Calcium Carbide 1

Calcium Carbide
Bernhard Langhammer, SKW Trostberg AG, Trostberg, Federal Republic of Germany

1. Introduction . . . . . . . . . . . . . . . 1 4.5. Furnace Gas . . . . . . . . .. . . . . . 8

2. Physical Properties . . . . . . . . . . . 2 4.6. Mass and Energy Balance . . . . . . 9
3. Chemical Properties . . . . . . . . . . 2 5. Further Treatment . . . . .. . . . . . 9
4. Production . . . . . . . . . . . . . . . . 2 5.1. Cooling . . . . . . . . . . . . .. . . . . . 9
4.1. Raw Materials and Their Prepara- 5.2. Size Reduction . . . . . . . .. . . . . . 10
tion . . . . . . . . . . . . . . . . . . . . . 3 5.3. Quality Specifications . . .. . . . . . 10
4.2. Electrothermic Reduction . . . . . . 4
5.4. Transport and Storage . . .. . . . . . 11
4.3. Furnaces . . . . . . . . . . . . . . . . . . 4
6. Environmental Protection . . . . . . 11
4.3.1. Single-Phase Furnaces . . . . . . . . . . 4
4.3.2. Three-Phase Furnaces . . . . . . . . . . 4 7. Uses . . . . . . . . . . . . . . .. . . . . . 11
4.3.3. Half-Covered Furnaces . . . . . . . . . 5 8. Economic Aspects . . . . . .. . . . . . 12
4.3.4. Closed Furnaces . . . . . . . . . . . . . 5 9. Toxicology . . . . . . . . . . .. . . . . . 12
4.4. Operation . . . . . . . . . . . . . . . . . 7 10. References . . . . . . . . . . .. . . . . . 12

Based on the article in Ullmann’s Fifth
Edition by Friedrich-Wilhelm Kampmann,
Wilhelm Portz, Friedrich-Karl Frorath,
Heinz Oettel and Bernhard Langhammer
1. Introduction
Of all the carbides (→ Carbides), calcium car-
bide [75-20-7] is the most important industri-
ally. It is still the basis of the acetylene welding-
gas industry where raw materials and energy are
available and petroleum is in short supply. Cal-
cium carbide is produced in a number of coun-
tries as the starting material for the products of
acetylene chemistry. The fertilizer cyanamide
(see→ Cyanamides) and derived products are
still produced to a limited extent. Besides these
classical applications, calcium carbide is used
for desulfurization of pig iron and steel, and in
foundry technology, where it is mixed with other
metal treatment additives.
History. The chemical composition of cal-
cium carbide was first recognized in 1862 by
Wöhler. He carried out a synthesis starting
from a calcium – zinc alloy and coal. Before this,
various others had prepared calcium carbide in
the laboratory, usually making use of the action
of an electric arc on coal or coke products in the
presence of calcium compounds. Towards the
end of the last century the industrial production
of calcium carbide in electrothermic furnaces
was developed. Independently of each other,
Moissan in France and Morehead and Will-
son in the United States laid the foundations,
in 1885 – 1895. The year 1895 saw the first pro-
duction carbide furnace, operated by the Willson
Aluminum Company, Spray, United States.
In 1897 Bertolus proposed the use of mul-
tiphase electric current for industrial furnaces.
In 1904 Helfenstein constructed a furnace
that used a three-phase current with three elec-
trodes. These first furnaces had a power rating
of 3000 – 7500 kW, and evenhad provisions for
waste-gas recovery (Helfenstein barrier); within
fifty years, 40 MW furnaces were in operation.
Modern large electric furnaces, with power
ratings up to 60 MW, have Söderberg electrodes
and are completely closed so that the carbon
monoxide byproduct can be recovered. Devel-
opment in recent years has been in the direction
of reliable, medium-sized closed furnaces more
suited to the market situation and available raw
material.
An alternative route to calcium carbide is the
carbothermic process, which was operated dur-
ing 1940 – 1960 by BASF in Germany, but has
not been used since.

c 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

10.1002/14356007.a04 533
2 Calcium Carbide
2. Physical Properties
Calcium carbide [000075-20-7], CaC2 , M r
64.10, is colorless and odorless when pure. Ow-
ingto the presence of impurities, various colors,
from gray to brownish black, occur in technical-
grade carbide, at times even violet or red-brown
tones. The typical odor of technical-grade cal-
cium carbide is that of phosphine, which is
formed in moist air from traces of calcium phos-
phide. The melting point of pure calcium carbide
is 2160 ◦ C [1]; above 2500 ◦ C complete decom-
position takes place [2], [3]. Four modifications
of calcium carbide are known:
– Phase I: tetragonal, stable between 25 and
440 ◦ C
– Phases II and III: lower symmetry, stable be-
low 440 ◦ C
– Phase IV, face-centered cubic, stable above
440 ◦ C
Commercial calcium carbide is mainly
phase I. Phase II is formed in some pure prepa-
rations [4–8]. The heat of transformation of cal-
cium carbide at 440 ◦ C is 8.68 J/g [9].
The CaC2 – CaO phase diagram (Fig. 1) [1] is
a simple eutectic system without compound for-
mation or solid solutions; the pure components
are not miscible with each other to a significant
extent in the solid state. Above the liquidus line
there is complete miscibility. Technical-grade
calcium carbide has a lower liquidus tempera-
ture owing to the presence of impurities.
Figure 1. Phase diagram CaC2 − CaO
The average specific heat capacity between
20 and 440 ◦ C is 1047 J kg−1 K−1 ; the heat of
fusion of pure calcium carbide is 1470 J/g [10].
The standard enthalpy of formation of CaC2
from the elements at 298 K and the standard en-
tropy of CaC2 at 298 K are ∆H = − 59.4 kJ/mol
and S = 70.3 J mol−1 K−1 [11], [12], [13].
The electrical conductivity of calcium car-
bide depends strongly on the degree of purity
and increases with increasing temperature. Val-
ues between 100 and 1000 Ω−1 have been re-
ported [14].
3. Chemical Properties
Commercially important reactions of calcium
carbide are conversion to calcium cyanamide
CaC2 + N2 −→ CaCN2 + C ∆H 298 = − 289 kJ/mol
hydrolysis to acetylene
CaC2 + 2 H2 O −→ C2 H2 + Ca(OH)2 ∆H 298
= − 128.4 kJ/mol
and the reaction with sulfur in molten iron
CaC2 + [S]Fe −→ CaS + 2 [C]Fe
Acetylene is produced smoothly at tempera-
tures below 300 ◦ C. Pure calcium carbide yields
346.89 L of dry acetylene per kg CaC2 at 0 ◦ C
and 101.3 kPa (372.66 L at 15 ◦ C, 101.3 kPa
(1013 mbar), saturated with water vapor). At red
heat, calcium oxide, hydrogen, and carbon diox-
ide are formed [15], [16]. The hydrogenation
of calcium carbide under pressure produces cal-
cium hydride and methane as well as other hy-
drocarbons [17].
Calcium carbide is soluble in molten salts,
such as lithium chloride, sodium potassium
chloride, and calcium chloride fluoride. Various
reductions can be carried out in these solutions
[18]. Electrolysis of calcium carbide dissolved
in a molten salt yields calcium at the cathode and
carbon at the anode.
4. Production
The preparation of pure CaC2 is only of aca-
demic interest. The industrial production of
technical-grade calcium carbide is based on the
reaction of quicklime with carbonaceous mate-
rials such as coke and anthracite:

CaO + 3 C −→ CaC2 + CO ∆H 298 = + 465 kJ/mol
The reaction rate becomes appreciable only
above 1600 ◦ C. Above 2000 ◦ C undesirable side
reactions become noticeable, especially
CaC2 −→ Ca + 2 C
CaC2 + 2 CaO −→ 3 Ca + 2 CO
For these reasons, all industrial processes op-
erate between 1800 and 2100 ◦ C and give a
technical-grade calcium carbide with a CaC2
content of ca. 80 %. The remainder is mainly
calcium oxide, but there are also other impuri-
ties from the raw materials, principally SiO2 and
Al2 O3 .
The energy for the production of the calcium
carbide must be introduced at very high temper-
atures. There are two possible routes:
1) Melting of the carbonaceous material with
CaO in a short electrothermic shaft furnace
2) Combustion of carbonaceous material with
pure or enriched oxygen in the presence of
CaO in a shaft furnace
The development of the second method has
now been discontinued after about 50 years be-
cause the synthesis gas byproduct can be made
more cheaply from petroleum. In Japan, research
has been undertaken to combine methods 1 and 2
[19], but all the calcium carbide produced today
is manufactured by method 1.
4.1. Raw Materials and Their
Preparation
The raw material or burden that is introduced
into the electrothermic furnace consists of a
carbonaceous component and a lime-bearing
component. The physical properties (particle
size, particle strength, conductivity, etc.) and
the chemical properties (content of volatiles, ash
content, etc.) of the raw material depend on the
type of carbide furnace and on the desired cal-
cium carbide quality. Smaller open furnaces do
not impose such strict demands because dur-
ing operation the conditions inside the furnace
may be observed and corrective action can be
taken, either manually or mechanically. With
high-capacity closed furnaces, the properties of
Calcium Carbide 3
the raw materials must allow the furnace to be
operated without outside intervention for at least
a few days.
The grain-size distribution of the raw mate-
rial must enable the carbon monoxide to escape.
In the reaction zone of the furnace the lime dis-
solves in the carbide melt, while the carbon com-
ponent reacts as a solid grain to produce calcium
carbide in the liquid. Therefore lime with a large
grain size can be used without affecting its reac-
tivity, but for the carbon component a finer grain
size is usually necessary.
Modern furnaces are fitted with hollow elec-
trodes through which fine-grained raw mate-
rial can be blown directly into the molten zone.
These manufacturing units only impose an up-
per limit to the grain size; the necessary fineness
is obtained by sieving.
Impurities, particularly metal oxides, cause
side reactions that waste energy. The principal
impurities are iron oxides, SiO2 , Al2 O3 , MgO,
and compounds of nitrogen, sulfur, and phos-
phorus. Oxides of iron and magnesium are com-
pletely reduced, the others only partially. The
iron combines with silicon to give FeSi, which is
liquid at reaction temperatures. It is partly emul-
sified in the carbide and can be tapped off. The
vaporization of magnesium and its oxidation by
carbon monoxide in the cooler parts of the fur-
nace lead to buildup of dust and solid incrus-
tations [20]. The oxides SiO2 and Al2 O3 are
generally dissolved in the carbide – CaO melt
along with the nitrides, sulfides, and phosphides
formed from the nitrogen, sulfur, and phos-
phorus compounds.
The following carbonaceous materials are
available: coke from bituminous coal or lignite,
anthracite, petroleum coke, and charcoal. Coke
from bituminous coal is used worldwide for cal-
cium carbide production.
Uncalcined anthracite and petroleum coke
can be used only as a part of the charge in a
closed furnace. If the volatile content is reduced
below 2 % by calcination, they can be used as
the sole charge. This is done in South Africa, a
country rich in anthracite. Charcoal can be used
only in small open furnaces.
Today for closed furnaces coke with a grain
size of 3 – 25 mm is used. The fraction below
3 mm is blown in through the hollow electrodes.
Small open furnaces can also use coarser grain
sizes. Before introduction, the coke must be
4 Calcium Carbide
dried below 2 % moisture content. Ash content
below 15 % is necessary to meet the quality stan-
dards for the calcium carbide product in many
countries.
The lime-containing component of the raw
material mixture is predominantly quicklime.
Manufacturing plants with large closed furnaces
specify a grain size of 6 – 50 mm, and the mate-
rial below 6 mm is blown in through the hollow
electrodes. For closed furnaces, the magnesium
content should be below 2 %. The lime must be
burnt so as to be as soft as possible, but resistant
enough for transport and storage. This is achiev-
able in modern lime kilns. At the same time the
CO2 content is reduced to less than 2 %.
The calcium hydroxide left behind after
acetylene generation from calcium carbide, af-
ter granulation or briquetting with calcination,
is also a cheap raw material. However, this lime
recycling is limited by the build-up of impuri-
ties.
Typical examples of compositions of raw ma-
terials for calcium carbide production are listed
in Tables 1 and 2.
Table 2. Composition of lime for calcium carbide production (wt %)
New lime
Total CaO 93.8
Free CaO 93.6
CaSO4 0.4
SiO2 1.3
Fe2 O3 0.4
Al2 O3 0.5
MgO 0.8
CO2 2.7
P2 O5 0.015
Loss on ignition (CO2 ) 0.5
4.2. Electrothermic Reduction
The raw material mixture is heated to a high tem-
perature in a short shaft furnace with an electric
current. Investigations of the reaction have led
to the conclusion that it takes place in two steps:
CaO + C −→ Ca + CO
Ca + 2 C −→ CaC2
The principal reaction in the furnace takes place
in a CaC2 – CaO melt. Electric current, energy
supply, temperature, and chemical reactions in-
teract in a manner that is not yet completely un-
derstood. According to [21] the rate-determining
step is the transport of the CaO dissolved in the
melt to the surface of the coke grain, where the
CaC2 is formed. This CaC2 then immediately
dissolves in the melt. The liquid calcium carbide
is tapped from the bottom of the furnace.
4.3. Furnaces
Carbide furnaces can be divided into vari-
ous classes according to their electrical sup-
ply (single-phase, three-phase), the arrangement
of the electrodes (serial, symmetrical), and the
means of excluding air (open, half-covered,
closed).
4.3.1. Single-Phase Furnaces
High-performance single-phase furnaces were
developed in 1928 by Miguet. This first furnace
had a power rating of 15 MW. These furnaces are
operated with low voltage and high current; opti-
Recycled mal arrangement of the electric circuit produces
lime
a power factor (cos ϕ) of up to 0.95.
89.0
–
–
2.9 4.3.2. Three-Phase Furnaces
0.4
2.4 The majority of today’s carbide furnaces are op-
0.8
3.0 erated with three-phase current. They can be
0.01 classified according to the arrangement of the
0.5
electrodes.
Serial. In a serial furnace the center lines
of the three electrodes lie in a straight line, or
they form an isosceles triangle. Rectangular and
oval furnaces were formerly equipped exclu-
sively with package electrodes made from pre-
coked coal; later, rounded rectangular Söderberg
electrodes were preferred. The serial furnace
has advantages over the round furnaces as re-
gards feeding and distribution of the burden and
can be operated half covered without any prob-
lems. Water-cooled barriers between the elec-
trodes not only provide for even distribution of
the burden but also promote cooling of the up-
per part of the solid material, hence reducing its
conductivity.

Table 1. Composition of carbonaceous raw materials for calcium carbide production (wt %)
Metallurgical coke
Fixed carbon 89.0
Volatile carbon 0.8
Moisture 0.8
Sulfur 0.8
Ash 9.4
The unsymmetrical arrangement of the sec-
ondary current conductors leads to an inductive
effect and consequently to dead and live phases
with respect to the middle phase. Output and
electrode consumption differ at the three elec-
trodes owing to the differences in power con-
sumption. (For the theoretical relationships, see
[22–25].) Difficulty can occur in discharging the
melt at the dead phase; this can be alleviated, for
example, by addition of lime. A further disad-
vantage compared with circular furnaces is the
unfavorable ratio of furnace capacity to surface
area, which leads to greater heat loss.
Furnaces of this type still exist and are op-
erated at up to 40 MW, sometimes with hol-
low electrodes (see page 5). However, all mod-
ern carbide furnaces are now symmetrical three-
phase furnaces.
Symmetrical. In symmetrical three-phase
furnaces the electrodes and as far as possible the
transformers together with the high current con-
ductors are arranged symmetrically about the
center. In a circular furnace vessel the electrodes
are situated at the corners of an equilateral trian-
gle [26]. Well-designed circular furnaces have
the advantage that high power factors can be
achieved. At a sufficiently high power, molten
zones are formed at all three electrodes and over-
lap at the center of the furnace. The tapping
points should be situated as near as possible to
the electrodes. On account of the high tempera-
ture, the furnace wall at the tapping point must
be water-cooled or constructed of highly heat
resistant material.
4.3.3. Half-Covered Furnaces
According to the equation
CaO + 3 C −→ CaC2 + CO (g)
Calcium Carbide 5
Anthracite Petroleum coke
80.0 81.6
6.0 9.0
8.0 8.0
0.8 1.9
6.0 0.3
one mole of CO is produced for each mole of cal-
cium carbide. In the first years of carbide pro-
duction this gas was simply burnt at the open
furnace. Because of the air pollution they cause,
large furnaces of this type have largely been re-
tired from service.
In Germany, Helfenstein attempted in 1910
[27] to construct above the linear furnace
rooflike covers made of welded, water-cooled
steel tubes between the electrodes. These gas
collectors can also consist of ceramic material
traversed by cooling coils. The liberated gas can
be collected in this way. For the symmetrical
three-phase furnace the construction of a gas col-
lection hood is more difficult.
4.3.4. Closed Furnaces
Closed three-phase furnaces permit 100 % gas
recovery and in normal operation do not cause
any pollution of the environment by escaping
dust-laden carbon monoxide. A schematic of a
typical closed furnace is shown in Figure 2.
Hearth. The hearth consists of a welded steel
outer casing stiffened with steel girders and ribs.
The horizontal steel sheets are fixed in a ring
shape round the hearth for reinforcement. A nat-
ural air current should flow around all sides.
The base of the hearth is lined with carbon
blocks and rammed carbon to a height of about
1.5 m. The side walls are lined with refractory
bricks or rammed refractory material. The region
of the tapping point, because of the especially
high temperatures, is more strongly constructed
or provided with water cooling.
Electrodes. For supplying electrical energy
to the molten region of the carbide furnace at
ca. 2000 ◦ C, carbon is the only suitable mate-
rial. The electrodes must have high electrical and
6 Calcium Carbide
Figure 2. Closed carbide furnace
thermal conductivity and adequate mechanical
strength.
The prebaked carbon electrode, which was at
one time the only type used, has with few excep-
tions been replaced by the Söderberg electrode,
first tried in 1921 [28]. In open rectangular fur-
naces prebaked packaged electrodes were used.
Round electrodes are manufactured up to 1.5 m
in diameter and 2.5 m in length. The current den-
sity achievable with prebaked carbon exceeds
10 A/cm2 .
The self-baking Söderberg electrode consists
of a sheet steel cylinder with internal vertical
ribs. This casing is filled with electrode paste.
Söderberg electrodes are the most economi-
cal type of electrode for furnace ratings from
about 10 MW upwards. The electrode paste is
manufactured from coke, calcined anthracite, or
petroleum coke and a tar/pitch binder. The most
important property of the paste is freedom from
breakage, even under high or variable load and
at low consumption. The consumption of the
Söderberg electrode is compensated by weld-
ing on a new steel casing and filling with new
electrode material during furnace operation. The
consumption of Söderberg paste can range from

15 to more than 20 kg per tonne of calcium car-
bide, especially if the electrode is not hollow.
The hollow Söderberg electrode has been
used increasingly since 1961 [9], [30]. Lime
and coke fines are introduced directly into the
molten region through a central pipe by a carrier
gas such as carbon monoxide or nitrogen. The
carbide-forming reaction causes a temperature
reduction and cools the tip of the electrode; a
reduction of the rate of electrode consumption
by up to 50 % is achieved, and cheap lime and
coke fines can be used. Prebaked electrodes can
also be provided with a central hole and oper-
ated as hollow electrodes. Large furnaces with
power loads higher than 30 MW should always
be equipped with hollow electrodes.
The electrode connection for continuous
electrodes consists of water-cooled metal con-
tact clamps, adjusted exactly to the shape of the
electrode to ensure optimum transfer of the elec-
tric current. Up to ten pressure plates are pressed
against the round electrode casing by a water-
cooled pressure ring. A remote-controlled slip-
ping device adapts the slipping rate to the rate of
consumption of the electrode, so that the baking
zone of the Söderberg electrode does not drop
below the clamps. Otherwise, burn-through of
the casing and breakage of the electrode can oc-
cur. The baking zone can be monitored by ther-
mocouples, mechanical sounding, or by measur-
ing the voltage between the casing and a steel rod
in the electrode. The electrode length is an im-
portant factor for furnace operation and can be
measured by mechanical sounding or weighing.
A new development is the modular elec-
trode holder, in which the electrode ribs extrude
through the casing into the contact assembly
[31]. The contact clamps and pressure ring are
replaced by a slipping unit at each rib. There are
no radial forces acting on the electrode, and heat
removal from the electrode is low.
The electrical supply to industry is today ex-
clusively three-phase alternating current.
In the oil-cooled transformers the oil is cir-
culated and cooled indirectly by water. The oil
pressure is usually higher than the water pres-
sure to prevent water from entering the oil cir-
cuit in the event of any leakage. On account of
the occasional violent load alterations of the fur-
naces, such as may be caused by variable current
demand and variable resistance of the burden,
the power of the transformer must be control-
Calcium Carbide 7
lable with the largest possible load variation. For
this purpose motor-driven sequence switches are
necessary. The operating voltage of today’s car-
bide furnaces is in the region of 100 – 300 V. The
secondary current (up to 150 kA) is carried by
water-cooled copper conductors or flexible ca-
bles.
A power diagram is used to represent the spe-
cific operating conditions of a three-phase fur-
nace. Apart from the negligible ohmic resistance
of the high-current cables and the electrodes, this
includes the constant, calculable reactance of the
transformer, cables, and electrodes, as well as
the variable resistance (impedance) of the fur-
nace itself [23–25]. The power must be variable
between wide limits for practical operation, e.g.,
starting up and shutting down the furnace, ad-
justing the electrical load to suit the conditions
in the furnace (temperature, pressure), or today’s
usual wide-ranging operating schedule for elec-
tricity consumption (day/night usage, etc.).
For the single-phase furnace a current regu-
lator is sufficient; for the multiphase furnace,
impedance control, i.e., the control of appar-
ent furnace resistance, by setting the immersion
depth of the electrodes is necessary.
Certain types of closed hood construction al-
low for raising and lowering of the feed chutes
so that, in addition to supplying the feed mate-
rial, they can be used to alter the configuration of
the surface of the burden and hence the furnace
resistance.
4.4. Operation
On start up, the carbide furnace is charged with
a layer of coarse coke. Then the electrodes, at a
low voltage, are brought towards the coke until
contact takes place, which can be seen by the
appearance of electric arcs between individual
pieces of coke. When the black material is at red
heat, the furnace bottom is gradually fed with
burden and the power is slowly increased.
Smooth operation of the furnace requires
smooth feeding of burden. Any variations in the
optimal composition of the burden are usually
compensated by addition of lime. This also ne-
cessitates a desirable deeper immersion of the
electrodes in the melt owing to the low conduc-
tivity of the lime. When the electrodes are raised
too high, carbide is produced in the upper layers
8 Calcium Carbide
of the burden, which leads to increased danger
of spurting from the melt. The mass of solid ma-
terial must remain permeable to gas at all times.
Closed three-phase furnaces have numerous
feed chutes, which are arranged around the elec-
trodes and automatically supply the burden. Spe-
cial attention must be paid to the composition
and grain size of the black – white mix to pre-
vent any segregation. The feed must above all
contain no dust, in order to reduce the danger
of crusting. However, if cheap, very impure raw
materials are used, crust and slag formation can-
not be eliminated, and they appear on the lower
electrical connectors and the hood. In such cir-
cumstances and also in the case of segregation of
the feed materials, short circuits can be produced
and can destroy the parts affected. A compro-
mise is necessary between cheap raw materials
and avoiding damage to the furnace.
The gas pressure inside the furnace hood
should be about equal to atmospheric pressure.
A lower pressure causes atmospheric oxygen
to leak into the furnace, severe excess pressure
leads to carbon monoxide contaminating the en-
vironment and can endanger operating person-
nel.
Where large units or groups of furnaces are in
production, the entire furnace operation is usu-
ally computer-controlled from a separate control
room.
To tap off the calcium carbide, the furnace
is opened mechanically or by burning a tap-
ping hole with an electric arc. The tapping elec-
trode is a baked electrode, 10 – 12 cm thick,
which is supplied with electricity from its own
transformer, a furnace transformer, or both. The
molten calcium carbide flows at 1700 – 2100 ◦ C,
depending on its purity, through cooled tapping
spouts into cast-iron ladles that can be handled
on a carousel arrangement or continuous track.
Owing to its high melting point and the rapid loss
of heat by radiation, technical-grade calcium
carbide (80 % CaC2 ) solidifies very quickly so
that the tapping holes must be kept open either
mechanically or manually with steel rods. When
tapping is completed, the hole can be closed with
a clay plug or plugging carbide is propelled or
blown into the tapping hole until it solidifies.
The fumes arising from the tapping hole are re-
moved by fume extraction equipment. As these
fumes have the character of an aerosol (particle
size, 20 % < 10 µm), purification is expensive.
During tapping the process operators must
be protected from the hot gases, dust, and spurt-
ing carbide with the aid of chain curtains, wire
netting, and steel shields installed in front of the
tapping point. The tapping men wear aluminum-
covered fireproof coats, dark glasses, and protec-
tive visors, in addition to fire-retardant working
clothes.
Modern tapping machines equipped with a
hydraulic manipulator can carry out all tapping
operations. They are fitted with interchangeable
tools such as tapping electrodes, reaming rods,
and plugging devices. In this way, the tapping
personnel can be reduced to one or two men per
shift.
The reduction (especially of Fe2 O3 and SiO2 )
by carbon yields iron and silicon, which react to
give ferrosilicon. This FeSi, on account of its ap-
preciably higher density, collects under the car-
bide melt and normally flows away on tapping
the furnace. As the melting point of this alloy
is however several hundred kelvin below that of
the carbide melt, there is a danger that FeSi could
flow through cracks in the extremely hot furnace
lining and cause damage in the area surrounding
the furnace before it solidifies. In every carbide
plant constant attention is paid to this problem.
4.5. Furnace Gas
Composition. The composition of the fur-
nace gas depends on the raw material. If moist
coke is used, the hydrogen content increases on
account of the water-gas reaction, C + H2 O

CO + H2 . The result is the same when any
appreciable amounts of volatiles in the black
material are thermally cracked. Incompletely
calcined limestone leads to the production of
carbon monoxide as a result of the reaction
CO2 + C
2 CO, which consumes both coke
and energy.
A sudden increase in hydrogen content sug-
gests a water leak in the furnace. If the carbon
dioxide and nitrogen contents increase, then the
hood can no longer be relied upon to be gastight.
If atmospheric oxygen enters the furnace hood,
combustion occurs and increases the tempera-
ture of the cooling water and gas. Explosions
are to be expected only on ignition of an un-
burnt mixture of oxygen and carbon monoxide
when the furnace is cool.

A typical analysis of the purified gas (vol %)
follows:
CO 80 – 90 CH4 1
H2 6 – 15 N2 2–7
CO2 0.5 – 3.0
The heat of combustion is ca. 11 720 kJ/m3
(STP).
Gas Purification. The carbon monoxide ob-
tained from half-covered or closed furnaces
must be dedusted. Both dry and wet dedusting
methods are used.
In the dry dedusting process, the gas is, e.g.,
filtered by self-supporting candle filters made of
ceramic fibers [33]. Their surfaces are cleaned
off-line by jet pulses of previously cleaned gas or
nitrogen. A final dust content of < 1 mg/m3 can
be attained. Finally the hot furnace gas is cooled
in a heat exchanger. The dust from the filter has
the composition 35 – 40 % CaO, 15 – 25 % MgO,
8 % Fe2 O3 + Al2 O3 , 7 % SiO2 , 10 % CO2 , 9 % C
and it is difficult to use. Owing to the presence
from time to time of soluble cyanide the dis-
posal of dust also is a problem. However, there
are methods of roasting that remove cyanide.
In the wet process the gas is passed through
several washing towers and sprayed with circu-
lating water. In the last stage, Theisen washers
reduce the dust content to ca. 5 mg/m3 at STP.
Cyanide in the slurry is precipitated as an iron
complex, and the slurry is separated in thicken-
ers, usually hydrocyclones. The clear liquor that
overflows is reused.
4.6. Mass and Energy Balance
A modern large furnace without hollow elec-
trodes requires per tonne of 300-L calcium car-
bide 950 kg lime (94 % CaO), 550 kg coke
(dry, 10 % ash), 20 kg electrode material, and
3100 kWh electricity [26].
The typical analysis (wt %) of a commercial
calcium carbide that yields 300 L of acetylene
per kilogram of calcium carbide follows:
CaC2 80.5 Fe 0.2
CaO (free) 12.9 S 0.5
Si 1.3 C 0.3
Al 1.1
The enthalpy of reaction (∆H) for such cal-
cium carbide is 465 kJ/mol, corresponding to
Calcium Carbide 9
ca. 2000 kWh per tonne. In practice, for 300-L
technical-grade calcium carbide, depending on
purity of raw materials, furnace type, and load-
ing, about 3000 – 3300 kWh/t are required. The
difference is accounted for by the heat contents
of the molten carbide and furnace gas and the
heat lost to the cooling systems.
5. Further Treatment
5.1. Cooling
Most carbide plants use the block casting
method, in which the liquid calcium carbide is
tapped off into a ladle or crucible and solidifies to
a block. The block is allowed to cool and is then
broken up, ground, and sieved to the required
size.
Generally, a cast-iron crucible receives the
liquid carbide at ca. 1900 ◦ C from the tapping
point. After a short time, a solid crust forms on
the walls of the crucible and isolates the iron
from the hot liquid core of the block. The heat
passing through this crust is then radiated from
the iron. To prevent cracking of the crucible, this
process is regulated so that the temperature of the
iron does not exceed 600 ◦ C, mainly by ensur-
ing that the mass ratio of iron to carbide exceeds
2 : 1. Depending on the power of the furnace,
crucibles with a capacity between 0.4 and 2.0 t
are used.
For further cooling of the block there are sev-
eral possibilities. If small molds are used, the
block is lifted or tipped from the mold after ca.
2 h and then cools further outside the mold, ei-
ther on a block transporter, or on steel conveyor
belts that transport it to the crusher. The cooling
times are ca. 20 h.
Higher power carbide furnaces are generally
equipped with crucibles of capacity over 1 t. In
one operating procedure the filled crucible is
placed in a cooling room, and after 25 – 30 h
the contents of the crucible are tipped into the
crusher. This procedure has the disadvantage
that for a 55 MW carbide furnace, 400 1.5 t cru-
cibles must be ready for use. As the weight of
the crucible must be at least twice the weight of
the contents, this means an investment in about
1200 t of cast iron for crucibles.
10 Calcium Carbide
A simpler procedure is to use a conical cru-
cible open at the bottom and placed on a steel
plate. After ca. 2 h the crucible can be lifted from
its bottom plate. The block is then pushed onto an
inclined plane and onto a band conveyor which
transports it to the crusher. Conveyor tapping
systems, which allow continuous transport of the
calcium carbide from the furnace to the crusher,
have been developed [34].
All attempts to use even a part of the heat
content of the calcium carbide block (ca. 33 %
of the energy used in production) have failed.
5.2. Size Reduction
Because calcium carbide reacts with atmo-
spheric water vapor, further processing of the
block is started when its average temperature
reaches ca. 400 ◦ C, to minimize the losses of
acetylene during processing. The method of pro-
cessing depends on the intended use of the cal-
cium carbide. The first step is always to crush
the block, usually to < 100 mm. Then the de-
sired size grading is produced by sieving, fur-
ther crushing, and, if necessary, milling in im-
pact mills. Magnetic impurities (iron and fer-
rosilicon) must be removed from the calcium
carbide. For this purpose, magnetic separators
are installed in all stages of the size reduction
process.
5.3. Quality Specifications
In many countries the quality requirements are
laid down in standard specifications:
United States Federal Specification 0-6-101 a
(July, 1949)
Australia Standards Association of Australia,
Publication No. K 49 (1931)
Belgium Norme Belge, NBN 211-01 (01.72)
France Norme Française, NF T 24-001
(10.54 + 09.55)
Germany DIN 53922 (07.79)
United Kingdom British Standard 642 (1965, 11.66)
India Indian Standard IS 1040 (1978)
Israel Israel Standard 267 T [250 × 4],
SJ 446 (07.62)
Japan Japanese Industrial Standard
JIS K 1901 (1974)
Mexico Norme Official K 23 (1945)
Normally these standards specify sieve anal-
ysis, dust content, gas generation, and phos-
phorus content.
The principal criterion of the quality of cal-
cium carbide is the amount of acetylene pro-
duced per unit mass of calcium carbide by re-
action with water – the so-called liter number,
because it is a direct measure of the CaC2 con-
tent of the carbide.
The method of determining this gas yield is
laid down in the standard specifications. The
British standard calculates the dry gas volume
at atmospheric pressure and 15 ◦ C, whereas the
German standard assumes that the gas is satu-
rated with water vapor at 15 ◦ C. (Such differ-
ences explain the differences in the liter num-
bers.)
When calcium carbide is crushed, the im-
purities concentrate in the finer fractions, and
thus the minimum liter number of commer-
cial calcium carbide depends on the grain size.
For the coarsest size fraction the British stan-
dard requires 295 L/kg, and the German stan-
dard 300 L/kg. For smaller size fractions, e.g.,
4 – 7 mm, the British standard is 275 L/kg, and
the German standard 260 L/kg.
Because the gas determination methods in all
specifications are time-consuming, industry has
developed methods of testing for liter number by
using small amounts of calcium carbide in more
compact apparatus. In this way a large number
of tests of sufficient accuracy can be carried out
in a short time, and calcium carbide producers
can continuously monitor their production.
The most important size ranges specified in
individual standards are (in mm): 2 – 4, 4 – 7,
7 – 15, 15 – 25, and 25 – 50. The British stan-
dard also gives the ranges 1 – 2, 4 – 80, 1 – 80,
and 0 – 80. It also mentions the well-known
commercial form 14 ND (0.4 – 1.7 mm), without
making it a standard.
The phosphine content of the acetylene pro-
duced is specified in all the standards. The maxi-
mum is in the region of 0.1 vol %. Detailed meth-
ods for the determination of sulfur and of ma-
terials insoluble in dilute sulfuric acid are also
given, but no upper limits are set.
For the determination of the quality of the
granular calcium carbide, samples must be taken
correctly. All standard specifications therefore
give precise instructions regarding sampling and
sample preparation.

5.4. Transport and Storage
Owing to the fact that calcium carbide produces
a flammable gas in the presence of water, it
is classed as a hazardous industrial material.
Therefore, in most countries special regulations
concerning packing and storage have been is-
sued.
In Britain “The Storage of Carbide of Cal-
cium”, published by the British Acetylene As-
sociation, states the regulations.
According to the “Verordnung über
Acetylenanlagen und Calciumcarbidlager”,
anyone in Germany who stores calcium car-
bide must register [35], [36]. The requirements
for these storage sites are stated in “Technische
Regeln für Acetylenanlagen und Calciumcar-
bidlager” (TRAC 301, 1982). In addition, the
provisions of the “Arbeitsstoffverordnung” (in-
dustrial materials regulations) are applicable.
The following international regulations gov-
ern the transport of calcium carbide [37–39]:
Land transport (ADR/RID)
Class 4.3
Item 17b
UN no. 1402
Sea transport (IMDG)
Class 4.3
UN no. 1402
PG II
MFAG 705
EMS 4.3-03
Air transport (ICAO-TI, IATA-DGR)
Class 4.3
UN no. 1402
PG II
Labelling (EU directives):
Calcium Carbide
EEC no. 200-848-3
Symbol: F – Highly Flammable
R phrases
R15: Contact with water liberates extremely flammable gases
S phrases
S8: keep container dry
S43: In case of fire use dry sand. Never use water.
In general, steel containers are permitted for
transport of calcium carbide, e.g., drums or kegs.
Under certain conditions transport in cardboard
cartons is allowed, provided that the carbide is
also sealed in airtight bags.
For the transport of larger amounts of calcium
carbide, containers with a capacity of 1 – 20 t
have been introduced. Fine granular calcium car-
bide is also conveyed in tankers that can be dis-
Calcium Carbide 11
charged pneumatically. For storage and transport
in the open, only suitably equipped containers
are allowed, not drums or kegs.
6. Environmental Protection
The raw materials used in manufacturing cal-
cium carbide are nonpoisonous and present no
hazard to the environment. During production,
transport, and preparation of these raw materi-
als, dust can cause a nuisance in the vicinity of
the factory and at the workplace and is therefore
removed by air extraction and retained by means
of filters.
Precautions, especially breathing protection,
must be taken when handling hot Söderberg ma-
terial. The carbide furnaces of the open construc-
tion emit lime and coke dust from the surface of
the burden. As a rule, open furnaces are fitted
with large extraction hoods so that these emis-
sions, together with lime dust arising during tap-
ping, can be extracted and filtered. Closed fur-
naces emit dust only on tapping. This dust, be-
cause of the extremely small particle size, makes
high demands on the filtration equipment.
Carbon monoxide gas from open furnaces
burns directly at the surface of the feed material
to harmless carbon dioxide. From closed fur-
naces it is usually used as fuel gas. The traces
of cyanide in the furnace gas are converted into
harmless compounds by special treatment in the
gas purification equipment. The residues from
wet purification are usually dumped.
7. Uses
Calcium carbide has three main uses: the
manufacture of acetylene (→ Acetylene,
Chap. 4.3.4.), reaction with nitrogen to give
cyanamide, see→ Cyanamides, and the desul-
furization of pig iron, cast iron, and steel. Since
1960 the use of carbide-based acetylene has de-
clined worldwide as a raw material for heavy
chemicals due to the widespread use of petro-
chemicals. Only a few chemical products are
still produced from acetylene. These include
butynediol, a component of plastics and fibers,
and acetylene black, used in dry batteries.
Acetylene from calcium carbide still holds a
firm position in the field of gas welding. The
12 Calcium Carbide

acetylene cylinder, in spite of the rapid develop- the increasing availability of petroleum in many
ment of techniques of joining materials, is indis- countries, including South Africa. Production
pensable, especially in pipeline construction, on in the former German Democratic Republic has
account of its adaptability and mobility. ceased. In Central and South America small in-
Calcium carbide has an important applica- stallations still take advantage of favorable local
tion in metallurgy because it reacts with sulfur. conditions. In Asia, especially China, calcium
The increasingly strict standards for steel have carbide production has increased in the last few
led to requirements for lower sulfur contents. decades.
The lowest sulfur contents can be achieved by Table 3. World calcium carbide production, 1000 t/a
desulfurizing the hot metal before the converter.
Injection of calcium carbide into the melt was Region 1962 1972 1982 1990
introduced in 1970 and is carried out in a trans- Western Europe 2540 1410 660 500
port ladle. Generally the sulfur content can be Eastern Europe 2200 3300 2600 1710
reduced from 0.2 % to 0.001 %. Since the reac- America 14 00 710 470 570
Asia and Africa 1860 2080 2670 2080
tion of calcium carbide with sulfur takes place World production 8000 7500 6400 4860
on the surface of the solid carbide, the calcium
carbide should be ground to < 100 µm. Combi- The general trend of calcium carbide produc-
nations of calcium carbide with magnesium are tion will remain stagnant or in a slightly down-
increasing in importance. A gas-evolving com- ward direction worldwide.
ponent is added to the desulfurization mixture
to improve the reactivity of the calcium carbide
in the hot metal [40], [41].
Consumption of calcium carbide for hot
9. Toxicology
metal desulfurization in 1997 was: Europe
The toxicological dangers of technical-grade
100 000 t/a; USA 15 000 t/a; India, Japan, and
calcium carbide arise only as a result of impu-
South Africa 30 000 t/a.
rities, which on reaction with water give rise to
In foundry technology, coarse-grained cal-
the formation of hydrides of phosphorus, etc. (→
cium carbide is used in combination with ad-
Acetylene, Chap. 8.).
ditives such as fluorspar. The calcium carbide
is stirred into the ladle after tapping and before
casting.
10. References

8. Economic Aspects 1. R. Juza, H. U. Schuster, Z. Anorg. Allg. Chem.

Between 1962 and 1965 the world output of cal-
cium carbide reached its maximum, nearly 10 ×
106 t/a. Since then the decline has been steady.
This decline has been accompanied by a shift of
the main production centers.
Table 3 lists production for the years 1962,
1972, 1982, and 1990. In the 1960s and 1970s,
there was a severe decline in North America,
Western Europe, and Japan on account of con-
version to petroleum-based products and re-
duced output of calcium cyanamide for fertilizer,
whereas Eastern Europe showed an increase in
calcium carbide production. In the 1980s, how-
ever, replacement of calcium carbide by petro-
chemical raw materials began in these countries,
too. The rapid decline in calcium carbide pro-
duction in the last few years has been due to
311 (1961) 62 – 75.
2. G. W. Healy, J. Met. 18 (1966) 643.
3. H. H. Franck, Z. Anorg. Allg. Chem. 232
(1937) 75 – 111.
4. M. Atoji, J. Chem. Phys. 54 (1971) 3514.
5. M. A. Bredig, J. Phys. Chem. 46 (1942) 801.
6. M. von Stackelberg, Z. Phys. Chem. Abt. B 9
(1930) 437.
7. N. G. Vannerberg, Acta Chem. Scand. 15
(1961) 769.
8. N. G. Vannerberg, Acta Chem. Scand. 16
(1962) 1212.
9. O. Kubaschewski, E. L. L. Evans,
Metallurgical Thermochemistry, Pergamon
Press, London 1967.
10. Winnacker-Küchler, 3rd ed., vol. 1, p. 426;
4th ed., vol. 2, p. 609.
11. G. Geiseler, W. Büchner, Z. Anorg. Allg.
Chem. 343 (1966) 286.

12. K. K. Kelley, Bull. US Bur. Mines 477 (1950)
101.
13. L. Barin, O. Knacke: Thermochemical
Properties of Inorganic Substances, Springer
Verlag, Berlin-Heidelberg-New York, Verlag
Stahleisen, Düsseldorf 1972.
14. W. Rettkowski, Chr. Geilhufe, K. H. Rüdiger,
Chem. Tech. (Leipzig) 28 (1976) 588.
15. E. Biesalski, H. van Eck, Angew. Chem. 41
(1928) 278.
16. O. Ruff, E. Förster, Z. Anorg. Allg. Chem. 131
(1923) 321.
17. Bayer, DE 944487, 1954.
18. W. A. Barber, C. L. Sloan, J. Phys. Chem. 65
(1961) 20 – 26.
19. S. Kiritani, T. Nishimaki, CEER Chem. Econ.
Eng. Rev. 16 (1984) no. 5.
20. K. Feldmann, Chem. Ing. Tech. 41 (1969) 199.
21. K. Budde, A. Strauss, B. Schmidt, Chem. Tech.
(Leipzig) 28 (1976) 585.
22. R. Toussig: Die Industrie des
Calciumcarbides, Knapp, Halle 1930.
23. J. Wotschke: Grundlagen des elektrischen
Schmelzofens, Knapp, Halle 1933.
24. E. Kluss: Einführung in die Probleme des
elektrischen Lichtbogen- und
Widerstandsofens, Springer Verlag, Berlin
1951.
25. E. Kluss, Z. Elektrotech. 72 (1951) 115.
26. AG für Stickstoffdünger, DE 545696, 1925;
DE 571711, 1928.
Calcium Carbonate → Lime and Limestone
Calcium Carbide 13
27. A. Helfenstein, DE 226956, 1910.
28. Det Norske Aktieselskab for Elektrokemisk
Industrie, DE 324741, 1919.
29. Union Carbide Corp., US 2996360, 1958.
30. D. E. Hamby, J. Met. 19 (1967) 45.
31. Elkem, DE 3 141 108, 1983.
32. W. Weiss, L. Bökelmann, L. Iltzsche, H.
Kleiner, Chem. Tech. (Leipzig) 36 (1984) 89.
33. SKW Trostberg AG, DE-OS 19 611 119, 1997.
34. Denki Kagaku Kogyo, DE 4 210 387, 1994.
35. Verordnung über Acetylenanlagen und
Calciumcarbidlager 27. 02. 1980, BGBl. I,
p. 173.
36. Technische Regeln für Acetylenanlagen und
Calciumcarbidlager (TRAC), July 1971.
37. European agreement concerning the
international carriage of dangerous goods by
road (ADR), 07. 1968.
38. Agreement concerning the international
carriage of dangerous goods by rail as annex I
of the international agreement on railroad
freight traffic (RID, CIM), 09. 1977, revised
01. 09. 1983.
39. International regulation for inland navigation
and for ocean navigation and for aviation
(IATA).
40. SKW Trostberg, DE 2 741 588, 1977.
41. SKW Trostberg, Thyssen Stahl, EP 0 164 592,
1985.