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which occurs at various temperatures. This re- where x = Fraction (%cOnverSion) of S03
100
action, and not the previous one having double the
quantities, has been chosen purely for convenience, K is calculated from assumed values of conversion
The equilibrium constant, K, differs for the two for a gas of specific SO 2 content, and then the
reactions, the former being the square of the latter, equilibrium temperature for that value of K cal-
but the calculated conversions would' be the same culated from the Lewis and Randall equation given
in each case. previously. . ,. ~
For the purpose of this paper, the equilibrium Table V and Graph Edetail the variation of
constant has been calculated from the average of equilibrium constant, K, with temperature, Tables VI
three authorities, viz. VII and Graphs F and G, record the equilibrium
temperature for any assumed degree of conversion
Fairlie 4- with a gas of known composition. '
4760
T
This completes the theoretical study of sulphur phide. The rhombic form melts at 112. 8°C. and the
burning, and all that remains is to observe what melt forms a mobile liquid which becomes more
occurs in practice. The theory is in fair agreement viscous as the temperature is increased, until at
with what is experienced in actual pant operation 200°C. it becomes so thick it will not flow. However,
andit is hoped that the connections between theory at 350°C., the melt again becomes mobile. It ignites
and practice will be obvious. at about 248°C., finally boiling at 444.6°C.2 The
above temperatures should be taken as approximate
PART II. PRACTICE. only as Mellor" gives specific figures for the known
The most convenient raw material for the pro- allotropic forms and any particular allotropic
duction of SO 2 is sulphur, and although there are mixture would probably have its own characteristic
many alternative sources available, sulphur still physical and chemical constants.
proves the popular choice for a variety of obvious A typical analysis of the sulphur supplied to the
reasons. The sulphur used in the sugar industry sugar industry is roughly as follows:- 1 6
in this country is obtained almost solely from the
U.S.A., this source being chosen with consideration Moisture at 105°C. 0.10%
to price, quality and availability. Total Residue on Burning 0.13%
Organic residue 0.03%
In 1949 the production of crude sulphur in Mineral residue 0.10%
America amounted to approximately 41 million Arsenic as As 20 3 ... 2 p.p.m.
long tons.v mined by the Frasch-process and it is Selenium as Se Negligible
interesting to note that the Texas Gulf Sulphur Acidity as H 2S0 4 <0.1 %
Company was the major producer. During the Sulphur (by difference) 99.6%
same period the Union of South Africa is credited Sulphur as supplied contains very little sulphuric
with the importation of just over 65,000 long tons acid, but storing in the presence of air and moisture
c.
of crude sulphur.P most of which was used in the may cause sulphuric acid to be formed." It has
manufacture of sulphuric acid. It can be seen, been found that the oxidation of sulphur is negligible
therefore, that the sugar industry's requirements of if moisture is absent." As sulphur contains a small
between 4,500 and 5,500 long tons per annum, are amount of hydrocarbons which form water on
quite small when compared with the total imports combustion, this causing mists in the burner, and
into the country. furthermore, as a finite quantity of moisture may be
Sulphur is abundantly distributed in nature, present originally, it is often considered good
and on the Gulf Coast it is usually associated with practice to melt and strain all sulphur going to the
salt dome intrusions. The element is found to burner. This process ensures that moisture and
occur in the limestone, gypsum and anhydrite cap hydrocarbons are removed before combustion takes
rock and a few of these domes contain commercial place.
quantities of sulphur.i! The occurrence of these From these brief observations, it is fairly safe
domes appears to be limited mainly to the Gulf to conclude that sulphur should be stored in a
Coast region of the States of Texas and Louisiana. cool, dry place under cover to prevent contamination
Details of the mining and production of sulphur by moisture, carbonaceous matter, etc. When
are contained in a highly informative circular en- stored in the open,a certain amount of moisture
titled "Sulphur-General Information" issued by will be absorbed from the air or rains, as will be
the United States Bureau of Mines-! and anyone carbon and silica which are present in the particles
interested would be well-advised to procure a copy of dust in the air. The first component, moisture,
of this publication. helps the oxidation of sulphur to H 2S0 4' while
The element sulphur is non-metallic and exists the second, carbon, may form a carbonaceous scum
in a variety of allotropic forms and therefore may on the surface of the molten sulphur in the burner,
be said to have a series of properties depending on or, alternatively, ignition of the carbon will occur,
the form in which it is found. Natural sulphur the CO2 formed causing dilution of the burner gas.
usually occurs as the more stable rhombic or The silica increases the ash content of the sulphur
a-sulphur form. However, it can exist in many and this in itself is a nuisance in that it would
forms," but they all tend to revert to the rhombic involve frequent ash removal from the burner.
form. A study of the various properties and Obviously, these three constituents, i.e. H 20,
allotropic forms of sulphur is outside the scope C and SiO 2' would, if present in sufficient quantity,
of this paper and a brief account of those properties affect the rate of burning of the sulphur in addition
of relative importance to sulphur burning only, to altering the final composition of the burner gas.
will be given. Sulphur, S 8' is a brittle, yellow ele- It is not suggested here that storing sulphur in the
ment which is solid at room temperature, is in- open would involve the above contaminants being
soluble in water, but will dissolve in carbon bisul- present in quantities sufficient to affect the efficiency
91
of the burner, but it is possible that in many cases The makers suggest the following capacities for
they may reach a proportion where they cause a burner 30 in. in diameter and 8 ft. long.
trouble.
Types of Burners. Capacity with l in. water draught is 1351bs. Sulphur
per hour.
(a) Rotary Burner.
This burner is proably the most commonly used Capacity with ~--1 in. water draught is 200 lbs.
and is known as the Glens Falls Rotary Burner. Sulphur per hour.
The makers, Glens Falls Machine Works of America,
claim that maximum efficiency can be attained with Capacity with 2 in. water draught is 270 lbs. Sulphur
unskilled labour and that installation and operating per hour.
costs are low. Furthermore, they emphasise that
losses due to sulphur sublimation or formation of A burner of identical diameter, but only 6 ft. long
SO 3 can be eliminated almost entirely.'! With would have corresponding capacities of about 75
this type of burner it is possible to operate con- per cent. of those given above. As a rough guide,
tinuously at SO 2 concentrations ranging between it may be taken that:- .
5 per cent. and about 18 per cent. In order to For a 1 in. draught, the burner consumes approxi-
prevent fluctuations in gas strength it is desirable mately 2 lbs. Sulphur/sq. ft.yhr.
to feed the sulphur by mechnical means and not
by hand. For a £-1 in. draught, the burner consumes approxi-
The sulphur in the lower part of the horizontal mately 3 lbs. Sulphur/sq. ft./hr.
rotating drum forms a molten pool as well as a thin For a 2 in. draught, the burner consumes approxi-
film around the circumference of the drum. This mately 4:.2 lbs. Sulphur/sq. ft.yhr.
film, in effect, increases the surface area of the
sulphur exposed to the incoming air and a further Another authoritv" considers that a burner 36 in.
increase in surface area is brought about by the in diameter and '·8 ft. long is capable ·of handling
sulphur that drips down from the top of the drum. nearly 8 lbs. of Sulphur/sq. ft./hour. Fairlie!
These factors help to increase the capacity of the finds it practical, without resorting to high draught,
burner and ensure that combustion is complete. to run a burner 4: ft. in diameter at a rate of 1 ton-
On top of this, it is claimed that the sulphur film of Sulphur per day per foot of length.
protects the drum metal from deterioration due to
hot SO 2 gases as the heat conductivity of sulphur The size of the combustion chamber is variable
is less than that of cork. between fairly wide limits and it should be borne
in mind that a large chamber permits a higher
A combustion chamber is fitted at the back of concentration of SO 2 in the burner gas without
the horizontal drum and this serves to complete danger of sulphur sublimation. It is suggested that
the combustion of any sublimed sulphur as well as
a chamber spa e of 60 cubic feet per ton of sulphur
to mix the gases and dilute them to the desired
per 24 hours- is adequate, while the makers of this
strength. This chamber is therefore constructed type of burner indicate that a minimum space of
so as to have air ports and one or more baffles. (it cubic feet per pound of sulphur per hour per
Impurities in the sulphur do not readily affect square foot of burner area should suffice for burners
the operation of these burners because the rotation up to 30 in. in diameter. These figures should be
of the drum agitates the molten sulphur sufficiently taken as approximate indications only and no hard
to prevent any blanketing films forming on the and fast rules seem to apply. The size of the
surface. A further refinement that can be added combustion chamber should be dictated by practical
is a sulphur melter and the heat of radiation from considerations and previous experience.
the burner may be utilised to keep the sulphur
molten. Steam heating coils in the Melting Tank Sutermeister'" states that rotary sulphur burners
are only required for starting up the burner after produce a gas of varying composition owing to
a long shut-down. In order to further improve sudden rushes of cold air through the apparatus,
the efficiency of this machine, the molten sulphur but Fairlie" claims that with a continuous feed, it is
should be strained prior to passing it to the burner. possible to maintain the gas at a uniform con-
The Teeding of molten sulphur ensures that the centration of SO 2 with only minor fluctuations.
burner is handling moisture-free material. He stipulates, however, that this is dependent on
Ideal results are obtained with this type of burner the depth of the molten sulphur in the rotating-
by using sulphur of a minimum purity of 99.6 cylinder being kept uniform. Any change in this
per cent. .The molten sulphur in the horizontal depth will alter the area of the unsubmerged film-
drum should be at the highest possible level without covered surface and this in tum will alter the rate
allowing any overflow to take place. of combustion of sulphur.
92
Anyone wishing' to study in detail the design of A rotary steel or cast-iron burner operating
a spray type burner is well-advised, to read the continuously has been found to convert between
paper by Conroy and johnstone" on this subject. 1 per cent. and 2 per cent. of the S02 into S032,
The authors indicate that the internal volume of a while a similar burner lined with refractory brick
rotary burner should be 13/14 cubic feet per ton of will produce a gas of much lower trioxide content.
Sulphur per day and on top of this a combustion Obviously, then, the materials of construction have
chamber space of 60 cubic feet per ton of Sulphur an effect upon the oxidation of SO 2and an investig-
per day is required, whereas the total volume of a ation led to the discovery that certain metals or
spray type burner is 24 cubic feet per ton of Sulphur their oxides could increase the rate at which trioxide
per day. was formed. These metallic substances are known
It is felt that the three burners listed cover the as catalysts and while they do not take part in the
types of particular and possible interest to the sugar reaction in a quantitative way, that is to say, they
industry. In order to complete our practical con- are not used up or depleted during the course of
siderations of sulphur burning, it is only necessary oxidation, they most certainly speed up the rate of
to study how SO3 formation. occurs and what can reaction. These substances, therefore, warrant
be done to minimise its formation as this information study as well. .
should then make it possible to successfully produce It will probably be advisable to study the various
a gas that is rich in SO2 and, at the same time, free effects of physical and chemical conditions tlpon
of all but traces of SO3' trioxide formation separately to ensure that the
The Formation and Dissociation of SO 3'
picture be complete.
The conditions favouring the formation of SO a Effects of Excess Air,
are:-
Comog'" and co-workers found that when sulphur
(i) Decomposition of any sulphuric acid that vapour was burned in the presence of 250 per cent.
may be present in the commercial sulphur. excess air at 4:60°C., approximately 3.4 per cent.
(ii) Formation of trioxide during the actual to 3.8 per cent of the sulphur appeared as the
burning of the sulphur. trioxide. However, Browning and Kress'" observed
(iii) Oxidation of the SO 2 present in the burner less than 0.02 per cent. conversion under similar
gas. conditions in the absence of a flame. The obvious
The first source accounts for only a relatively inference is that atomic oxygen in a flame has a
small amount of the SO3 normally found in burner considerable influence upon the reaction. The
gas. Naturally, sulphur will oxidise. to a certain results of their experiinents indicated that trioxide
extent in the presence of moist air, but the amount formation could be reduced by decreasing the
of sulphuric acid formed is bound to be extremely equilibrium conversion of SO2 to SO 3 by keeping
small. the quantity of excess air at a minimum in con-
junction with high combustion chamber temper-
Undoubtedly, a certain amount of trioxide will atures. A perusal of the theory will show agreement
be' formed during the burning of the sulphur, but with this statement.
this is difficult to determine accurately. It will
depend, to a large extent, upon the proportion of Obviously, then, the amount of air supplied to
excess air present and upon the temperature reached the burner should be carefully metered, or, failing
in the burner. It can be seen therefore that the that, regular analyses of the gases from the com-
SO ~ content of the gas should be as high as possible bustion chamber should be carried out to ensure
for the type of burner in use. that the SO 2 content is being maintained at a
maximum.
The third source, i.e. the oxidation of SO2.
accounts for the major portion of trioxide found in A rough guide to the correct amount of air re-
a burner gas and consequently this aspect of the quired is based on observation of the flame in the
problem will have to be examined in fairly minute burner. If the sulphur burns with a blue flame,
detail. In practice it has been found that oxidation conditions are just right. A flame with a brown
will take place only until a certain ratio of dioxide tinge indicates insufficient air and sublimation of
to trioxide is reached.. At this point equilibrium sulphur. However, these observations do not
is established between the reactants and products prevent one from operating the burner with' an
oof the reaction and as fast as SO 3 is being formed, excess quantity of air and one is well-advised to
it"is again decomposed into SO2 and oxygen.. This rely more on chemical tests and mechanical aids
equilibrium may be distrubed or changed by altering than on rule-of-thumb methods such as those men-
the concentration of the reactants on either side of tioned above.
the equation: A study of Table VII will show how the quantity
O 2 + 2S0 2 ~ 2S0 3 of excess air can influence the formation of SO 3'
94
Should the burner be operated with insufficient It ' is well worth .remembering 'that the final
air to complete the combustion of sulphur, then equilibrium condition of the reaction depends only
sublimation takes place and slight mists of unburned upon the temperature and the composition of the
sulphur may form. gas mixture, and oxidation of SO 2 will take place
until a certain ratio of trioxide to dioxide is reached.
Influence of Temperature. High temperatures favour a low ratio and low
temperatures a high ratio of SO 3 to SO 2. 7
Theory has already indicated to us that temper-
ature exerts a considerable influence upon the
Presence of Moisture.
amount of trioxide formed. In practice it has been
found that the optimum temperature range favour- The air drawn into a burner is not normally
able to the formation of SO 3 lies between MO°C dried, but to prevent the formation of corrosive
and 980°C22. Frohberg-" found that maximum sulphuric acid mists, the water content of the air
oxidation occurred at 4000 - 5 0 0 ° e . , while at an used should not be more than 5 mgm. per cubic
approximate temperature of 900°/1,000°C., dissoci- foot of air at S.T.P.24 Under conditions prevailing
ation took place. It has been shown that at in Natal, this would involve drying the air with
1,000°C. nearly 50 per cent. of the SO 3 formed is either concentrated sulphuric acid or P 20 5 or :a
decomposed, this decomposition starting at 700°e. similar efficient drying agent.
at which temperature the conversion of SO2 to
S03 is about 60 per cent." Above 1,000°e. the If the air is thoroughly dried with P 205' there
dissociation of the trioxide is more rapid than its is little oxidation of SO 2 up to a temperature of
formation. It may be generally stated that below 450°e. and in general it may be stated that dry
400°e. the rate of formation of SO 3 is too slow to air helps to retard oxidation. In the presence of
be regarded as a nuisance, while above 1,000°e., water vapour, oxygen does not combine with SO2
even though SO 3 is formed rapidly, the rate of at 100°e. but oxidation does occur, even at this
decomposition predominates. However, even at low temperature, if particles of liquid water are
305°e., oxidation of S02 has been found to occur, present. 6 Mellor" found that moisture does not
albeit at a very slow rate." Thus we have two con- appear to affect the oxidation of SO 2' but the
flicting states, viz. where the rate of conversion of presence of CO2 and nitrogen causes more SO 3
SO 2 to SO 3 increases rapidly with increasing to be formed.
temperature, but where the dissociation of SO 3
overhauls the rate of conversion, and at the higher Moisture has a poisoning effect on some catalysts
temperature (above 1,000°e.), therefore, the per- and Tolley" has shown this to be true for iron
centage conversion, as measured, tends to decrease. oxide. Upon continued exposure, however, cata-
lysis slowly increases until after 40 hours the
The reaction: catalysis with wet gases is half that of dry gases.
He found that water vapour has its greatest in-
2S0 2 + O 2 ¢ 2S0 3 hibiting action at a temperature of 475°e., put
takes place nearly to completion at 450°C. in the even at 635°e., the catalytic activity of iron oxide
presence of a catalyst, and. it has been shown that, is reduced to ! of that with dry gases.
'while the rate of the forward reaction is only
moderate at 400°e., it increases to 40 times this Browning and Kress? investigated the dew-point
value at 500°e.,the decomposition reaction only of burner-gas mixtures and showed that the cor-
becoming perceptible at 550°e. and upwards. rosion to be expected would be greatest at the dew-
It may therefore be said that up to a temperature point of the particular gas because of the combined
of 450°C., reaction of formation prevails, and only action of scale and condensed liquid upon the metal
well above this temperature does dissociation come base. Above the dew-point, only gases are present
into play.25 and corrosion is much reduced, while at temper-
atures below the dew-point, the rate of corrosion
Sulphur trioxide is very stable in the absence is considerably less on account of the slowing up
of contact substances. and once formed is difficult of the chemical reactions at these lower temperatures.
to dissociate. Generally, decomposition will not Their experiments revealed that the dew-point
take place completely at temperatures as high as increased as the SO 2 content of the gas was raised
1,100°/1,200°e. Decomposition of trioxide already and for safe operating practice, using moist air,
formed cannot be relied upon to keep the loss from the temperature of the gas in iron should be kept-
this source at a reasonable value at temperatures above 200°C. to prevent undue corrosion of the
below 1,00°e., the amonnt of dissociation at this metal. When the gas is required to be cooled
temperature only reducing the loss by an amount below this temperature, it should be transferred to
of less than 0.5 per cent. a lead pipe.
95
As previously stated,. moisture in the air can The catalytic effect of iron compounds depends to
cause mists to form in the burner gas and these are a large extent upon their physical and chemical
most difficult to, remove. A method which helps state. Experiments have shown that iron oxides,
in the removal of mists consists of cooling the mixed as such, are not good catalysts, but their activity
gas to below 46°C., when the S03 will condense. may be increased after a certain period by the
The gas should now be passed through a filter-box formation of sulphates and other compounds.
packed with charcoal or iron borings and then At elevated temperatures both the dioxide and
through a water-spray .scrubbing tower. This trioxide react with iron, and this would explain
method, however, is not always very successful the short life of iron under these conditions of
and it is easier to prevent mists than, having once service.
formed, to remove them.
In a rotary sulphur burner, there will be surges
of SO 3 formed when starting up or burning down
Action of Catalysts.
as more iron will be exposed during these periods.
Catalysts do not affect the equilibrium point of Furthermore, the temperature range at which -
a gas, mixture, but merely alter the rate at which maximum SO 3 formation occurs will be passed
equilibrium is approached. The ratio of the original through during these stages."
and final substances present in the gas will not be
Reverting to the influence of physical state upon
changed upon contact with a catalyst. The contact
catalytic activity, it is worth noting that ferric
substance will only ensure that this equilibrium
ratio, is reached in less time. oxides may exhibit contact properties, and the
surface of the material will exert the least influence
A list of various contact substances normally when freshly precipitated oxides, which are not yet
encountered follows, and these, with their effects dried, are used. The activity increases if the oxide
upon SO 3 formation, have been listed separately has been moderately heated or kept for a long time
for the sake of clarity. Anyone wishing to know so as to become dry. Oxides obtained by heating
more about the effects of various catalysts on SO 3 ferric- or ferrosulphate give a much lower contact
formation, should read the monumental work of action than that obtained with an oxide prepared
Browning and Kress," as this covers the subject by igniting a precipitated hydroxide or pyrites-
most comprehensively. cinders." An oxide containing 21 per cent. Arsenic
as As shows considerably more contact reaction
A. Iron Compounds. than that of a pure oxide at 700°C., while the
Iron or its oxides have long been known to exhibit addition of copper oxide to an oxide of iron is
catalytic properties as far as the oxidation of SO 2 favourable to the formation of S03. 26
is concerned and the Mannheim Process for the Observations have shown that when a burner
manufacture of suphuric acid utilised iron oxide gas is in contact with an iron pipe, maximum
as a catalyst. For reasons of efficiency, this oxide conversion occurs at 750°C., there being a 13 per cent.
has been replaced by either platinum or vanadium maximum conversion for a gas with a 10.5 per cent.
in the Contact Process. S02 concentration. This conversion drops to 10
per cent. when the SO 2 content is raised to 14 per
Tolley" predicted that the first reaction to occur· cent. and a further decrease in conversion to 3 per
when steel was in contact with sulphur dioxide cent. for a gas of 19.5 per cent. content is observed. 23
and oxygen at reasonably high temperatures, would At 1,000°C., the conversion at all concentrations
be a combination of oxide and sulphide formation, IS zero.
represented as:-
Ferric oxide begins to exhibit catalytic activity
2Fe + S02-+ 2FeO + S
at 550°C., and this activity increases to a maximum
Fe + S-+ FeS in the temperature range 6000 - 6 2 0 ° C . 6 Increasing
or alternatively:- the S02 content of the gas from 2-12 per cent.
5Fe + 2S0 2-+ 2FeS' + Fe 30 4 does not affect the conversion to any appreciable
He pointed out that as FeO cannot exist below extent, although with higher concentrations, the
570°C., the first reaction shown above could only yield of SO3 is lower. As a contact substance,
occur above this temperature. The experiments this oxide only becomes really effective at a temper-
showed that the catalytic activitiy of mild steel ature of 600°C. when a percentage conversion of
increased rapidly during the first few hours of SO 2 to SO3 of 40 to 50 per. cent.! is attainable.
exposure to S02' but after about 10 hours the In practice, however, the conversion never exceeds
activity became reasonably constant. It was felt 60-66 per cent.!"
that this initial rapid increase in the rate of oxid- Iron oxide formed from pyrites-cinders shows
ation of SO 2 was probably due to the formation of little activity, and this only begins above 650°C., .
iron oxide. increasing with temperature and reachirig a con-
96
version of 1 percent. at 1,000°C. with a gas con- Furthermore, the sulphur feed should be
taining 15 per cent. SO 2' However, it should be mechnical to enable a constant rate of feed to be
considered worthy of note that if 3 per cent. of SO 3 maintained. With. all these refinements it is
is formed in a burner gas during normal burning possible to arrange for high combustion temper-
operations, this figure may, under favourable atures and a burner gas containing the highest
conditions, be raised to three or four times this concentration of SO2 possible with the type of
value if the gases are passed through red-hot apparatus in use. Even better results will be
pyrites-cinders. 26 obtained if the sulphur. is melted and strained
before it is fed to the burner, for reasons already
Pure iron oxide exhibits maximum contact action gIven.
at 650°C., the respective conversion figures being
15 and 5t per cent. for gases of 10.5 and 19.5 per The combustion chamber should be fitted with
cent. SO 2 content. These conversion figures drop one or more baffles to ensure thorough mixture of
•to 4i and Ii per cent. respectively when the temper- the gases and prevent any possibility of unburned
ature is raised to 1,000°C., the activity in this sulphur passing to the absorption plant. Coolers
case being only above 500°C.7 are normally fitted after the combustion chamber,
and it is imperative that cooling of the gas be as
Ferrous sulphate has a maximum contact action rapid as possible to minimise SO 3 formation.'
at 650°C. when the conversion of a gas containing Initially the gases would be air- or. water-cooled
15 per cent. S02 is 12t per cent., this conversion and then passed to either a direct or indirect cooler
decreasing to t per cent. at 1,000°C. Similar con- to bring the temperature down to 200°/300°C.
version figures for ferric sulphate are 8 per cent. at At this stage, if further cooling is attempted, the
650°C. and t per cent. at 1,000°C.; indicating that pipes conducting the gases should be lead-lined.
it is less active than the ferrous form. The subject of cooling is outside the scope of this
paper, but is well-worth : pursuing. by reading
All the above observations indicate that iron in Lundberg- and others.
its many forms exhibits varying degrees of catalytic
activity and if the formation of. SO 3 is to be mini- Summary.
mised then obviously gases of high S02 concen-
tration must be produced at the highest possible The practice of sulphur burning, the production
combustion chamber temperature that can be of SO 2 and the formation and dissociation of SO 3
attained in practice. It is of further benefit to has been outlined and the effects of:
note that in many instances, the amount of SO 3 Excess Air,
that will be formed according to theory will not be Temperature, and
reached in practice as the gas passes through the
Catalysts
combustion apparatus before equilibrium is reached.
upon SO 3 formation detailed. Where possible a
comparison with the theory has been made and it
Silica and Silicates.
has been shown that the following points all help
It is generally conceded that vitreous fused to increase the efficiency of this type of plant:-
silica exerts no catalytic effect on the oxidation of
S02.7 The same applies to Dialite brick, and (a) It is preferable to feed the sulphur con-
therefore these materials are considered satisfactory tinuously by mechnical feeder. The feeding
for the lining of furnaces, combustion chambers, of strained molten sulphur is preferable as
etc. this eliminates moisture and deleterious hydro-
carbons.
The Efficient Operation of a Burner. (b) The quantity of excess air should be carefully
controlled and the SO2 content of the burner-
In America it is a generally accepted fact that gas kept at a maximum.
the air to the burner should be carefully metered
by mechanical means and furthermore, allowance (c) The temperature of the burner and com-
is made for fluctuations in the burner. These bustion chamber must be maintained above
changes in burning rate are catered for by the 1,000°C. if at all possible.
installation of an automatic recording device which (d) Automatic recording and operating apparatus
continuously analyses the SO2 content of the .to maintain an even feed of sulphur and
gases from the combustion chamber. A diaphragm constant SO2 content of the gas is helpful.
operated valve then automatically operates the
air inlet and sulphur feed and regulates these, (e) The gas from the combustion chamber should
thereby keeping the SO 2 content of the burner gas be filtered and cooled as rapidly as possible
constant within fairly narrow limits. to prevent formation of SO 3'
97
Many of the improvements listed may possibly Glens Falls Machine Works.
12 Darrah: The Preparation of S02-Paper Trade Journal,
make the production of SO 2 by these methods rather pp. 132, Nov. 30, 11.)50.
costly and their inclusion should not be taken as 13 Sutermeister: Chemistry of Pulp and Paper Making.
a recommendation, but rather as a guide or example 14 Josephson and Downey: Sulphur and Pyrites-U.S. Bureau
of how efficiency may be improved. .These refine- of Mines Yearbook, lU49.
ments are in practice in America in many of the 15 Ridgway: Sulphur-General Information-U.S. Bureau
of Mines I.C. 6329. . .
larger paper mills, so obviously they are economical 16 Sulphur: Technical Service Note No. 32-African Explosives
for the production of large quantities of SO 2' and Chemical Industries, Ltd.
17 Furniss: Rogers Manual of Industrial Chemistry.
It is admitted that it is literally impossible to 18 General Description of Acme Burner-Pamphlet from
prevent the formation of SO 3 entirely, but if pre- Acme Coppersmithlng and Machine Co.
cautions, along the lines of those mentioned in this 10 Cain and Chatelain: New Low-Capacity Sulphur Burner-
paper, are taken, the quantity of SO 3 can be reduced Chemical and Metallurgical Engineering, 46, Oct. 1939.
to such a low level that it no longer constitutes 20 Kress and Others: Spray Type. Sulphur Burner-The Paper
Mill, Oct. 11.)34.
a nuisance. 21 Conroy and Johnstone: Combustion of Sulphur in a Venturi
Spray Burner-Industrial and Engineering Chemistry 41, pp.
The types of burners listed were limited to those 2741, Dec. 194U.
generally used in the. Sugar Industry and those 22 Barker: Sulphite Acid Preparation-Paper Trade Journal,
which may be of interest. The spray type burner pp. 136, Nov. 30, lU50.
is proving very popular in America and it produces 23 Newell. Stephenson: Pulp and Paper Manufacture, Vols. I
II and III.
a gas of low SO 3 content and furthermore it is very 2< Modern Chemical Processes.
flexible in that it may be started or shut down in 25 Riegel: Industrial Chemistry.
a very short space of time. Control is easier than 26 Lunge: Manufacture of Sulphuric Acid and. Alkali, 3rd
with the conventional rotary burner and paper Edition.
mills in America have found that installation costs 27 Tolley: The Catalytic Oxidation of SO 2 on Metal Surfaces
Journal Society for Chemical Industry, 67, pp. 369, Oct. 1948.
are not excessive. Maintenance costs are low
and power consumption compares most favourably READING LIST.
with other types. Chemical Engineering-53, 225 (1946).
F or the sake of those who would like to know 54, 221 (1947).
Chemical Engineering Process-46,614 (1950).
more about sulphur burning and its applications,
Chemical Markets-30, 261 (1932).
a reading list has been added. Chemical and Metallurgical Engineering 42, No. 7,374-7 (1935)
Chemical Process Principles-Hougen and Watson.
Acknowledgments. Industrial and Engineering Chemistry-17, 593 (1925).
Our sincere appreciation and thanks are duly 34, No.9, 1017 (1942).
35, 522, 541-5 (1943).
made to those firms and Institutions in America
41, 2741 (1949).
who corresponded with us, supplied technical 42, No.4, 713-8 (1950).
articles and generally went out of their way to be 42, 2215-7 (1950)
helpful.' In particular we would like to mention:- Industrial Chemistry-Riegel.
The Paper Institute, Texas Gulf Sulphur Company, Journal Am. Chern. Soc.-48, No. 11 (1926).
Acme Coppersmithing and Machine Co., and the Chern, Soc.-123, 3203 (1923).
Glens Falls Machine Works-all American organis- Paper Trade Journal-94, No. 15, 39-42 (1932).
ations that were extremely helpful and co-operative. " " " 99, No. 17,48-51 (1934).
Proc. Roy. Soc. London-Series A, 138, 635 (1932).
REFERENCES. Pulp and Paper Mag. Canada-31, No. 52, 1390-3 (1931).
1 Beater: The Distribution of Temperature in the Sugar Belt 33, No.2, 78-80 (1932).
of Natal and Zululand-S.A.S.T.A. 1949. Conv. 37, No.3, 140-8 (1938).
2Lundberg: Acid Making in the Sulphite Pulp Industry. 44, No.4, 320 (1943).
3 Chemical Control Plant Data: Booklet issued by Chemical 52, 108-111 115 (1951).
Construction Company.
"" "" Conv. 243-8 (1951).
4 Fairlie: Sulphuric Acid Manufacture.
Soc. Chern. Ind. Journal-67, 369-73 401-4 (1948).
5 Lewis and Randall: Thermodynamics and the Free Energy
of Chemical Substances. Textbook of Physical Chemistry-Glasstone.
6 Mellor: A Comprehensive Treatise on Inorganic and Trans. Am. Inst. Chern. Engs.-27, 264 (1931).
Theoretical Chemistry-Vol. X .. U.S. Bureau of Mines-Bulletin 406 (1\)37),.
98,
15 6 79 12.48 187.0 16.02 187.0 15. I 6000 9.53 9.75 9.74 9.67 0.985
13 8 79 16.31 140.3 12.26 140.3 1l.3
II 10 79 19.98 112.2 10.01 112.2 9.1 7000 2.62 2.55 2.56 2.58 0.412
9 12 79 ' 23.50 93.5 8.51 93.5 7.5
5 16 79 30.1.5 70.1 6.63 70.1 5.7 800 0
0.915 0.859 0.864 0.879 1. 944
3 18 79 33.30 62.3 6.01 62.3 5.0
1 20 79 36.33 56.1 5.51 56.1 4.5 ,900° 0.384 0.349 0.353 0.362 1.559
1000° 0.1845 0.163 0.167 o. in 1.236
TABLE II. 1200° 0.0573 0.0485 0.O511 0.0523 2.719
Weight and Volume'of Burner Gas at S.T.P. based on One Pound
of Sulphur-Air Saturated with Water Vapour. 14000 0.0235 0.0193 0.0209 0.0212 2.326
Compositionof Burner Gas. Quantity of Quantity of Air. 16000 0.01l7 0.0093 0.0104 0.0105 2.021
% by Volume.. %50, Burner Gas.
Oxygen. SO, Nitrogen. Water Weight CubicFeet, Lbs. CubicFeet. Lbs. 1800° 0.0066 0.0052 0.0060 0.0059 3.771
14.8 5.9 77.7 1.6 12.36 190.2 16.18 190.2 15.3 2000° 0.0041 0.0032 0.0038 0.0037 3.568
12.8 7.9 77.7 1. 6. 16.21 142.0 12.34 142.0 1l.4
10.9 9.8 77.7 1.6 19.71 114.5 10.15 114.5 9.2
8.9 1l.8 77.7 1. 6, 23.26 95.1 8.60 95.1 7.6 TABLE VI.
4.9 15.8 77.7 1.6 29.97 71. 0 6.67 71. 0 5.7 V!'riation of Equilibrium Temperature with Burner Gas Com-
3.0 17.7 77.7 1.6 32.99 63.4 6.06 63.4 5.1 position Assuming Degree of Conversion of S02 to SOa-Dry Air.
1.0 19.7 77.7 1:6 36.05 57.0 5.55 57.0 4.6
Equilibrium Temperature
Degrees Centigrade.
Gas SO, 6% 8% 10% 12% 16% 18%
TABLE III. % Conversion. Composition 0, 15% 13% 11% 9% 5% 3%
17
VOLUME OF BURNER GAS-DRY AIR.
WEIGHT OF BURNER GAS DRY AIR
IS
SCALE A: UNITS = LBS.
UNITS x 10 "CUBIC FEET.
~ 13
Z
:J
Cl:
":"1
III
oJ
~III " ~ ;
6 10 -e- 6 18 2
% SO, BY VOLUME.
GRAPH "B"
17
VOLUME OF BURNER GAS MOIST AIR.
~ WEIGHT OF BURNER GAS-MOIST AIR.
IS
SCALE A: UNITS LBS.
UNITS x 10 co CUBIC FEET.
13
"
9
6 20
0;.50, BY VOLUME.
100
1500
U
0
III
~.
a: 1250
~
36 36
...
:J
~-4i
~o ,{J"" U 8'Pi
<t':
~o
~..
~
.
III
J:
o ' q,1i
~ $\0
~i'
...
~..~~
\ r-
0
:r
m
n
III
a:
SI~
~O~""'"
. , ~",1l
34
:r
0
r:
m
...
III ~..I ~\~ n
~\tf-~ C
s
:JD
.
III
J:
III
otP\V C
s
:JD
~ ... -750 32 ~
m m
Ci s:I
:I
:-4 :-4
30 500 30
6 I~ I~ 6 10 104 18 22
%50, BY VOLUME. %50, BY VOLUME.
GRAPH "E"
Log" K. \'I. TEMPERATURE
FOR REACTION: S0, + ~O, SO,.
+
+1
0
500 700 900 1100 1,3pO l~ h l.7oo 1900 2100
il
I
TEMPERATURE °C.
'-1
101
GRAPH "F"
EQUILIBRIUM TEMPERATURE VI. % CONVERSION.
100
80
Z
0 -60
iii
II:
'"
>
Z
0
U --40
~
20
5 1,100
TEMPERATURE C.
GRAPH "G"
VARIATION OF EQUILIBRIUM TEMPERATURE WITM
5
SO, CONCENTRATION AT LOW CONVERSION PERCENTAGES.
Z ~
0ll'
0
~ -!<~
0ll'
'"
>
z
9
0
U
2
~
BOO 1000 12 20 2
TEMPERATURE C.
102
Mr. Dymond said that they were indebted to the of capacity or interruption for cleaning, the sulphur
authors for this very important paper: .He expressed had to be kept free from dust and moisture. It
the view that the standard of papers at the Congress was therefore routine at the Java factories to store
was very high. This paper provided data that had the sulphur in a separate compartment, and
been wanted for many years. particularly not in the store-room where lime was
kept.
Mr. Main agreed and said that the paper was a
most valuable addition to the technical knowledge. Mr. Main expressed the view that sulphur storage
He referred to Maxwell's book on sulphur burning conditions did not materially affect the sulphur
which was now out of print. Since then he had not used in burners in Natal.
found anything as valuable as the paper presented. Mr. Hogarth said he was inclined to agree with
He hoped that it might be possible to provide Mr. Main, as the contaminants in the sulphur
illustrations. supplied to the Sugar Industry were very small
Mr. Hogarth said the point had been discussed indeed.
and photostat copies of a paper dealing more Mr. Rault said the problem in the Sugar Industry
especially with one type of sulphur burner could be was not only to burn the sulphur but also to absorb
made. He hoped that these could be fairly generally it. He asked whether there was a more modern,
distributed. compact' and controllable absorbtion system than
the "eye sore" and dirty plant called the sulphur
Mr. Rohloff said he thought the three types of
tower, commonly used in our factories.
sulphur burners could be classed as three separate
stations in the development of sulphur burners. Mr. Hogarth said that the absorption of SO2 was
Much the same could besaid about the development a most complicated question, but there was equip-
of boilers. He drew a parallel between the different ment available which would assist in the absorption
types of sulphur burners and the different types of more efficiently than was done at the moment in
boilers. This development seemed to suggest that the Industry. He offered to, supply this inform-
the trend was towards greater flexibility and he ation to Mr. Rault.
thought it was fit to mention this, as it indicated Mr. Dymond agreed that the problem of hot
a desire to make sulphur burners for the Sugar gases going into the juices required further in-
Industry more flexible and more applicable to sugar vestigation and he hoped this would be done by the
production. Mr. Rohloff said that they had asked S.M.R.I.
the S.M.R.I. about the Acme burner and were told
that this had been investigated, but the type of Mr. Barnes referred to the possibility of using
sulphur used in the Industry was not applicable to S02 instead of raw sulphur in the Sugar Industry, as
this burner. increasing quantities of SO 2 were being generated
by industry.. He thought the possibility of using
Mr. Hogarth .said the sulphur supplied to the cold gases should be investigated more thoroughly.
Sugar Industry did not vary in composition froin the He referred to the use of liquid ammonia as a
sulphur used overseas and presumably used in fertiliser and said it was not many yeCjlrs since this
Acme burners. had been thought impossible, but today most of the
Mr. Perk said that speaking from memory, he nitrogen used in Louisiana was applied in the form
had told Mr. Rohloff that the method of storing of gas or liquid. He felt the same might apply to
sulphur in Natal precluded the sulphur being used gaseous S02 in the Sugar Industry.
in the closed type of burner used in J ava. In order Mr. Dymond concluded by calling for a hearty
to operate these burners for months without loss vote of thanks to Mr. Hogarth for hisexcellent paper.