning assessment of the infrared measure- Explosion Protection Regulations:
must be classed, therefore, as a dan- ment process and the catalytic bead BGR 104: Regulations for Occupa-
gerous and non-detectable error. If measurement process, outlining their tional Safety and Health, Expert
poisonous substances are likely to respective advantages and disadvan- Committee on Chemicals of the BGZ,
occur and cannot be kept away from tages. (July 2000)
the catalytic bead sensor, it would Available only in German from:
be wise not to use this method of EN 50 073 (April 2000): Werbe-Druck Winter,
measurement in the interests of Guide for Selection, Installation, 69 207 Sandhausen, Germany
safety. It should be checked whether Use and Maintenance of Apparatus
perhaps an infrared method, for for the Detection and Measurement Dr. Wolfgang Jessel *
example, could be used to better of Combustible Gases or Oxygen. Dräger Safety AG & Co. KGaA
effect. [email protected]
Information Sheet T 023 of the Ger- UVV Gases (VBG 61):
man professional associations states German Accident Prevention
the following in this context: Regulations: Gases (1.4.1995), * Dr Wolfgang Jessel is also the
“If due to the presence of interfering Main Association of Industrial author of a 900-page compendium
gases at the site of measurement a Professional Associations for fixed gas detection systems,
entitled “Gases – Vapours – Gas
sudden and dramatic drop in sensitiv- Available only in German from: Detection Technology” (available
ity can be expected, the gas warning Carl Heymanns Verlag KG, only in German, order number
instrument should be adjusted at 50 939 Cologne, Germany 90 23 672), price EUR 49,--.
much more frequent intervals and
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Table: Comparative summary

Catalytic bead sensor Infrared sensor

Detectability of combustible A wide variety of combustible gases and There are other combustible gases and
gases and vapours vapours can be detected so long as the vapours apart from hydrogen which can-
molecular weights or flash points are not be detected. Contact manufacturer
not too high. Contact manufacturer in in case of doubt.
case of doubt.

Effects of non-combustible Besides a shortage of oxygen, con- A lack of oxygen does not affect the
gases stituents of non-combustible gases output signal. Beyond straightforward
with a heat conductivity which is very LEL measurement, non-combustible
different from air, e.g. inert gases like gases (e.g. the refrigerant R 134a) are
CO2, He or SF6, may drastically affect also detectable.
the measurement properties.

Possible measurement Generally 50 or 100 % of the LEL; even Generally 100 % of the LEL, and for
range end values 10 % of the LEL in the case of special certain gases also 10 or even 100 % by
sensors volume. 10 % of the LEL or 2000 ppm
are also possible.

External effects Catalytic bead sensors should not Dust, drops of oil, aerosol fats and
be used in locations where sensor poi- condensation can contaminate the
sons are likely to occur and an infrared optical system.
sensor offers a reasonable alternative An infrared sensor equipped with a re-
method of measurement (see also ference system detects the contamina-
Information Sheet T 023 (BGI 518), tion, sends a request for maintenance
Page 18) and, initially, continues to remain func-
Any contamination of the catalytic tional. If the degree of contamination
bead sensor must be paid particular is intolerably high, the infrared sensor
attention. issues a fault signal. An infrared sensor,
therefore, unlike a catalytic bead sen-
sor, is fail-safe.

Maintenance Low maintenance only in clean environ- Low

ments, for other cases refer to Informa- Thanks to self-diagnostics, much longer
tion Sheet T 023. Even in clean environ- maintenance intervals are possible (one
ments, T 023 stipulates calibration at year maximum).
least every 16 weeks. Of particular interest is the fact that
Only by exposing the detector to the an infrared sensor suffers no ageing
gas or vapour under investigation can effects which reduce sensitivity.
the proper functioning of the catalytic
bead sensor be checked.

Sensor lifespan Roughly 5 years in clean environments. Very high, no parts subject to wear.
Poisoning or contamination can signifi-
cantly shorten the sensor life.

Cost-benefit ratio Very good if only the purchase costs Good: purchase costs are higher than
are taken into account, but much less for the catalytic bead sensor, but the
positive if frequent maintenance is maintenance costs are much lower.
necessary and sensor suffers wear
due to poisoning.

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