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

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


10.1002/14356007.a04 533
2 Calcium Carbide

2. Physical Properties The standard enthalpy of formation of CaC2


from the elements at 298 K and the standard en-
Calcium carbide [000075-20-7], CaC2 , M r tropy of CaC2 at 298 K are ∆H = − 59.4 kJ/mol
64.10, is colorless and odorless when pure. Ow- and S = 70.3 J mol−1 K−1 [11], [12], [13].
ingto the presence of impurities, various colors, The electrical conductivity of calcium car-
from gray to brownish black, occur in technical- bide depends strongly on the degree of purity
grade carbide, at times even violet or red-brown and increases with increasing temperature. Val-
tones. The typical odor of technical-grade cal- ues between 100 and 1000 Ω−1 have been re-
cium carbide is that of phosphine, which is ported [14].
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- 3. Chemical Properties
position takes place [2], [3]. Four modifications
of calcium carbide are known: Commercially important reactions of calcium
– Phase I: tetragonal, stable between 25 and carbide are conversion to calcium cyanamide
440 ◦ C
CaC2 + N2 −→ CaCN2 + C ∆H 298 = − 289 kJ/mol
– Phases II and III: lower symmetry, stable be-
low 440 ◦ C hydrolysis to acetylene
– Phase IV, face-centered cubic, stable above
440 ◦ C CaC2 + 2 H2 O −→ C2 H2 + Ca(OH)2 ∆H 298
= − 128.4 kJ/mol
Commercial calcium carbide is mainly
phase I. Phase II is formed in some pure prepa- and the reaction with sulfur in molten iron
rations [4–8]. The heat of transformation of cal-
cium carbide at 440 ◦ C is 8.68 J/g [9]. CaC2 + [S]Fe −→ CaS + 2 [C]Fe
The CaC2 – CaO phase diagram (Fig. 1) [1] is
a simple eutectic system without compound for- Acetylene is produced smoothly at tempera-
mation or solid solutions; the pure components tures below 300 ◦ C. Pure calcium carbide yields
are not miscible with each other to a significant 346.89 L of dry acetylene per kg CaC2 at 0 ◦ C
extent in the solid state. Above the liquidus line and 101.3 kPa (372.66 L at 15 ◦ C, 101.3 kPa
there is complete miscibility. Technical-grade (1013 mbar), saturated with water vapor). At red
calcium carbide has a lower liquidus tempera- heat, calcium oxide, hydrogen, and carbon diox-
ture owing to the presence of impurities. 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
Figure 1. Phase diagram CaC2 − CaO The preparation of pure CaC2 is only of aca-
demic interest. The industrial production of
The average specific heat capacity between technical-grade calcium carbide is based on the
20 and 440 ◦ C is 1047 J kg−1 K−1 ; the heat of reaction of quicklime with carbonaceous mate-
fusion of pure calcium carbide is 1470 J/g [10]. rials such as coke and anthracite:
Calcium Carbide 3

CaO + 3 C −→ CaC2 + CO ∆H 298 = + 465 kJ/mol the raw materials must allow the furnace to be
operated without outside intervention for at least
The reaction rate becomes appreciable only a few days.
above 1600 ◦ C. Above 2000 ◦ C undesirable side The grain-size distribution of the raw mate-
reactions become noticeable, especially rial must enable the carbon monoxide to escape.
In the reaction zone of the furnace the lime dis-
CaC2 −→ Ca + 2 C solves in the carbide melt, while the carbon com-
ponent reacts as a solid grain to produce calcium
CaC2 + 2 CaO −→ 3 Ca + 2 CO carbide in the liquid. Therefore lime with a large
For these reasons, all industrial processes op- grain size can be used without affecting its reac-
erate between 1800 and 2100 ◦ C and give a tivity, but for the carbon component a finer grain
technical-grade calcium carbide with a CaC2 size is usually necessary.
content of ca. 80 %. The remainder is mainly Modern furnaces are fitted with hollow elec-
calcium oxide, but there are also other impuri- trodes through which fine-grained raw mate-
ties from the raw materials, principally SiO2 and rial can be blown directly into the molten zone.
Al2 O3 . These manufacturing units only impose an up-
The energy for the production of the calcium per limit to the grain size; the necessary fineness
carbide must be introduced at very high temper- is obtained by sieving.
atures. There are two possible routes: Impurities, particularly metal oxides, cause
side reactions that waste energy. The principal
1) Melting of the carbonaceous material with impurities are iron oxides, SiO2 , Al2 O3 , MgO,
CaO in a short electrothermic shaft furnace and compounds of nitrogen, sulfur, and phos-
2) Combustion of carbonaceous material with phorus. Oxides of iron and magnesium are com-
pure or enriched oxygen in the presence of pletely reduced, the others only partially. The
CaO in a shaft furnace iron combines with silicon to give FeSi, which is
liquid at reaction temperatures. It is partly emul-
The development of the second method has sified in the carbide and can be tapped off. The
now been discontinued after about 50 years be- vaporization of magnesium and its oxidation by
cause the synthesis gas byproduct can be made carbon monoxide in the cooler parts of the fur-
more cheaply from petroleum. In Japan, research nace lead to buildup of dust and solid incrus-
has been undertaken to combine methods 1 and 2 tations [20]. The oxides SiO2 and Al2 O3 are
[19], but all the calcium carbide produced today generally dissolved in the carbide – CaO melt
is manufactured by method 1. along with the nitrides, sulfides, and phosphides
formed from the nitrogen, sulfur, and phos-
phorus compounds.
4.1. Raw Materials and Their The following carbonaceous materials are
Preparation available: coke from bituminous coal or lignite,
anthracite, petroleum coke, and charcoal. Coke
The raw material or burden that is introduced from bituminous coal is used worldwide for cal-
into the electrothermic furnace consists of a cium carbide production.
carbonaceous component and a lime-bearing Uncalcined anthracite and petroleum coke
component. The physical properties (particle can be used only as a part of the charge in a
size, particle strength, conductivity, etc.) and closed furnace. If the volatile content is reduced
the chemical properties (content of volatiles, ash below 2 % by calcination, they can be used as
content, etc.) of the raw material depend on the the sole charge. This is done in South Africa, a
type of carbide furnace and on the desired cal- country rich in anthracite. Charcoal can be used
cium carbide quality. Smaller open furnaces do only in small open furnaces.
not impose such strict demands because dur- Today for closed furnaces coke with a grain
ing operation the conditions inside the furnace size of 3 – 25 mm is used. The fraction below
may be observed and corrective action can be 3 mm is blown in through the hollow electrodes.
taken, either manually or mechanically. With Small open furnaces can also use coarser grain
high-capacity closed furnaces, the properties of sizes. Before introduction, the coke must be
4 Calcium Carbide

dried below 2 % moisture content. Ash content supply, temperature, and chemical reactions in-
below 15 % is necessary to meet the quality stan- teract in a manner that is not yet completely un-
dards for the calcium carbide product in many derstood. According to [21] the rate-determining
countries. step is the transport of the CaO dissolved in the
The lime-containing component of the raw melt to the surface of the coke grain, where the
material mixture is predominantly quicklime. CaC2 is formed. This CaC2 then immediately
Manufacturing plants with large closed furnaces dissolves in the melt. The liquid calcium carbide
specify a grain size of 6 – 50 mm, and the mate- is tapped from the bottom of the furnace.
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 4.3. Furnaces
burnt so as to be as soft as possible, but resistant
enough for transport and storage. This is achiev- Carbide furnaces can be divided into vari-
able in modern lime kilns. At the same time the ous classes according to their electrical sup-
CO2 content is reduced to less than 2 %. ply (single-phase, three-phase), the arrangement
The calcium hydroxide left behind after of the electrodes (serial, symmetrical), and the
acetylene generation from calcium carbide, af- means of excluding air (open, half-covered,
ter granulation or briquetting with calcination, closed).
is also a cheap raw material. However, this lime
recycling is limited by the build-up of impuri-
ties. 4.3.1. Single-Phase Furnaces
Typical examples of compositions of raw ma-
terials for calcium carbide production are listed High-performance single-phase furnaces were
in Tables 1 and 2. developed in 1928 by Miguet. This first furnace
Table 2. Composition of lime for calcium carbide production (wt %)
had a power rating of 15 MW. These furnaces are
operated with low voltage and high current; opti-
New lime Recycled mal arrangement of the electric circuit produces
lime
a power factor (cos ϕ) of up to 0.95.
Total CaO 93.8 89.0
Free CaO 93.6 –
CaSO4 0.4 –
SiO2 1.3 2.9 4.3.2. Three-Phase Furnaces
Fe2 O3 0.4 0.4
Al2 O3 0.5 2.4 The majority of today’s carbide furnaces are op-
MgO 0.8 0.8
CO2 2.7 3.0 erated with three-phase current. They can be
P2 O5 0.015 0.01 classified according to the arrangement of the
Loss on ignition (CO2 ) 0.5 0.5
electrodes.

Serial. In a serial furnace the center lines


of the three electrodes lie in a straight line, or
4.2. Electrothermic Reduction they form an isosceles triangle. Rectangular and
oval furnaces were formerly equipped exclu-
The raw material mixture is heated to a high tem- sively with package electrodes made from pre-
perature in a short shaft furnace with an electric coked coal; later, rounded rectangular Söderberg
current. Investigations of the reaction have led electrodes were preferred. The serial furnace
to the conclusion that it takes place in two steps: has advantages over the round furnaces as re-
gards feeding and distribution of the burden and
CaO + C −→ Ca + CO can be operated half covered without any prob-
lems. Water-cooled barriers between the elec-
Ca + 2 C −→ CaC2 trodes not only provide for even distribution of
the burden but also promote cooling of the up-
The principal reaction in the furnace takes place
per part of the solid material, hence reducing its
in a CaC2 – CaO melt. Electric current, energy
conductivity.
Calcium Carbide 5
Table 1. Composition of carbonaceous raw materials for calcium carbide production (wt %)

Metallurgical coke Anthracite Petroleum coke

Fixed carbon 89.0 80.0 81.6


Volatile carbon 0.8 6.0 9.0
Moisture 0.8 8.0 8.0
Sulfur 0.8 0.8 1.9
Ash 9.4 6.0 0.3

The unsymmetrical arrangement of the sec- one mole of CO is produced for each mole of cal-
ondary current conductors leads to an inductive cium carbide. In the first years of carbide pro-
effect and consequently to dead and live phases duction this gas was simply burnt at the open
with respect to the middle phase. Output and furnace. Because of the air pollution they cause,
electrode consumption differ at the three elec- large furnaces of this type have largely been re-
trodes owing to the differences in power con- tired from service.
sumption. (For the theoretical relationships, see In Germany, Helfenstein attempted in 1910
[22–25].) Difficulty can occur in discharging the [27] to construct above the linear furnace
melt at the dead phase; this can be alleviated, for rooflike covers made of welded, water-cooled
example, by addition of lime. A further disad- steel tubes between the electrodes. These gas
vantage compared with circular furnaces is the collectors can also consist of ceramic material
unfavorable ratio of furnace capacity to surface traversed by cooling coils. The liberated gas can
area, which leads to greater heat loss. be collected in this way. For the symmetrical
Furnaces of this type still exist and are op- three-phase furnace the construction of a gas col-
erated at up to 40 MW, sometimes with hol- lection hood is more difficult.
low electrodes (see page 5). However, all mod-
ern carbide furnaces are now symmetrical three-
phase furnaces. 4.3.4. Closed Furnaces

Symmetrical. In symmetrical three-phase Closed three-phase furnaces permit 100 % gas


furnaces the electrodes and as far as possible the recovery and in normal operation do not cause
transformers together with the high current con- any pollution of the environment by escaping
ductors are arranged symmetrically about the dust-laden carbon monoxide. A schematic of a
center. In a circular furnace vessel the electrodes typical closed furnace is shown in Figure 2.
are situated at the corners of an equilateral trian-
gle [26]. Well-designed circular furnaces have Hearth. The hearth consists of a welded steel
the advantage that high power factors can be outer casing stiffened with steel girders and ribs.
achieved. At a sufficiently high power, molten The horizontal steel sheets are fixed in a ring
zones are formed at all three electrodes and over- shape round the hearth for reinforcement. A nat-
lap at the center of the furnace. The tapping ural air current should flow around all sides.
points should be situated as near as possible to The base of the hearth is lined with carbon
the electrodes. On account of the high tempera- blocks and rammed carbon to a height of about
ture, the furnace wall at the tapping point must 1.5 m. The side walls are lined with refractory
be water-cooled or constructed of highly heat bricks or rammed refractory material. The region
resistant material. of the tapping point, because of the especially
high temperatures, is more strongly constructed
or provided with water cooling.
4.3.3. Half-Covered Furnaces
Electrodes. For supplying electrical energy
According to the equation to the molten region of the carbide furnace at
ca. 2000 ◦ C, carbon is the only suitable mate-
CaO + 3 C −→ CaC2 + CO (g) rial. The electrodes must have high electrical and
6 Calcium Carbide

Figure 2. Closed carbide furnace

thermal conductivity and adequate mechanical ribs. This casing is filled with electrode paste.
strength. Söderberg electrodes are the most economi-
The prebaked carbon electrode, which was at cal type of electrode for furnace ratings from
one time the only type used, has with few excep- about 10 MW upwards. The electrode paste is
tions been replaced by the Söderberg electrode, manufactured from coke, calcined anthracite, or
first tried in 1921 [28]. In open rectangular fur- petroleum coke and a tar/pitch binder. The most
naces prebaked packaged electrodes were used. important property of the paste is freedom from
Round electrodes are manufactured up to 1.5 m breakage, even under high or variable load and
in diameter and 2.5 m in length. The current den- at low consumption. The consumption of the
sity achievable with prebaked carbon exceeds Söderberg electrode is compensated by weld-
10 A/cm2 . ing on a new steel casing and filling with new
The self-baking Söderberg electrode consists electrode material during furnace operation. The
of a sheet steel cylinder with internal vertical consumption of Söderberg paste can range from
Calcium Carbide 7

15 to more than 20 kg per tonne of calcium car- lable with the largest possible load variation. For
bide, especially if the electrode is not hollow. this purpose motor-driven sequence switches are
The hollow Söderberg electrode has been necessary. The operating voltage of today’s car-
used increasingly since 1961 [9], [30]. Lime bide furnaces is in the region of 100 – 300 V. The
and coke fines are introduced directly into the secondary current (up to 150 kA) is carried by
molten region through a central pipe by a carrier water-cooled copper conductors or flexible ca-
gas such as carbon monoxide or nitrogen. The bles.
carbide-forming reaction causes a temperature A power diagram is used to represent the spe-
reduction and cools the tip of the electrode; a cific operating conditions of a three-phase fur-
reduction of the rate of electrode consumption nace. Apart from the negligible ohmic resistance
by up to 50 % is achieved, and cheap lime and of the high-current cables and the electrodes, this
coke fines can be used. Prebaked electrodes can includes the constant, calculable reactance of the
also be provided with a central hole and oper- transformer, cables, and electrodes, as well as
ated as hollow electrodes. Large furnaces with the variable resistance (impedance) of the fur-
power loads higher than 30 MW should always nace itself [23–25]. The power must be variable
be equipped with hollow electrodes. between wide limits for practical operation, e.g.,
The electrode connection for continuous starting up and shutting down the furnace, ad-
electrodes consists of water-cooled metal con- justing the electrical load to suit the conditions
tact clamps, adjusted exactly to the shape of the in the furnace (temperature, pressure), or today’s
electrode to ensure optimum transfer of the elec- usual wide-ranging operating schedule for elec-
tric current. Up to ten pressure plates are pressed tricity consumption (day/night usage, etc.).
against the round electrode casing by a water- For the single-phase furnace a current regu-
cooled pressure ring. A remote-controlled slip- lator is sufficient; for the multiphase furnace,
ping device adapts the slipping rate to the rate of impedance control, i.e., the control of appar-
consumption of the electrode, so that the baking ent furnace resistance, by setting the immersion
zone of the Söderberg electrode does not drop depth of the electrodes is necessary.
below the clamps. Otherwise, burn-through of Certain types of closed hood construction al-
the casing and breakage of the electrode can oc- low for raising and lowering of the feed chutes
cur. The baking zone can be monitored by ther- so that, in addition to supplying the feed mate-
mocouples, mechanical sounding, or by measur- rial, they can be used to alter the configuration of
ing the voltage between the casing and a steel rod the surface of the burden and hence the furnace
in the electrode. The electrode length is an im- resistance.
portant factor for furnace operation and can be
measured by mechanical sounding or weighing.
A new development is the modular elec- 4.4. Operation
trode holder, in which the electrode ribs extrude
through the casing into the contact assembly On start up, the carbide furnace is charged with
[31]. The contact clamps and pressure ring are a layer of coarse coke. Then the electrodes, at a
replaced by a slipping unit at each rib. There are low voltage, are brought towards the coke until
no radial forces acting on the electrode, and heat contact takes place, which can be seen by the
removal from the electrode is low. appearance of electric arcs between individual
The electrical supply to industry is today ex- pieces of coke. When the black material is at red
clusively three-phase alternating current. heat, the furnace bottom is gradually fed with
In the oil-cooled transformers the oil is cir- burden and the power is slowly increased.
culated and cooled indirectly by water. The oil Smooth operation of the furnace requires
pressure is usually higher than the water pres- smooth feeding of burden. Any variations in the
sure to prevent water from entering the oil cir- optimal composition of the burden are usually
cuit in the event of any leakage. On account of compensated by addition of lime. This also ne-
the occasional violent load alterations of the fur- cessitates a desirable deeper immersion of the
naces, such as may be caused by variable current electrodes in the melt owing to the low conduc-
demand and variable resistance of the burden, tivity of the lime. When the electrodes are raised
the power of the transformer must be control- too high, carbide is produced in the upper layers
8 Calcium Carbide

of the burden, which leads to increased danger During tapping the process operators must
of spurting from the melt. The mass of solid ma- be protected from the hot gases, dust, and spurt-
terial must remain permeable to gas at all times. ing carbide with the aid of chain curtains, wire
Closed three-phase furnaces have numerous netting, and steel shields installed in front of the
feed chutes, which are arranged around the elec- tapping point. The tapping men wear aluminum-
trodes and automatically supply the burden. Spe- covered fireproof coats, dark glasses, and protec-
cial attention must be paid to the composition tive visors, in addition to fire-retardant working
and grain size of the black – white mix to pre- clothes.
vent any segregation. The feed must above all Modern tapping machines equipped with a
contain no dust, in order to reduce the danger hydraulic manipulator can carry out all tapping
of crusting. However, if cheap, very impure raw operations. They are fitted with interchangeable
materials are used, crust and slag formation can- tools such as tapping electrodes, reaming rods,
not be eliminated, and they appear on the lower and plugging devices. In this way, the tapping
electrical connectors and the hood. In such cir- personnel can be reduced to one or two men per
cumstances and also in the case of segregation of shift.
the feed materials, short circuits can be produced The reduction (especially of Fe2 O3 and SiO2 )
and can destroy the parts affected. A compro- by carbon yields iron and silicon, which react to
mise is necessary between cheap raw materials give ferrosilicon. This FeSi, on account of its ap-
and avoiding damage to the furnace. preciably higher density, collects under the car-
The gas pressure inside the furnace hood bide melt and normally flows away on tapping
should be about equal to atmospheric pressure. the furnace. As the melting point of this alloy
A lower pressure causes atmospheric oxygen is however several hundred kelvin below that of
to leak into the furnace, severe excess pressure the carbide melt, there is a danger that FeSi could
leads to carbon monoxide contaminating the en- flow through cracks in the extremely hot furnace
vironment and can endanger operating person- lining and cause damage in the area surrounding
nel. the furnace before it solidifies. In every carbide
Where large units or groups of furnaces are in plant constant attention is paid to this problem.
production, the entire furnace operation is usu-
ally computer-controlled from a separate control
room. 4.5. Furnace Gas
To tap off the calcium carbide, the furnace
is opened mechanically or by burning a tap- Composition. The composition of the fur-
ping hole with an electric arc. The tapping elec- nace gas depends on the raw material. If moist
trode is a baked electrode, 10 – 12 cm thick, coke is used, the hydrogen content increases on
which is supplied with electricity from its own account of the water-gas reaction, C + H2 O 
transformer, a furnace transformer, or both. The CO + H2 . The result is the same when any
molten calcium carbide flows at 1700 – 2100 ◦ C, appreciable amounts of volatiles in the black
depending on its purity, through cooled tapping material are thermally cracked. Incompletely
spouts into cast-iron ladles that can be handled calcined limestone leads to the production of
on a carousel arrangement or continuous track. carbon monoxide as a result of the reaction
Owing to its high melting point and the rapid loss CO2 + C  2 CO, which consumes both coke
of heat by radiation, technical-grade calcium and energy.
carbide (80 % CaC2 ) solidifies very quickly so A sudden increase in hydrogen content sug-
that the tapping holes must be kept open either gests a water leak in the furnace. If the carbon
mechanically or manually with steel rods. When dioxide and nitrogen contents increase, then the
tapping is completed, the hole can be closed with hood can no longer be relied upon to be gastight.
a clay plug or plugging carbide is propelled or If atmospheric oxygen enters the furnace hood,
blown into the tapping hole until it solidifies. combustion occurs and increases the tempera-
The fumes arising from the tapping hole are re- ture of the cooling water and gas. Explosions
moved by fume extraction equipment. As these are to be expected only on ignition of an un-
fumes have the character of an aerosol (particle burnt mixture of oxygen and carbon monoxide
size, 20 % < 10 µm), purification is expensive. when the furnace is cool.
Calcium Carbide 9

A typical analysis of the purified gas (vol %) ca. 2000 kWh per tonne. In practice, for 300-L
follows: technical-grade calcium carbide, depending on
CO 80 – 90 CH4 1
purity of raw materials, furnace type, and load-
H2 6 – 15 N2 2–7 ing, about 3000 – 3300 kWh/t are required. The
CO2 0.5 – 3.0 difference is accounted for by the heat contents
of the molten carbide and furnace gas and the
The heat of combustion is ca. 11 720 kJ/m3 heat lost to the cooling systems.
(STP).

Gas Purification. The carbon monoxide ob- 5. Further Treatment


tained from half-covered or closed furnaces
must be dedusted. Both dry and wet dedusting 5.1. Cooling
methods are used.
In the dry dedusting process, the gas is, e.g., Most carbide plants use the block casting
filtered by self-supporting candle filters made of method, in which the liquid calcium carbide is
ceramic fibers [33]. Their surfaces are cleaned tapped off into a ladle or crucible and solidifies to
off-line by jet pulses of previously cleaned gas or a block. The block is allowed to cool and is then
nitrogen. A final dust content of < 1 mg/m3 can broken up, ground, and sieved to the required
be attained. Finally the hot furnace gas is cooled size.
in a heat exchanger. The dust from the filter has Generally, a cast-iron crucible receives the
the composition 35 – 40 % CaO, 15 – 25 % MgO, liquid carbide at ca. 1900 ◦ C from the tapping
8 % Fe2 O3 + Al2 O3 , 7 % SiO2 , 10 % CO2 , 9 % C point. After a short time, a solid crust forms on
and it is difficult to use. Owing to the presence the walls of the crucible and isolates the iron
from time to time of soluble cyanide the dis- from the hot liquid core of the block. The heat
posal of dust also is a problem. However, there passing through this crust is then radiated from
are methods of roasting that remove cyanide. the iron. To prevent cracking of the crucible, this
In the wet process the gas is passed through process is regulated so that the temperature of the
several washing towers and sprayed with circu- iron does not exceed 600 ◦ C, mainly by ensur-
lating water. In the last stage, Theisen washers ing that the mass ratio of iron to carbide exceeds
reduce the dust content to ca. 5 mg/m3 at STP. 2 : 1. Depending on the power of the furnace,
Cyanide in the slurry is precipitated as an iron crucibles with a capacity between 0.4 and 2.0 t
complex, and the slurry is separated in thicken- are used.
ers, usually hydrocyclones. The clear liquor that For further cooling of the block there are sev-
overflows is reused. 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-
4.6. Mass and Energy Balance
ther on a block transporter, or on steel conveyor
A modern large furnace without hollow elec- belts that transport it to the crusher. The cooling
trodes requires per tonne of 300-L calcium car- times are ca. 20 h.
bide 950 kg lime (94 % CaO), 550 kg coke Higher power carbide furnaces are generally
(dry, 10 % ash), 20 kg electrode material, and equipped with crucibles of capacity over 1 t. In
3100 kWh electricity [26]. one operating procedure the filled crucible is
The typical analysis (wt %) of a commercial placed in a cooling room, and after 25 – 30 h
calcium carbide that yields 300 L of acetylene the contents of the crucible are tipped into the
per kilogram of calcium carbide follows: crusher. This procedure has the disadvantage
CaC2 80.5 Fe 0.2
that for a 55 MW carbide furnace, 400 1.5 t cru-
CaO (free) 12.9 S 0.5 cibles must be ready for use. As the weight of
Si 1.3 C 0.3 the crucible must be at least twice the weight of
Al 1.1
the contents, this means an investment in about
The enthalpy of reaction (∆H) for such cal- 1200 t of cast iron for crucibles.
cium carbide is 465 kJ/mol, corresponding to
10 Calcium Carbide

A simpler procedure is to use a conical cru- The principal criterion of the quality of cal-
cible open at the bottom and placed on a steel cium carbide is the amount of acetylene pro-
plate. After ca. 2 h the crucible can be lifted from duced per unit mass of calcium carbide by re-
its bottom plate. The block is then pushed onto an action with water – the so-called liter number,
inclined plane and onto a band conveyor which because it is a direct measure of the CaC2 con-
transports it to the crusher. Conveyor tapping tent of the carbide.
systems, which allow continuous transport of the The method of determining this gas yield is
calcium carbide from the furnace to the crusher, laid down in the standard specifications. The
have been developed [34]. British standard calculates the dry gas volume
All attempts to use even a part of the heat at atmospheric pressure and 15 ◦ C, whereas the
content of the calcium carbide block (ca. 33 % German standard assumes that the gas is satu-
of the energy used in production) have failed. rated with water vapor at 15 ◦ C. (Such differ-
ences explain the differences in the liter num-
bers.)
5.2. Size Reduction When calcium carbide is crushed, the im-
purities concentrate in the finer fractions, and
Because calcium carbide reacts with atmo- thus the minimum liter number of commer-
spheric water vapor, further processing of the cial calcium carbide depends on the grain size.
block is started when its average temperature For the coarsest size fraction the British stan-
reaches ca. 400 ◦ C, to minimize the losses of dard requires 295 L/kg, and the German stan-
acetylene during processing. The method of pro- dard 300 L/kg. For smaller size fractions, e.g.,
cessing depends on the intended use of the cal- 4 – 7 mm, the British standard is 275 L/kg, and
cium carbide. The first step is always to crush the German standard 260 L/kg.
the block, usually to < 100 mm. Then the de- Because the gas determination methods in all
sired size grading is produced by sieving, fur- specifications are time-consuming, industry has
ther crushing, and, if necessary, milling in im- developed methods of testing for liter number by
pact mills. Magnetic impurities (iron and fer- using small amounts of calcium carbide in more
rosilicon) must be removed from the calcium compact apparatus. In this way a large number
carbide. For this purpose, magnetic separators of tests of sufficient accuracy can be carried out
are installed in all stages of the size reduction in a short time, and calcium carbide producers
process. can continuously monitor their production.
The most important size ranges specified in
individual standards are (in mm): 2 – 4, 4 – 7,
5.3. Quality Specifications 7 – 15, 15 – 25, and 25 – 50. The British stan-
dard also gives the ranges 1 – 2, 4 – 80, 1 – 80,
In many countries the quality requirements are and 0 – 80. It also mentions the well-known
laid down in standard specifications: commercial form 14 ND (0.4 – 1.7 mm), without
making it a standard.
United States Federal Specification 0-6-101 a
(July, 1949) The phosphine content of the acetylene pro-
Australia Standards Association of Australia, duced is specified in all the standards. The maxi-
Publication No. K 49 (1931) mum is in the region of 0.1 vol %. Detailed meth-
Belgium Norme Belge, NBN 211-01 (01.72)
France Norme Française, NF T 24-001 ods for the determination of sulfur and of ma-
(10.54 + 09.55) terials insoluble in dilute sulfuric acid are also
Germany DIN 53922 (07.79)
United Kingdom British Standard 642 (1965, 11.66) given, but no upper limits are set.
India Indian Standard IS 1040 (1978) For the determination of the quality of the
Israel Israel Standard 267 T [250 × 4], granular calcium carbide, samples must be taken
SJ 446 (07.62)
Japan Japanese Industrial Standard correctly. All standard specifications therefore
JIS K 1901 (1974) give precise instructions regarding sampling and
Mexico Norme Official K 23 (1945)
sample preparation.
Normally these standards specify sieve anal-
ysis, dust content, gas generation, and phos-
phorus content.
Calcium Carbide 11

5.4. Transport and Storage charged pneumatically. For storage and transport
in the open, only suitably equipped containers
Owing to the fact that calcium carbide produces are allowed, not drums or kegs.
a flammable gas in the presence of water, it
is classed as a hazardous industrial material.
Therefore, in most countries special regulations 6. Environmental Protection
concerning packing and storage have been is-
sued. The raw materials used in manufacturing cal-
In Britain “The Storage of Carbide of Cal- cium carbide are nonpoisonous and present no
cium”, published by the British Acetylene As- hazard to the environment. During production,
sociation, states the regulations. transport, and preparation of these raw materi-
According to the “Verordnung über als, dust can cause a nuisance in the vicinity of
Acetylenanlagen und Calciumcarbidlager”, the factory and at the workplace and is therefore
anyone in Germany who stores calcium car- removed by air extraction and retained by means
bide must register [35], [36]. The requirements of filters.
for these storage sites are stated in “Technische Precautions, especially breathing protection,
Regeln für Acetylenanlagen und Calciumcar- must be taken when handling hot Söderberg ma-
bidlager” (TRAC 301, 1982). In addition, the terial. The carbide furnaces of the open construc-
provisions of the “Arbeitsstoffverordnung” (in- tion emit lime and coke dust from the surface of
dustrial materials regulations) are applicable. the burden. As a rule, open furnaces are fitted
The following international regulations gov- with large extraction hoods so that these emis-
ern the transport of calcium carbide [37–39]: sions, together with lime dust arising during tap-
ping, can be extracted and filtered. Closed fur-
Land transport (ADR/RID)
Class 4.3
naces emit dust only on tapping. This dust, be-
Item 17b cause of the extremely small particle size, makes
UN no. 1402 high demands on the filtration equipment.
Sea transport (IMDG)
Class 4.3 Carbon monoxide gas from open furnaces
UN no. 1402 burns directly at the surface of the feed material
PG II
MFAG 705
to harmless carbon dioxide. From closed fur-
EMS 4.3-03 naces it is usually used as fuel gas. The traces
Air transport (ICAO-TI, IATA-DGR) of cyanide in the furnace gas are converted into
Class 4.3
UN no. 1402 harmless compounds by special treatment in the
PG II gas purification equipment. The residues from
wet purification are usually dumped.
Labelling (EU directives):
Calcium Carbide
EEC no. 200-848-3 7. Uses
Symbol: F – Highly Flammable
R phrases Calcium carbide has three main uses: the
R15: Contact with water liberates extremely flammable gases
S phrases manufacture of acetylene (→ Acetylene,
S8: keep container dry Chap. 4.3.4.), reaction with nitrogen to give
S43: In case of fire use dry sand. Never use water.
cyanamide, see→ Cyanamides, and the desul-
furization of pig iron, cast iron, and steel. Since
In general, steel containers are permitted for 1960 the use of carbide-based acetylene has de-
transport of calcium carbide, e.g., drums or kegs. clined worldwide as a raw material for heavy
Under certain conditions transport in cardboard chemicals due to the widespread use of petro-
cartons is allowed, provided that the carbide is chemicals. Only a few chemical products are
also sealed in airtight bags. still produced from acetylene. These include
For the transport of larger amounts of calcium butynediol, a component of plastics and fibers,
carbide, containers with a capacity of 1 – 20 t and acetylene black, used in dry batteries.
have been introduced. Fine granular calcium car- Acetylene from calcium carbide still holds a
bide is also conveyed in tankers that can be dis- 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.


311 (1961) 62 – 75.
Between 1962 and 1965 the world output of cal- 2. G. W. Healy, J. Met. 18 (1966) 643.
cium carbide reached its maximum, nearly 10 × 3. H. H. Franck, Z. Anorg. Allg. Chem. 232
106 t/a. Since then the decline has been steady. (1937) 75 – 111.
This decline has been accompanied by a shift of 4. M. Atoji, J. Chem. Phys. 54 (1971) 3514.
the main production centers. 5. M. A. Bredig, J. Phys. Chem. 46 (1942) 801.
6. M. von Stackelberg, Z. Phys. Chem. Abt. B 9
Table 3 lists production for the years 1962,
(1930) 437.
1972, 1982, and 1990. In the 1960s and 1970s,
7. N. G. Vannerberg, Acta Chem. Scand. 15
there was a severe decline in North America, (1961) 769.
Western Europe, and Japan on account of con- 8. N. G. Vannerberg, Acta Chem. Scand. 16
version to petroleum-based products and re- (1962) 1212.
duced output of calcium cyanamide for fertilizer, 9. O. Kubaschewski, E. L. L. Evans,
whereas Eastern Europe showed an increase in Metallurgical Thermochemistry, Pergamon
calcium carbide production. In the 1980s, how- Press, London 1967.
ever, replacement of calcium carbide by petro- 10. Winnacker-Küchler, 3rd ed., vol. 1, p. 426;
chemical raw materials began in these countries, 4th ed., vol. 2, p. 609.
too. The rapid decline in calcium carbide pro- 11. G. Geiseler, W. Büchner, Z. Anorg. Allg.
duction in the last few years has been due to Chem. 343 (1966) 286.
Calcium Carbide 13

12. K. K. Kelley, Bull. US Bur. Mines 477 (1950) 27. A. Helfenstein, DE 226956, 1910.
101. 28. Det Norske Aktieselskab for Elektrokemisk
13. L. Barin, O. Knacke: Thermochemical Industrie, DE 324741, 1919.
Properties of Inorganic Substances, Springer 29. Union Carbide Corp., US 2996360, 1958.
Verlag, Berlin-Heidelberg-New York, Verlag 30. D. E. Hamby, J. Met. 19 (1967) 45.
Stahleisen, Düsseldorf 1972. 31. Elkem, DE 3 141 108, 1983.
14. W. Rettkowski, Chr. Geilhufe, K. H. Rüdiger, 32. W. Weiss, L. Bökelmann, L. Iltzsche, H.
Chem. Tech. (Leipzig) 28 (1976) 588. Kleiner, Chem. Tech. (Leipzig) 36 (1984) 89.
15. E. Biesalski, H. van Eck, Angew. Chem. 41 33. SKW Trostberg AG, DE-OS 19 611 119, 1997.
(1928) 278. 34. Denki Kagaku Kogyo, DE 4 210 387, 1994.
16. O. Ruff, E. Förster, Z. Anorg. Allg. Chem. 131 35. Verordnung über Acetylenanlagen und
(1923) 321. Calciumcarbidlager 27. 02. 1980, BGBl. I,
17. Bayer, DE 944487, 1954. p. 173.
18. W. A. Barber, C. L. Sloan, J. Phys. Chem. 65
36. Technische Regeln für Acetylenanlagen und
(1961) 20 – 26.
Calciumcarbidlager (TRAC), July 1971.
19. S. Kiritani, T. Nishimaki, CEER Chem. Econ.
37. European agreement concerning the
Eng. Rev. 16 (1984) no. 5.
20. K. Feldmann, Chem. Ing. Tech. 41 (1969) 199. international carriage of dangerous goods by
21. K. Budde, A. Strauss, B. Schmidt, Chem. Tech. road (ADR), 07. 1968.
(Leipzig) 28 (1976) 585. 38. Agreement concerning the international
22. R. Toussig: Die Industrie des carriage of dangerous goods by rail as annex I
Calciumcarbides, Knapp, Halle 1930. of the international agreement on railroad
23. J. Wotschke: Grundlagen des elektrischen freight traffic (RID, CIM), 09. 1977, revised
Schmelzofens, Knapp, Halle 1933. 01. 09. 1983.
24. E. Kluss: Einführung in die Probleme des 39. International regulation for inland navigation
elektrischen Lichtbogen- und and for ocean navigation and for aviation
Widerstandsofens, Springer Verlag, Berlin (IATA).
1951. 40. SKW Trostberg, DE 2 741 588, 1977.
25. E. Kluss, Z. Elektrotech. 72 (1951) 115. 41. SKW Trostberg, Thyssen Stahl, EP 0 164 592,
26. AG für Stickstoffdünger, DE 545696, 1925; 1985.
DE 571711, 1928.

Calcium Carbonate → Lime and Limestone