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Review

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Production of Acetylene and Acetylene-based Chemicals from Coal


Harold Schobert*
The EMS Energy Institute, The Pennsylvania State University, University Park, Pennsylvania 16803, United States
6. Conclusions
Author Information
Corresponding Author
Notes
Biography
Acknowledgments
References

1. INTRODUCTION
Acetylene has been known since the mid-19th century, when it
was discovered by Edmund Davy in Ireland and later studied
extensively by Marcellin Berthelot in France. The triple bond in
acetylene, and the fact that acetylene is thermodynamically
unstable, give acetylene a very rich chemistry, with many
applications. The accidental discovery of calcium carbide,
produced from coal or coke and limestone in an attempt to
prepare calcium metal, and the recognition of the reaction of
calcium carbide with water to form acetylene, opened a route to
the large-scale production of acetylene. In the 20th century, the
two giants in the eld of acetylene chemistry were Julius
Nieuwland, at Notre Dame University in the United States, and
Walter Reppe, at I.G. Farbenindustrie and BASF in Germany.
Their extensive studies, along with contributions from many
others, created a role for acetylene as a vital feedstock for the
production of commodity chemicals. Acetylene, along with the
byproduct tar from metallurgical coke plants, were the two
pillars of the organic chemical industry to about the middle of
the 20th century.
The global availability of inexpensive petroleum after about
1950 led to the development of a variety of petrochemical
processes, especially based on ethylene. This was a factor in the
steady displacement of coal tar and acetylene by petroleum- or
gas-derived feedstocks. As a feedstock for production of
chemicals, acetylene increased in importance after the Second
World War and peaked in the 1960s.1 In 1960, world acetylene
production was 10 million metric tons.2 By the early 1990s,
annual worldwide production had declined to about half that
value,2 and currently only several hundred thousand metric
tons are made, mostly from sources other than coal.

CONTENTS
1. Introduction
2. Production of Acetylene
2.1. Indirect Production via Calcium Carbide
2.2. Direct Production via Arc Plasma Reactions
2.2.1. Eects of Coal Composition
2.2.2. Eects of Reaction Conditions
2.2.3. Yields and Selectivity
2.2.4. Pilot-Scale Testing
2.3. Alternatives to the Arc-Plasma Process
2.4. Other Methods
3. Purication and Handling of Acetylene
3.1. Purication
3.2. Handling Acetylene
4. Acetylene as a Fuel
5. Conversion of Acetylene to Commodity Chemicals and Materials
5.1. Acetaldehyde
5.2. Acetic Acid and Acetic Anhydride
5.3. Acetylene Tetrabromide
5.4. Acrylic Acid
5.5. Acrylonitrile
5.6. Aromatic Hydrocarbons
5.7. Alkynes
5.8. 1,4-Butanediol
5.9. Carbon Black
5.10. Chlorinated Solvents
5.11. Ethanol
5.12. Ethylene
5.13. Heterocyclic Compounds
5.14. Isoprene and Chloroprene
5.15. Lewisite
5.16. Norbornadiene
5.17. Polyacetylene
5.18. Propargyl Alcohol
5.19. Resins
5.20. Vinyl Acetate
5.21. Vinyl Chloride
5.22. Vinyl Esters and Ethers
5.23. Vinyl Fluoride
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2. PRODUCTION OF ACETYLENE
The eld of coal liquefaction is divided into indirect processes
(coal to synthesis gas to liquids) and direct processes (making
liquids straight from the coal). Acetylene production from coal
can be thought of in an analogous fashion. Indirect production
of acetylene involves using coal, or coal-derived coke, to
Special Issue: 2014 Chemicals from Coal, Alkynes, and Biofuels
Received: May 21, 2013
Published: November 20, 2013
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aggregates, rather than the batch operation of a traditional coke


oven.13 Along the same line, lignite has been carbonized with
calcium hydroxide or calcium carbonate at 9001400 C to
form an aggregated solid that is then fed to an oxygen-thermal
furnace for calcium carbide production, as discussed further
below.14
Methods have been developed to take advantage of low-rank
coal feedstocks for calcium carbide production, as alternatives
to the more expensive anthracite or coke. One such method
includes the partial combustion of some of the coal in the
furnace charge.15 The most recent involves the conversion of
low-rank coal to a process middle coke containing 87%
carbon.16 This material is mixed with calcium oxide and heated
electrically, but with the addition of some oxygen to the
furnace. Combustion of a portion of the process middle coke
reduces the electricity consumption and helps to heat the
charge. Calcium carbide formation in a plasma reactor has also
been demonstrated.17
In the context of modern chemical technology, calcium
carbide production has the negative characteristics of being an
energy-intensive, long-residence-time batch process involving
the handling and feeding of solids. Furthermore, the severe
reaction conditions result in a relatively short working life for
an expensive electric furnace. Electricity consumption is
approximately 3.3 kWh/kg of calcium carbide produced.8,16,18,19 Despite these disadvantages, some 12 million
metric tons of calcium carbide were produced in China in
2006.15 This represents by far the greatest share of worldwide
production, which has been estimated to be >15 million metric
tons/year.20 Growth rates in calcium carbide demand are
forecast to be about 12% annually in the United States and
western Europe but 810% in China.21
Commercial calcium carbide is available in various grades and
particle sizes. The best-quality material produces 288 L of
acetylene/kg of carbide.10
Acetylene is produced by the reaction of calcium carbide with
water.1,2,6,11,22 Details of the generating equipment and its
operation are provided in the early literature6,11 and have not
undergone fundamental changes in the years since.
The reaction can be eected in so-called wet or dry
generators.8 The wet generator uses an excess of water, in at
least a 6:1 ratio of water to carbide;23 more recent data suggest
ratios in the range 79 t of water/t of calcium carbide.16
Calcium hydroxide is produced in a water slurry as byproduct,
at a rate of 2.8 t of Ca(OH)2/t of acetylene.1 The dry generator
is run with a near-stoichiometric quantity of water and
produces a pourable powder of calcium hydroxide, any excess
water being evaporated by the heat of reaction.2 The largest dry
generators have an output of 3750 m3/h, equivalent to 32 000
t/year.2 The acetylene yield amounts to 1 t per 3.1 t of 80%
pure calcium carbide.8 A portion of the byproduct calcium
hydroxide could be recycled to carbide production16 or could
have markets in the agricultural sector as fertilizer and in
chemical industries as, for example, raw material for cement
production. Recycle is limited to a maximum of 60%, to avoid
accumulation of impurities in the furnace.8 Of the two types of
generators, the wet system is considered to be safer to
operate,24 presumably because the excess water helps dissipate
the heat of reaction.
The reaction of calcium carbide with water is highly
exothermic. If no cooling were used, the heat of reaction
could raise the temperature of the reacting mixture to 700 C.23
Temperatures in this range could trigger further exothermic

produce calcium carbide and then making acetylene from the


carbide. The direct process involves various ways of making
acetylene directly from a coal feedstock, without an
intermediate step of calcium carbide.
2.1. Indirect Production via Calcium Carbide

Calcium carbide belongs to the family of carbide compounds


known as acetylenides, which can be considered to be salts of
the C22 anion. Numerous elements are known to form
acetylenides, including all of the alkali and alkaline earth
elements, the metals of groups 11 and 12 of the periodic table,
and some of the lanthanides.3 Calcium carbide is the only one
to have achieved large-scale commercial production. Friedrich
Wohler discovered calcium carbide in 1862.3 Supposedly, the
rst synthesis of calcium carbide from calcium carbonate and
coke was the unintended outcome of an attempt to obtain
metallic calcium by carbothermic reduction of a calcium
compound.4 Production of calcium carbide in an electric arc
furnace goes back at least 120 years.5 Details of Willsons
discovery and other 19th-century work on calcium carbide and
acetylene production are reviewed by Thompson.6 The
importance of Willsons work, relative to the earlier studies of
Davy, Wohler, and Berthelot, is twofold: it was the rst
synthesis of calcium carbide that could be applied commercially, and the product was a nearly pure, crystalline material.7
The highly endothermic reaction of calcium oxide with
metallurgical coke occurs in an electric furnace with three
Soderberg electrodes at temperatures of 20002300 C.1,8
Other carbon sources can be used; however, the two that
appear to be most suitable are metallurgical coke and
anthracite.9 The reaction can be written as
CaO + 3C CaC2 + CO

Production of 1000 metric tons (t) of calcium carbide requires


875 t of calcium oxide and 650 t of carbon, usually in the form
of anthracite or coke.10 Calcium carbide formation begins at
temperatures above 1600 C; below this temperature, the
reaction runs from right to left as written above, and carbon
monoxide will decompose the carbide.3 Calcium carbide and
calcium oxide form a eutectic at 1630 C.9 At temperatures
>2200 C, calcium carbide will begin to react further with
calcium oxide to produce calcium metal and carbon monoxide.3
The furnaces operate with 100250 V alternating current and a
current density in the electrodes of <10 A/cm2.8 Molten
calcium carbide is tapped from the furnace into crucibles. There
is a substantial production of byproduct gas, primarily carbon
monoxide, amounting to about 400 m3/t.8 In the early years of
the industry, this gas was allowed to burn inside the furnace; in
more up-to-date installations, the gas was collected and used as
a fuel.8
The furnace charge can be a loose mixture of the calcium
oxide and carbon source (e.g., anthracite) charged in powder
form. It is important for these materials to have sulfur and
phosphorus contents as low as practically possible, to limit the
amounts of hydrogen sulde and phosphine impurities in the
acetylene.11 Alternatively, the feed can be formed into
briquettes, incorporating the reactants in stoichiometric
proportions with a hydrocarbon or carbohydrate binder in
small amounts. Aggregates of calcium oxide and bituminous
coal provide a third option; in this case, the mixture is rst
coked in a standard byproduct recovery coke oven and then fed
hot into the arc furnace.12 A subsequent modication of this
third approach allowed for continuous production of the
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a plasma, in which the thermal decomposition of coal is very


rapid. The temperature of the arc is estimated to be 10 00015
000 C.33,34 Because acetylene is thermodynamically more
stable than other hydrocarbons at temperatures >1200 C,
reaction in a plasma oers a route to direct production of
acetylene from coal. Compared to the indirect route, reaction of
coal in a plasma or arc process oers the advantages of an
overall simpler process scheme and less impact on the
environment.35
Work on plasma conversion of coal to acetylene is continuing
in China.36,37 The process has been scaled up to a 2-MW pilotplant reactor38 and then to a 5-MW reactor, for which a useful
model is available.39 The 5-MW reactor is thought to be the
largest arc-plasma pyrolysis reactor in the world.40
2.2.1. Eects of Coal Composition. Acetylene yield is
inversely related to coal rank, with coals of higher volatile
matter content (i.e., of lower rank) providing higher
yields.27,33,41,42 It is proposed that acetylene formation is a
two-step process, involving rst the rapid thermal decomposition of the coal into volatiles and solid (char, coke, or soot)
and then reaction of the volatiles in the plasma, accounting for
the actual formation of acetylene.33,43
Rank also impacts the formation of byproduct coke. Tests
with Chinese coals showed that anthracite had low tendency for
formation of coke and adhesion of coke particles to the reactor
walls, while bituminous coals had signicant coking and
adhesion.44 This same rank relationship might be expected to
be observed at much lower temperatures and heating rates as
well.
Thermodynamic modeling indicates that two properties
impact acetylene yield: the volatile matter content, which has a
positive eect, and the oxygen content, which diminishes
acetylene formation with concomitant increase in carbon
monoxide yield.45 Both of these parameters decrease with
increasing rank. Qualitatively, coals of high volatile matter but
low oxygen content give the best yields of acetylene.46 Rather, a
coal of about 80% carbon and 12% oxygen gives a better
acetylene yield.45 Other work has suggested 2544% volatile
matter and <9% oxygen [on a dry ash free (daf) basis] as
optimum.47 Coals in this volatile matter range have produced
acetylene yields of 1722%.35 Related work using a solvent
extract from coal, the extract having 43% volatile matter,
resulted in about 24% acetylene yield.48 The suggested
optimum volatile matter range has been narrowed to 32
39%.43 (The high acetylene yield from a coal of 33% volatile
matter was noted above.) Coals of >37% volatile matter should
ideally contain <13% oxygen.49 The key problem arising from
the formation of carbon monoxide, that is, a higher oxygen
content in the feed coal, is that carbon incorporated in the
monoxide is unavailable for formation of acetylene.47,49 This is
illustrated in Figure 1.
The competitive, and unwanted, formation of carbon
monoxide accounts for the fact that lignites, despite their
high volatile matter contents, produce only modest yields of
acetylene.43 After passing through an optimum of acetylene
formation in the rank range corresponding to 3040%
volatile matter, yield then decreases at higher ranks.50 A few
reports claim that no correlation of acetylene yield with volatile
matter exists.51
The interplay of volatile matter and oxygen content is
illustrated by tests on four coals of dierent ranks.52 In this
work, a high-volatile A bituminous coal of 38% volatile matter
and 8% oxygen provided the highest acetylene yield, better than

reactions of the acetylene. If air is present in the reactor, the


worst-case outcome would be an acetyleneair explosion.
Nowadays acetylene made via the calcium carbide route is
primarily used as a fuel for oxyacetylene welding and cutting
torches, with the notable exception of its use in China for
manufacturing vinyl chloride monomer (discussed below).
Calcium carbide production is limited to locations that have
both cheap electrical energy for operating the furnace and ways
of handling and disposing of the calcium hydroxide byproduct.
Nevertheless, possible future limitations on petroleum
supplywhether real or stemming from geopolitical events
could be overcome in part by relying on carbide-based
acetylene with coal as the carbon source, despite the
accompanying signicant economic and environmental issues.
Wartime restrictions on petroleum resulted in nearly 90% of
the acetylene used in the German chemical industry being
made from calcium carbide.25
Barium carbide, made from barium carbonate, has been
suggested as an alternative to calcium carbide.9 The advantage
claimed, relative to calcium carbide, is that the barium
compound could be produced in a coal-red furnace at about
1650 C, not requiring the use of a high-temperature electric
furnace with its attendant high energy costs.9 Specically, one
route to barium carbide involves heating the carbonate with a
carbon source and magnesium: BaCO3 + 3Mg + C BaC2 +
3MgO.6 However, the production of barium carbide and its
subsequent hydrolysis to acetylene are more complicated than
with calcium carbide, such that the barium-based process was
never commercialized. Lithium carbide is also an alternative
starting material.26 Electrolytic decomposition of the lithium
hydroxide or oxide provides lithium, which can be recycled by
reacting again with coal to regenerate the carbide.
Over the years, process improvements have been made,
including reuse of the calcium hydroxide formed when calcium
carbide is reacted with water, recovery of carbon monoxide
from the carbide furnace, minimizing other emissions from the
furnace, and reduction of heat losses.23 Nevertheless, negative
factors, including the very large electricity requirement, which
dictated the siting of large carbide plants near sources of
inexpensive electricity, and the problems of handling large
quantities of solids, outweighed the perceived benets of the
carbide process. China is now the largest producer of calcium
carbide, with most of it going to acetylene production.27
Production of acetylene from pyrolysis or steam cracking of
petroleum fractions accounts for most of the acetylene used
nowadays.
2.2. Direct Production via Arc Plasma Reactions

Production of acetylene via pyrolytic routes takes advantage of


the fact that acetylene is the thermodynamically stable form of
hydrocarbons at temperatures above 1200 C28,29 and that its
free energy of formation decreases at higher temperatures.30
However, even under these circumstances acetylene is unstable
with respect to decomposition to carbon and hydrogen, thus
requiring that residence times during pyrolysis be extremely
short and that the pyrolysis products be cooled rapidly.30 It has
been questioned whether the acetylene produced in experiments using lasers, shock tubes, or plasmas is a true primary
pyrolysis product from coal or arises from secondary
reactions.31
Berthelot may have been the rst to observe the formation of
acetylene when an electric arc is stuck, by use of carbon
electrodes, in a hydrogen atmosphere.32 The ionized gas forms
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Figure 1. Eect of volatile matter content [moisture ash free (maf)


basis] on conversion of carbon to () acetylene and to (---) carbon
monoxide, based on data from Bittner and Wanzl.43

Figure 2. Dependence of carbon conversion to () acetylene and to


(---) carbon monoxide on ash yield, dry basis, based on work of Bittner
et al.50

a high-volatile C bituminous coal with higher volatile matter,


43%, but also higher oxygen, 15%. Both were superior to a
lignite of 54% volatile matter and 22% oxygen. The lowest
acetylene yield was obtained from an anthracite of 4% oxygen,
but only 8% volatile matter. Plasma pyrolysis of a Polish brown
coal (for which the oxygen content was not reported in the
original literature but can reasonably be presumed to be high
for coals of this rank, that is, some 2025%)53 showed
formation of acetylene and carbon monoxide in 100:77 ratio.54
Perhydrous coals show a dierent dependence on volatile
matter. For example, a perhydrous British coal of 46% volatile
matter gave a 38% yield of acetylene (equivalent to conversion
of 46% of the carbon in the coal).
Some reports claim that the inorganic components of coal
have no eect on acetylene formation.41,45 However, these
ndings contradict other work that showed an inuence of the
ash value, acetylene yield being inversely related to ash value.50
The apparent relationship of acetylene yield with ash was
attributed to the eect of oxygen being released from the
decomposition of mineral matter and reacting with carbon to
produce carbon monoxide.49,50,54 Figure 2 shows a relationship
of ash value to acetylene and carbon monoxide yields.
The mineral matter content would aect the energy
requirement per unit acetylene yield, since the minerals will
be heated right along with the carbonaceous part of the coal.41
With respect to the heteroatoms, oxygen forms primarily
carbon monoxide, especially above 1227 C;54,55 sulfur
produces primarily carbonyl sulde, especially between 727
and 1527 C, along with some hydrogen sulde and carbon
disulde;45,54 and hydrogen cyanide represents the main
nitrogen-containing product.33,45,55,56 Tests with a series of
four British coals showed that carbon monoxide formation was
quite close to the amount that would have been predicted on
the basis of oxygen content of the coals,57 conrmed by a study
on six Chinese coals.49 Addition of nitrogen to the reactor
increases the yield of hydrogen cyanide at the expense of
acetylene,33 suggesting that, as in formation of carbon
monoxide, there is a competition for available carbon.
Coal-derived liquids have been shown to produce a gaseous
product that is 35% acetylene in a submerged-arc reactor.48
2.2.2. Eects of Reaction Conditions. On the basis of
thermodynamic modeling of the reactions of Chinese coals, a
hydrogen atmosphere would give the highest acetylene yield,

followed, in order of decreasing yield, by argon and nitrogen.45


However, the yields reported in this work, 10%,45 are
signicantly lower than conversions of 3540% reported by
other authors.33,47,56,58 Use of an argonhydrogen mixture
substantially increased acetylene yields relative to reaction in
pure argon, for example, from 15% to 40%.52 Compared to
reaction in pure argon, the introduction of hydrogen, up to a
maximum of 50% in the mixture, improves acetylene yield, in
part by retarding the decomposition reaction C2H2 2C +
H2.51 On the other hand, hydrogen concentrations >50% in an
Ar/H2 mixture have been argued to reduce acetylene yield by
reducing the bulk plasma temperature.51 The highest acetylene
yield, 60% (corresponding to conversion of 74% of the carbon
in the coal) was achieved with a British coal of 33.4% volatile
matter in the 90:10 Ar/H2 atmosphere.57 A 40% conversion of
the carbon in coal to acetylene was achieved by reaction in a
90:10 argon/hydrogen plasma.33,56 Nonetheless, it is argued
that an abundance of hydrogen in the reactor atmosphere
enhances conversion of coal to acetylene.59
Acetylene yield in a hydrogen atmosphere is 3 times greater
than from a comparable reaction performed in argon.60 The
importance of hydrogen is attributed to its role in retarding the
decomposition of acetylene.47 These reports are consistent with
a doubling of acetylene yield in a 90:10 argon/hydrogen plasma
compared to the yield obtained in pure argon.56 The yields of
acetylene, and corresponding energy consumptions, vary
considerably among reports in the literature.
Thermodynamic analysis suggests optimum temperatures for
acetylene production at atmospheric pressure in the range
32004200 C.55 In practice, reaction temperature >1400 C is
important.2 High temperature is critical; plasma treatment at
temperatures <1000 C favors methane formation rather than
acetylene,61 even at very rapid heating rates.62 The 2- and 5MW pilot-scale reactors in China run at about 3200 C.40
The extent of reaction depends greatly on particle size.33,34,52
Small particle size is important.27,41 Particle size must be <200
m, preferably 50 m.33,63,64 As particle size increases, coking
becomes more of a problem;44 the solid carbon is not reactive
in hydrogen.65 The outer surface area of the particles is
recommended to be in the range 0.52.0 m2/cm3.47 Coals of
high uidity, as measured by the Gieseler test,53 appear to
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residence times are inversely proportional to the cube root of


the specic outer surface area of the coal particles.47
Energy consumption has been estimated to be 23 kWh/kg
for acetylene production, on the assumption that the reaction
proceeds via the breakdown of aromatic ring systems.58
However, the actual energy consumptions are reported to be
much higher, estimated to be possibly as great as 100 kWh/
kg,58 though values so high as this do not seem required. Values
of power requirements in the range of 110 kWh/kg (4000
40 000 kJ/kg) have been suggested.47 More recent work
suggests that the best (i.e., lowest) practical values would be on
the order of 20 kWh/kg, with acetylene yields of 2030% at
these conditions.35 The Huls process (discussed below)
operates at 8 kWh/kg of coal.70 Data for a Canadian
bituminous coal show a specic energy requirement of 10
kWh/kg of acetylene;43 comparable to the value of 13 kWh/
kg of acetylene reported earlier,71 and comparable to other
work reporting values of 1115 kWh/kg of acetylene.74 It
would seem reasonable to expect a 35% yield of acetylene on a
daf coal basis with an energy consumption of 9 kWh/kg.58
Quenching of the gases leaving the reactor should be nearly
instantaneous,27,43,58,75 on the order of milliseconds.28,76 Rapid
quenching of the product gases is important,2,28,41,46,51,76,77 to
retard the decomposition of acetylene to the elements or to
other hydrocarbons. If allowed to cool slowly, hot acetylene can
revert to tar and oil in about 2 s.78 Water or cold liquid
hydrocarbons can be used as quenching media.47,76 This
requirement for rapid quenching is a consequence of the fact
that acetylene can rapidly decompose to the elements or
combine to form higher hydrocarbons unless promptly brought
down to near-ambient temperatures. Therefore, quenching is a
general issue for high-temperature acetylene-formation processes and is not unique to formation of acetylene from coal in
arc-based processes. As an example, similar issues exist with
formation of acetylene via the partial combustion of methane.79
2.2.3. Yields and Selectivity. The yield of acetylene from
the arc-plasma process depends on numerous factors of coal
composition and of specic choices of reaction variables. Not
surprisingly, numerical values of yields reported in the literature
vary widely, over an order of magnitude. Further, some papers
report yields on the basis of, say, kilograms of acetylene
produced per kilogram of carbon reacted, while others use
kilograms of acetylene per kilogram of coal. These
complications aside, it seems reasonable to expect acetylene
yields of 3540% on a daf coal basis,58,71 with a suitable coal
feedstock and optimum reaction conditions.
The products are only gases and solid; no tars are
formed.33,41,51,54,56,57,69 The lack of tar formation may be due
to the fact that the aromatic components of the volatiles
contribute to the formation of carbon deposits in the reactor.80
A process has been disclosed that incorporates a second-stage
reactor for gasication of the residual solid, producing synthesis
gas.71 In addition to being a potential feedstock for gasication,
the residual carbon could also be burned to raise steam for
electricity generation.40
The best selectivity (i.e., the proportion of acetylene relative
to the total hydrocarbon gases in the product) is about 95%,
based on tests with a suite of 10 Chinese coals,35 in agreement
with earlier work with British coals.33,56 Unlike the dependence
of yield on volatile matter (discussed above), selectivity does
not appear to relate to volatile matter content, an eect that is
attributed to variations in coal structure.27

produce particles that shrink, or even burst, in the plasma,


further reducing the size of the reacting particles.43 The
decrease in acetylene yield with increasing particle size is
considered to be due to inecient heating of the
particles,27,33,41 or to inadequate quenching of the product
gases, or possibly to both factors.33 Heat-transfer rate limits the
temperature rise and extent of coal devolatilization.66
Mathematical modeling of heat-transfer processes inside coal
particles shows that a decreased heat-transfer coecient
between the particles and hot gas reduces the devolatilization
rate.67 Heat and mass transfer between coal particles and
surrounding gas is the rate-limiting step in acetylene
production.38 These eects become more noticeable at particle
diameters >80 m.67
High yields of acetylene require slow feed rates57 and ne
particle sizes, ideally 50 m.33,58 Both conversion of coal and
acetylene yield decrease as the coal feed rate is increased.28,33,35,68 Coal conversion appears to approach an
asymptotic limit with increasing feed rate, while acetylene yield
decreases monotonically as a function of increasing feed rate.35
The eect of coal feed rate is illustrated in Figure 3 for the Avco
laboratory-scale reactor; the specic numerical values would
dier for reactors of other sizes, but the trend would be the
same.

Figure 3. Eect of coal feed rate on acetylene yield, based on data


from the Avco laboratory-scale reactor.77

Contradictory reports indicate that feed rate had no


signicant eect on acetylene yield34,52,66 but attributed this
to poor mixing of the coal particles with the plasma, resulting in
insucient heating of the particles. (Mixing eciency between
the coal particles and hydrogen stream has an important
inuence on the release of volatiles.)38 With increased feed rate,
the extent and rate of byproduct coke formation increase.44 A
higher coal feed rate corresponds to longer heating times and a
lower nal temperature of the coal particles, causing a lower
yield of volatiles and longer time for complete devolatilization.67,69
Residence times are on the order of milliseconds,2,40,43,63,64,70,71 optimally <2.5 ms,72 with a heat-up rate
of about 1 ms to,33 at most, a few milliseconds.73 Short
residence times help maximize yields of acetylene.57 Optimum
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2.2.4. Pilot-Scale Testing. Modication of the Huls


process to operate on coal has been tested at pilot-plant
scale. Acetylene yields of up to 35% were obtained, depending
on the specic coal used.2 General aspects of operation, such as
residence times, the need for product quenching, coal particle
size, etc., are similar to those described in the previous section.
An electric arc process, related to the HoechstHuls process
discussed below, was tested by Huls and by Avco.2,28,71,77,81
Pulverized coal is fed to a hydrogen plasma arc. The best yields
of acetylene are about 35%, depending on the nature of the coal
feedstock. Compared to the processes that use gaseous or liquid
hydrocarbons as feeds, the direct use of coal is more
complicated, because of slag produced from the inorganic
components of the coal and because of the need to separate
various byproducts containing nitrogen, sulfur, and/or oxygen
that derived from the presence of these elements in the coal.
Residence times are 0.120 ms at 2000 C, after which the
product must be quenched rapidly to <400 C.82 The major
technical problems appear to be the energy balance (i.e., the
energy input to the arc) and the treatment of the gaseous
product stream to separate the acetylene and recycle hydrogen
to the reactor.83 A methane-rich gaseous feed has also been
tried as the reacting medium.84

The decline in funding for research and development in


synthetic fuels, chemicals, and materials from coal some 20
years ago seems to have ended most concerted eorts to scale
up the direct coal-to-acetylene processes mentioned above, as
well as investigation of other possible routes from coal to
acetylene. Coal-to-acetylene research is continuing in China up
to the present; most of the citations to work of the past 1015
years refer to work being done in China.
2.4. Other Methods

Because of the problems with calcium carbide production


mentioned above, most acetylene production today relies on
other routes. These do not involve coal but are mentioned
briey here to complete the discussion of acetylene production.
Further details are available in several sources.1,2,8,23,89 The
feedstocks discussed in this subsection could, in principle, be
made from coal, though doing so would result in an
exceptionally cumbersome route to acetylene.
Thermal or steam cracking processes of ethane, propane, or
their mixtures that are run at high severity to maximize ethylene
production also produce some acetylene as byproduct. Propane
cracking gives a yield of about 2% acetylene.1 The Kureha
process, using superheated steam from combustion of
methane/hydrogen mixtures, produces a 23% yield each of
acetylene and ethylene at 2000 C.2 The plant operates with
contact times of 310 ms.8 A ow sheet and additional process
details are available.8 If the acetylene is desired as a product, it
can be absorbed from the gas stream into such solvents as Nmethylpyrrolidone or dimethylformamide.1 The latter solvent
can dissolve up to 32 cm3 of acetylene/cm3 of solvent at 25 C
and 0.1 MPa.90 If the acetylene is not intended to be a separate
product, it can be hydrogenated to ethylene. A block ow
diagram of an ethane or propane cracking process that includes
hydrogenation of acetylene is given by Chenier.91
The Wul process involves pyrolysis of methane in a furnace
of which the interior is a lattice of bricks.1,23 The bricks are
preheated to 1300 C by burning a portion of the gas; then the
feed is passed through under pyrolysis conditions. These two
operations are then repeated by having the gas ow through the
furnace in the opposite direction. Each step takes approximately
1 min, requiring a 4-min cycle. The gaseous product is about
33% acetylene and 67% ethylene.1 Additional details, including
a ow sheet, are available.8 The Wul process has also been
operated with naphtha as a feedstock, but apparently no plants
are currently running with this feed. Further details on cracking
of hydrocarbon liquids to acetylene and coproducts are
available.92 The Wul process is accompanied by signicant
soot formation; most plants based on this process are now
closed. It has been suggested that the methane source could be
coal-bed methane,9 thus, in a sense, making this a coal-based
route to acetylene. Remarkably, it is also suggested that the
carbonaceous byproduct from conversion of methane to
acetylene could be used as synthetic coal.93
The Huls arc process involves pyrolysis of hydrocarbon feeds
in electric arcs, in which the temperature of the arc is estimated
to be 20 000 C.2,23 As with processes based on electric arcs
and coal feedstocks, pyrolyses of other hydrocarbons also have
contact times of milliseconds70 and require a rapid water
quench to drop the temperature of the exiting gases to 250
C.30 Acetylene and ethylene are produced in approximately
2:1 ratio, the acetylene yield being 1 t per 1.8 t of feed, or about
55%.2 The related HoechstHuls process involved using
hydrogen, preheated to 3500 C in an electric arc, as a

2.3. Alternatives to the Arc-Plasma Process

Shock-tube heating of bituminous coal, of 40 m particle size,


at 0.43.7 MPa, 475875 C, and 1.32.0 ms residence time,
showed a steady increase in acetylene yield with pyrolysis
temperature.31 Laser irradiation of Pittsburgh seam high-volatile
A bituminous coal produced gaseous products in which
acetylene was the dominant hydrocarbon.84 This work used a
1.7 J ruby laser. Acetylene amounted to about 20% of the
product; the gas in highest concentration was hydrogen, at
45%.84 Use of a 10-J laser in vacuum resulted in 91% of the
gaseous hydrocarbons being acetylene (no information was
given on the amount of hydrocarbons in the total gaseous
product).84 The coal rank eects on acetylene yield from laser
pyrolysis are similar to those discussed for arc-plasma pyrolysis.
The best yields appear to be from coals in the middle of the
rank range, for example, around high-volatile bituminous.85
Acetylene yield from high-volatile bituminous coals is a factor
of about 15 higher than the yield from anthracite.85
Pyrolysis of Kentucky high-volatile bituminous coal in a
microwave oven at 2 Torr produces acetylene, along with
methane, ethane, and ethylene, but quantitative yield and
selectivity data were not given.86 Acetylene has been produced
from the reaction of activated carbon with water in a microwave
reactor.87 Although this work focused on the use of activated
carbon, it would be interesting to determine the feasibility of
using high-carbon-content coals (i.e., anthracites), since such
coals are not optimum feedstocks for the arc-plasma reaction.
An approach much dierent from the plasma processes
involves high-temperature, high-velocity gas reactions.88 In this
case, a hot gas stream, envisioned to be at 16502500 C, is
accelerated to 1501200 m/s through a series of nozzles.
Bituminous or subbituminous coal, at particle size <75 m, is
entrained in the gas for residence times of 230 ms. As with
plasma processes, a very rapid quenching of the product gases is
necessary, <2 ms. Tests with a Kentucky bituminous coal
showed that about 8% of the carbon in the coal was converted
to acetylene. However, it appeared that the acetylene
concentration in the product gas, which is mostly steam,
carbon monoxide, nitrogen, and hydrogen, is quite dilute.
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heat-transfer agent;2 apparently this process has been tested in


a pilot plant but never commercialized. It was claimed that
almost any hydrocarbon feed, up to and including crude oil,
could be accommodated. The extraordinary energy consumption required for this process is illustrated by data for the plant
in Recklinghausen, Germany, which used medium naphtha as
feedstock. Operating with 19 furnaces, the plant produced 120
000 t of acetylene per year.8,70 Its energy consumption of 1440
GWh was estimated to be equivalent to the annual electricity
consumption of a city of 400 000 people.8 The residual coke
was said to be very reactive and could represent a
commercially interesting byproduct of the process.70
Controlled partial oxidation of methane at approximately
1500 C leads to acetylene.22,23 The Sachssee process is one
variation.1,2,23 Other processes have been developed by
BASF.8,23 The reaction is

Specications and standards for acetylene dier somewhat


among dierent countries. As a rule, acetylene to be used as a
fuel, in metal-cutting torches for example, must be about 98%
pure in the United States.89 Acetylene to be used as a feedstock
for chemical manufacture has higher standards of purity. As one
example, the requirements in India for carbide-derived
acetylene of so-called quality A is 99.0 vol % acetylene, with
allowable impurities of 0.15% hydrogen sulde, 0.06%
phosphine, 0.001% arsine, and 0.10% ammonia.10 Quality B
acetylene is also 99.0 vol % acetylene but diers in terms of
impurity limits of 0.08% phosphine and 0.0001% arsine.10
3.2. Handling Acetylene

Details of the safety issues of handling acetylene on an


industrial scale and engineering approaches to safe handling are
covered in the excellent review by Gannon et al.89 In this paper,
only a few points are raised to illustrate the concerns. Aside
from the economic issues that currently favor use of ethylene
rather than acetylene, this is the other major factor militating
against revival of large-scale production of chemical products
from acetylene.
A principal concern in working with acetylene, both in the
laboratory and at commercial scale, is its tendency to explode
when under pressure, when compressed to 0.2 MPa.97
Tedeschi23 warns of the fact that people can work with
acetylene in apparent safety for many years, but an explosion
could occur at almost any time due to equipment failure or
human error. At room temperature, acetylene is thermodynamically unstable with respect to decomposition to carbon and
hydrogen. Its decomposition liberates 224 kJ/mol; the heat
liberated drives the pressure increase. If no heat loss is assumed,
the pressure could increase by a factor of 12; however, the
decomposition proceeds so rapidly that a detonation occurs,
reaching pressures 200 times greater than the initial pressure.98
Furthermore, as the temperature of the system increases, the
pressure at which acetylene will explode decreases.98 The
procedures that appear to represent the best safety practices are
to dilute the acetylene with an unreactive gas, such as nitrogen
or carbon dioxide, or to minimize the amount of free space in
the reaction system, for example by lling voids with Raschig
rings or similar packing material.98
German experience shows that acetylene cannot be shipped
safely in 50300 mm pipes, even at 0.10.2 MPa, without
explosion risk.23 However, use of <50 mm pipes packed with
steel or ceramic Raschig rings or small-diameter tubes allowed
acetylene to be shipped 80 km in safety. For pipes of <25 mm,
several hundred kilopascal pressure could be used. A mixture of
acetylene with 50% nitrogen could be piped at 0.3 MPa.
At 0.1 MPa and 15 C, acetylene is soluble in acetone to the
extent of 25 cm3 of acetylene/cm3 of acetone; at 1.2 MPa, the
solubility at this temperature increases to 300 cm3/cm3 of
solvent.90 This solubility is the basis of a common way of
handling and storing acetylene with good safety. A cylinder
lled with some type of porous solid thoroughly saturated with
acetone has become a standard method for handling and
transporting acetylene. Acetylene is often handled in steel tanks
by dissolving it in acetone; the tanks also contain some type of
porous ller such as diatomaceous earth (kieselguhr), pieces of
rebrick, or, in years past, asbestos. Under these conditions,
acetylene can be handled safely at pressures to about 1.5 MPa.
Because it is dicult to ship acetylene easily, it is
advantageous if large-scale users would be colocated with, or
at least near, the source of acetylene.18 Although the calcium

6CH4 + O2 2C2H 2 + 2CO + 10H 2

In this process, some of the hydrogen was used as fuel to help


maintain the necessary reaction temperatures of 1500 C. The
product contains about 10% acetylene.1 Methane pyrolysis in
the presence of steam at 1200 C also produces acetylene, with
a coproduct of hydrogen.94 This reaction is
2CH4 C2H 2 + 3H 2

Carbon monoxide and part of the hydrogen could also be used


as feed for various applications of synthesis gas, such as
production of alcohols via the synthol or oxyl syntheses.58 A
related process uses the controlled partial oxidation of methane
and coal, preferably subbituminous or bituminous rank.76

3. PURIFICATION AND HANDLING OF ACETYLENE


3.1. Purication

Crude acetylene from these processes will contain a variety of


impurities, which usually need to be removed before the
acetylene can be used. Separation of entrained, partially or
unreacted particles can be eected in a cyclone.71,95 Purication
of acetylene is done in a multistep process, each step of which is
similar to other conventional or better-known gas cleanup
operations. Ammonia can be removed in a sulfuric acid wash.2
Hydrogen cyanide and hydrogen sulde are removed in an
acid-gas treatment by scrubbing with amines,76,95 or alkyl
pyrrolidone solvents.95 Hydrogen sulde can also be removed
in a Claus plant.71 Other alternatives involve oxidizing sulfur
and phosphorus compounds in chlorine water or sulfuric acid.2
Carbon dioxide can be absorbed in aqueous sodium hydroxide.
This caustic wash can also remove carbon disulde.
Alternatively, acetylene can be separated from the other
products by dissolution in selective solvents such as methanol
or N-methylpyrrolidone,71,76 tetrahydrofuran, dimethylformamide, dimethyl sulfoxide, acetone, or kerosene.2,76
A fully integrated system that includes solvent cleanup and
recycling, as well as methanation of the tail gases and use of the
methane as a co-feed to the acetylene production reactor, has
been disclosed.96
Crude acetylene has a characteristic odor that is due to small
quantities of impurity gases such as phosphine, arsine, and
hydrogen sulde. These impurities derive from calcium
phosphate or sulfate that may have been present in the
limestone used for production of calcium carbide.3,9,11 These
impurities must be removed for many of the chemical syntheses
from acetylene, because of their eects in poisoning catalysts.30
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5. CONVERSION OF ACETYLENE TO COMMODITY


CHEMICALS AND MATERIALS
Acetylene is a versatile feedstock for production of chemical
products or carbon materials, because it can undergo several
kinds of reactions. These include formation of carbanions by
loss of one or both hydrogen atoms; addition of one or two
reactants across the triple bond; participation in DielsAlder
reactions as a dienophile; and dimerization to vinylacetylene,
trimerization to aromatic compounds, or polymerization to
polyacetylene.19 Acetylene can, in principle, be used to
manufacture any product that can otherwise be made from
ethylene.105 Acetylene derivatives oer a possibility of
polyfunctionality in the primary product, which is generally
not the case with alkene derivatives.106 In many cases,
acetylene-based routes to commodity chemicals have been
operated on an industrial scale at some time, somewhere,
during the past century, so that the know-how for such
operations exists.
This section focuses on the use of acetylene to produce
chemicals, monomers, and carbon materials that are, or have
been, of commercial importance. Table 1 summarizes estimated

carbide route to acetylene has the several disadvantages


discussed above, the potential exists to ship calcium carbide,
rather than acetylene, over some distance and generate the
acetylene itself on site. If the acetylene were to come from
calcium carbide, the carbide plant in turn needs to be located
near a source of cheap electricity. Despite these legitimate
safety concerns, it must be said that acetylene was, and is,
handled in large quantities by the chemical industry worldwide
for many decades, including at elevated pressures.

4. ACETYLENE AS A FUEL
Acetylene is the fuel used in the oxyacetylene torch, used for
cutting or welding metal.11,22,90,99 Its usefulness in this
application comes from its ability to produce ame temperatures of 3000 C. Acetylene has a lower heat of combustion
than either of the related compounds ethylene or ethane but
achieves higher ame temperatures. This is due to the much
lower heat capacity of the gaseous products of combustion.100
Complete combustion of acetylene produces 1 mol of water/
mol of acetylene; ethylene or ethane produce 2 or 3 mol of
water, respectively. Because less water is formed in the
combustion reaction, less of the liberated heat of combustion
is needed to raise the combustion products to the ame
temperature. Production of acetylene for welding or cutting is
still based on the coal-to-carbide-to-acetylene route and
represents one of the last remaining signicant markets for
coal-based acetylene.
The best-known example of the use of acetylene for smallscale illumination was the miners lamp, which has now been
supplanted by electric lamps. Acetylene was also used for
domestic or small commercial illuminating applications in
locations where neither gas mains nor electric service was
available. Examples include acetylene-fueled table lamps and
cooking stoves.11 Acetylene lamps were used on bicycles, motor
vehicles, and railway rolling stock.11 In these cases the acetylene
was produced by reacting calcium carbide with water.
Phosphine, which was a common impurity in acetylene
produced this way, would burn to phosphorus(V) oxide. In
domestic illumination applications in closed rooms, the P2O5
would produce a haze of phosphoric acid in the room.101 At
one time, automated lighting systems relied on acetylene-fueled
lights. Prior to World War II, acetylene lamps were used as the
light source in about 75% of the worlds lighthouses,4 as well as
in beacons for aviation. Extensive information on small-scale
use of acetylene as an illumination source, as well as the
appliances for its use, is given in the reviews by Thompson6 and
by Pond.11
Acetylene has been tested from time to time as a possible fuel
for internal combustion engines. In a spark-ignition engine it
appears to oer some potential for reduced NOx emissions.102
This potential is outweighed by the tendency for engine knock.
That problem, combined with the safety issues of handling
acetyleneits wide ammability limits and a potential for
explosive decompositionled to the conclusion that acetylene
would not be a practical fuel for spark ignition engines.102 (The
explosive limits in air are 382%.)103 Acetylene has been tried,
apparently successfully, as a fuel for gas (not gasoline)
engines.11,104 It has been claimed to have been successfully
tested as a motorcycle fuel.6 The suggestion was made that
liqueed acetylene could be used as a vehicle fuel,6 remarkable
because the grave risk of violent explosions while compressing
acetylene have been known for well over a century.

Table 1. Estimated Annual Worldwide Production of Major


Commodity Chemicals That Could Be Made from Acetylene
compd

annual production (106 t)

acetaldehyde
acetic acid
acrylic acid
acrylonitrile
benzene
1,4-butanediol
carbon black (all forms)
ethanol
ethylene
isoprene
vinyl acetate
vinyl chloride

1
7
1
4.5
30
1
10
850
105
0.8
7
30

annual production for some of the major commodity chemicals


that have been produced from acetylene in the past and, in
principle, could be made from acetylene again in the future.
All of the chemicals discussed in this section, as well as the
various consumer products made from them (Table 2), could
be produced from coal via acetylene.
Today, most of these products are made from petrochemical
ethylene and, in the case of ethanol, from biomass resources as
well. Table 2 is not intended to be a complete catalogue of
products that could derive from acetylene chemistry and,
ultimately, from coal. Rather, the examples presented there
show how wide a spectrum of everyday substances could, in
principle, be made from coal via acetylene.
While the chemistry is as practical as ever, as industrial
processes these methods are largely obsolete; in almost all
cases, coal-based processes have been displaced by alkenes or
byproduct acetylene from petroleum or natural gas processing.22 Acetylene also has many interesting uses in laboratoryscale chemistry, for example, in the synthesis of acetylene
complexes of transition metals.3 None of the products of these
reactions has, so far, achieved large-scale production, so they
are not covered here.
Many of the advances in the utilization of acetylene for
production of commercially useful compounds are due to
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immense quantities of shale gas in many parts of the world, or


from possible geopolitical maneuvering in global oil markets,
remains to be seen.

Table 2. Examples of Consumer Products Deriving from


Acetylene-based Chemicalsa
consumer product
adhesives
anesthetic
aviation fuel
blood plasma extender
building siding
corrosion inhibitors
electrically conducting
polymers
electrical insulation
electrodes (batteries or fuel
cells)
ooring
fungicides and herbicides
hair spray
insecticides
motor vehicle fuel
paint
pharmaceuticals
photocopying compounds
plastics
rubber
solvents
textiles or clothing
vitamins

acetylene chemical as source

5.1. Acetaldehyde

acrylic acid, vinyl acetate


divinyl ether
norbornadiene
vinylpyrrolidone
vinyl chloride
propargyl alcohol
polyacetylene

Acetaldehyde production exceeds 1 Mt/year, nowadays almost


entirely from controlled oxidation of ethylene. Acetaldehyde
serves primarily as a precursor to various other useful chemical
products. It also forms a resin by condensation with urea.
Hydration of acetylene in the presence of mercury(II) sulfate
produces acetaldehyde.1,90,110112 Early work employed a
suspension of platinum in dilute aqueous nitric acid113 or
mercury(II) bromide.114 Manganese dioxide has also been used
as a catalyst.115 Reaction conditions are 0.10.2 MPa acetylene
pressure and 9095 C.30 Conversions are about 55%, with
unreacted acetylene being recycled to the reactor.30 Vinyl
alcohol has been suggested as being the initial product, which
undergoes extremely rapid and irreversible enolketo tautomerism to the aldehyde.29,32,111,116 It has also been suggested
that the intermediate is a mercury acetylide, which is then
decomposed by the acid to yield the desired acetaldehyde and
regenerate the mercury(II) sulfate.32 If higher alkynes are used
in this reaction, the products are ketones.107
Traditionally, the reaction was conducted in 1825% sulfuric
acid at 70100 C.23 In the Grunstein process, the reaction is
performed in concentrated sulfuric acid at 50 C.32,90 It was
suggested that a transitory geminal disulfate formed rst,
followed by hydrolysis to 1,1-ethanediol, which in turn
promptly eliminated water to produce acetaldehyde.117 An
alternative process, developed by what was then the
Konsortium fur elektrochemische Industrie, ran the reaction
in a hot solution of dilute sulfuric acid.32 The Montecatini
process provides a 95% yield of acetaldehyde, operating at 85
C.30 The Chisso process also operates at relatively mild
conditions, 6873 C and 0.15 MPa.115 This process has a
less complicated ow sheet than other acetylene-to-acetaldehyde processes, in part due to clever approaches to taking
advantage of the heat release during hydration to help in the
distillation recovery of acetaldehyde; it also avoids the need for
recycling unreacted acetylene, which had been a requirement in
other processes.115 Conversion of acetylene to acetaldehyde in
the Chisso process is 96.5%.115
Although these were once commercial routes to acetaldehyde, they have since been supplanted by the more economical
direct oxidation of ethylene30,118 or dehydrogenation of
ethanol.30

vinyl chloride
acetylene black
vinyl acetate, vinyl chloride
-picoline, pyridine, propargyl alcohol
methyl vinyl ether
1,4-butenediol, pyridine
ethanol
acrylic acid, vinyl acetate
acetic anhydride, pyrazole, pyridine, propargyl
alcohol
N-vinylcarbazole
acrylic acid, acrylonitrile, 1,4-butanediol,
ethylene
acrylonitrile, isoprene, chloroprene
1,4-butenediol, tetrachloroethane
acrylic acid, vinyl chloride
propargyl alcohol

These products could be made from coal via the carbide or arcplasma routes.

Walter Reppe and his group, at I.G. Farbenindustrie in the


period 19251945.106 A good postwar summary of the
advances in acetylene chemistry in Germany, mainly due to
Reppe and colleagues, is available.98 These processes are
collectively known as Reppe chemistry. Reppe chemistry
encompasses three classes of reactions.107 First, vinylation
involves the introduction of a vinyl group, CH2=CH, into a
compound having a slightly acidic hydrogen atom, of which
acetylene is one example.108 Production of acrylonitrile from
acetylene and hydrogen cyanide is the most important such
reaction on an industrial scale. Second, ethynylation introduces
the CHC group into a molecule. For example, acetylene
reacts with formaldehyde to produce propargyl alcohol. Third,
carboxylation involves reaction of carbon monoxide and a
hydroxyl-containing compound with acetylene. Production of
acrylic acid and acrylate esters is an industrially important
example. Further details on these reactions are given in the
subsections below. Products from Reppe chemistry represented
only about 2.5% of acetylene-based chemical production in
Germany during World War II.109 Nonetheless, postwar
investigation of the German chemical industry identied
Reppe chemistry as one of three areas from which the Allies
could derive useful knowledge (the others were synthetic fuels
from coal and production of synthetic rubber).109
Generally, whatever chemical products or materials can be
produced from acetylene can be made more cheaply by use of
appropriate alkenes as the feedstocks. In part, this is due to the
energy-intensive nature of the carbide, Sachsse, and related
processes for making acetylene. A further consideration is that
the alkenes are generally easier and safer to handle than
acetylene.2 What future impacts may derive from extraction of

5.2. Acetic Acid and Acetic Anhydride

Current annual production of acetic acid is around 7 Mt. Its


industrial uses include the production of vinyl acetate, the
monomer for poly(vinyl acetate), and cellulose acetate, used in
some applications for plastics, such as the frames for eyeglasses.
The once-major application of cellulose acetate was for the
production of photographic lm, the market for which largely
collapsed with the widespread acceptance of digital photography. Acetic acid production today is dominated by
petrochemicals. With the demise of the market for lm, acetic
anhydride nds its major use in the synthesis of aspirin by
acetylation of salicylic acid.
Acetylene can be used as starting material for the production
of acetic acid.22,111 Acetaldehyde is an intermediate in this
process; it is catalytically oxidized with air to give the acid.111
Cerium or manganese acetates serve as catalysts.110 In a further
reaction step, acetic acid will add to another molecule of
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acetylene to produce acetic anhydride.111,119 The addition


reaction occurs at 6085 C in glacial acetic acid, in the
presence of mercury(II) acetate or sulfate as catalyst. The
intermediate is ethylidene diacetate, CH3CH(OCOCH3)2. The
diacetate then is converted to the desired acetic anhydride by
atmospheric-pressure thermal decomposition at 300400
C.119

into charcoal.119 The necessary hydrogen cyanide can be made


from reaction of acetylene with ammonia.123 Hydrocyanation of
some acetylene derivatives proceeds at 60120 C in the
presence of tetrakis(triphenylphosphite)nickel(0).124 The
reaction apparently was not tested on acetylene itself nor has
been used in industrial practice.

5.3. Acetylene Tetrabromide

Trimerization of acetylene leads to benzene.6,90,107 Historically,


the reaction has been performed by owing acetylene through a
tube heated to 600 C or, qualitatively, a dull red heat.125
Extensive details of the early work in this eld are reviewed by
Nieuwland and Vogt.90 Various forms of carbon appear to
catalyze the reaction.90 An 80% yield of benzene can be eected
by trimerizing acetylene in tetrahydrofuran (in which acetylene
is highly soluble) in the presence of nickel cyanide and
triphenylphosphine at only 70 C.126 More recent work
indicates the conversion of acetylene to a variety of hydrocarbon products, including benzene derivatives, using nickel- or
cobalt-modied shape-selective zeolite catalysts and a coreactant (such as a light alcohol) that serves as a hydrogen
donor.127 Reaction temperature is 350 C; under optimum
conditions an 85% conversion of acetylene is achieved.127
Aromatization of acetylene in the presence of hydrogen, over
zeolite catalysts, provides yields of up to 56% BTX (mixture of
benzene, toluene, and xylenes) at 400 C, along with smaller
amounts of C9 and C10+ aromatics.128
Of course, there are easier routes to benzene from coal or
coal tar than making acetylene as an intermediate step. Today
benzene is produced almost entirely from petrochemical
processes, including various petroleum rening operations
such as steam cracking and catalytic reforming. Most benzene
goes to production of other chemicals, including ethylbenzene,
the precursor to styrene; cumene, used to make phenol; and
cyclohexane, a precursor to nylon.
Reppe synthesized an array of benzene derivatives beginning
with the cyclization of acetylene. Examples include di- and
tricarboxylic acids, di- and tribenzyl alcohols, their corresponding ester and ether derivatives, and hydroaromatic versions of
these compounds.129 The Reppe hydroquinone synthesis
involves trimerization of acetylene in the presence of carbon
monoxide and steam by use of ruthenium or rhodium
catalysts.2

5.6. Aromatic Hydrocarbons

This compound is noteworthy because of its remarkable


density, 3 g/mL. Its high density makes acetylene
tetrabromide useful in mineral separation processes in which
it is desired to exploit dierences in density between a valuable
ore and accompanying low-value, or useless, rock. Preparation
of acetylene tetrabromide is eected easily by passing acetylene
into a solution of bromine in an inert solvent.19
5.4. Acrylic Acid

Acrylic acid is a major commodity chemical, worldwide annual


production being over 1 million metric tons. Virtually all acrylic
acid production now comes from propylene. Esters of acrylic
acid, that is, acrylates, are polymerized to form a large variety of
consumer products that includes adhesives, paints, coatings
such as oor polishes, and many kinds of plastics.
Acetylene will react with carbon monoxide and water to
produce acrylic acid.2,23,120 The reaction is now known as
Reppe hydrocarbonylation. Reaction occurs at 220230 C and
10 MPa with nickel bromide catalyst2 or with metal
carbonyls.19,98,121 Selectivities to acrylic acid are about 90%.2
The BASF process operates at 225 C and 320 MPa in
tetrahydrofuran.30,119 If an alcohol is used instead of water, the
product is an acrylate ester. For example, the use of methanol
produces methyl acrylate. In this case, nickel carbonyl is used as
catalyst.18,91,111,119 Major uses of acrylates include the
production of coatings and textiles. Reaction conditions are
3050 C and 0.10.7 MPa.30 These reactions are examples of
Reppe chemistry, of which other examples are discussed
elsewhere. A modication of the carbonylation in the presence
of water leads to hydroquinone,2 used mainly as a water-soluble
reducing agent. The modications involve increasing the
CO:H2O ratio and using higher pressures, up to 90 MPa,
and catalysts based on Fe, Co, Ru, or Rh, such as Ru3(CO)12.121
5.5. Acrylonitrile

5.7. Alkynes

Acrylonitrile is used in production of polyacrylonitrile as well as


various copolymers, such as its copolymer with styrene.
Polyacrylonitrile (PAN) is the starting material for the
production of carbon bers, which enjoy steadily growing
applications in a wide variety of products that range from
badminton rackets to rocket motors. The styreneacrylonitrile
(SAN) copolymer is a synthetic rubber. The related
acrylonitrile butadiene styrene terpolymer (ABS) is used to
make an array of injection-molded plastic items, including the
famous Lego bricks.
Until the 1970s, the reaction of acetylene with hydrogen
cyanide was a commercial route to acrylonitrile.2,23,30 At
present, the process cannot compete with ammoxidation of
propylene.19 This reaction occurs at 8090 C and 0.1 MPa in
the presence of copper(I) chlorideammonium chloride2,119,122 or barium cyanide on carbon111 as catalysts. The
process was developed by Bayer and was used by several large
chemical companies up to 1970.119 An alternative approach,
developed by Goodrich, involved a vapor-phase reaction at
500600 C in the presence of sodium hydroxide impregnated

Higher n-alkynes can be produced in the Picon synthesis.


Sodium acetylide in liquid ammonia reacts with alkyl chlorides
to produce alkynes up to at least 1-hexadecyne.19,110 An
alternative route to sodium acetylide involves reaction of
acetylene with molten sodium at 110 C.19 The higher alkynes
will undergo many of the reactions discussed elsewhere in this
section, producing the corresponding homologous products.
5.8. 1,4-Butanediol

Total worldwide production of 1,4-butanediol from all sources


is 1 Mt/year. Alternatives to acetylene chemistry for the
production of 1,4-butanediol include use of maleic anhydride
and propylene oxide as starting materials and a biochemical
route from sugar.
Possibly the last remaining major application of acetylene in
chemicals production, and last major application of Reppe
chemistry, is the reaction of acetylene with formaldehyde to
produce 1,4-butynediol.116 The formaldehyde is supplied as its
37% aqueous solution (i.e., formalin). The reaction occurs at
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100 C and 0.1 MPa over copper(I) acetylide catalyst on a


magnesium silicate support,1,119 in a trickle-bed reactor.2 A
copperbismuth catalyst has also been used.130 The desired
product, 1,4-butanediol, is produced by two-stage hydrogenation of the original 1,4-butynediol. The rst occurs in a
liquid-phase reactor at 55 C and 1.42 MPa over Raney
nickel, followed by reaction at 130 C and 1430 MPa over a
coppermanganesenickel catalyst on silica gel.1,2,119 Alternatively, hydrogenation can be conducted in a trickle-bed
reactor at 100200 C and 20 MPa over copper- or chromiumpromoted nickel catalysts.2 The selectivity to 1,4-butanediol is
about 95%.2
Hydrogenation can be stopped at the 1,4-butenediol stage if
catalysts of lesser activity are used, such as iron catalysts or
nickel catalysts with iron additives.2 1,4-Butenediol diacetate
reacts with hexachlorocyclopentadiene to produce the
insecticide endosulfan or Thiodan.2,19
Most of the production of 1,4-butanediol is used in the
manufacture of poly(butylene terephthalate).19 1,4-Butanediol
is useful in the production of tetrahydrofuran, which
subsequently is converted to poly(tetramethylene ether glycol).
This reaction occurs in the presence of acids that are good
dehydrating agents, such as sulfuric or phosphoric acids, at
110125 C, with nearly quantitative conversion.2 The latter
compound is a feedstock for producing Hytrel thermoplastic
elastomers, polyurethanes (used, for example, in the production
of wheels for skates), and Spandex elastomeric bers.1 1,4Butanediol is also the feedstock for making compounds that
have use as solvents or as precursors to solvents, particularly butyrolactone and pyrrolidone. -Butyrolactone, formed by gasphase dehydrogenation at 200250 C over copper catalysts,2
can be converted to N-methylpyrrolidone, which has
applications as a replacement for chlorinated solvents. Also,
pyrrolidone can be converted to N-vinylpyrrolidone, polymers
of which are used in such commercial products as hairspray.
This reaction occurs with acetylene at 180 C in the presence
of 2% potassium hydroxide.122 The subsequent polymerization
is initiated by peroxides.
Reppe developed the conversion of 1,4-butanediol to
butadiene.131 Using coal-derived acetylene as the feedstock
opened a route to producing useful butadiene-based synthetic
rubbers, such as Buna-S, from coal. Commercialization of an
alternative route, based on Nieuwlands preparation of
vinylacetylene, followed by its conversion to butadiene, stalled
because it was estimated that synthetic rubber plants would
require the entire world supply of palladium for catalysts.131

Because acetylene is thermodynamically unstable relative to


the elements, once reaction has begun, conversion of acetylene
to carbon black and hydrogen is highly exothermic.133 The
temperature eventually reaches >2500 C.132 To begin the
reaction, a portion of acetylene is burned to heat the interior of
the reactor. Once the air supply is shut o, thermal
decomposition of the acetylene takes over, permitting
formation of carbon black.
Unlike the feedstocks used in most other carbon black
production processes, acetylene is chemically homogeneous.
That, combined with the substantial heat liberated by the
reaction, results in a product, acetylene black, that is very pure
and with a high degree of crystallization relative to other kinds
of carbon blacks.132134 About 96% of the carbon atoms are in
aromatic sheets stacked in 67 parallel layers.133 Particle sizes
are 4055 nm.134 Acetylene blacks are used principally as
electrical conductors in various electrochemical, plastic, and
rubber applications.133 A major application has been in the
production of electrodes for batteries.19,23 Acetylene blacks also
have a low degree of chemical reactivity.132 Processes have been
developed to produce acetylene black from other feedstocks,
such as via the decomposition of methane in a plasma
reactor.135
Acetylene black anodes have been evaluated for use in
molten salt electrolyte fuel cells.136 Oxidation rates are not so
low as for similar anodes made of graphite or calcined
petroleum coke but are better than those for other forms of
carbon black or various types of activated carbons.136
Co-pyrolysis of coal with waste tires in an argonhydrogen
plasma can improve the yield of acetylene and the relative
volume fraction of acetylene in the product gases, relative to
reaction with coal alone.137 This work involved Chinese coals
and styrenebutadiene rubber containing 30% carbon black.
These results suggest the possibility of designing a process that
could regenerate carbon black for tire manufacture by making
acetylene from waste tires and coal and using the acetylene as
feed for carbon black production.
5.10. Chlorinated Solvents

Production of various chlorinated solvents was one of the rst


large-scale applications of acetylene chemistry. Reaction of
acetylene with chlorine produces 1,1,2,2-tetrachloroethane;23
however, this reaction is dangerous, with the possibility of
explosion.110 Many catalysts have been proposed for this
reaction, including aluminum chloride,113 antimony(V) chloride,90,110,113 and iron(III) chloride.90 Tetrachloroethane can
also be prepared by reaction of acetylene with antimony(V)
chloride, a discovery attributed to Berthelot in the 1870s.110
This compound serves as an intermediate in the production of
1,1,2-trichloroethylene. Tetrachloroethane is formed by reaction of acetylene with chlorine, with an excess of the tetrachloro
compound serving as diluent. Iron(III) chloride is used as a
catalyst. Without the diluent, direct reaction of acetylene and
chlorine can lead to the formation of highly explosive
chloroacetylenes. Subsequent conversion to trichloroethylene
is eected by dehydrochlorination in calcium hydroxide slurry
at 100 C or by reaction over barium chloride on carbon as
catalyst at 230320 C.23 Trichloroethylene (also known as
chlorothene) is used as an industrial solvent in numerous
applications, perhaps the highest volume use being as a
degreaser for metal surfaces. Years ago it was also used as a
refrigerant. It nds some use as an anesthetic. However,
recognition of the many potential environmental impacts and

5.9. Carbon Black

Production of all forms of carbon black is a large industry on a


worldwide scale, with total production of all types of carbon
blacks being about 10 Mt/year, of which 95% is used in the
manufacture of tires.3 The two general routes to carbon blacks
are via incomplete combustion of some hydrocarbon feedstock,
giving the so-called combustion blacks or furnace blacks, and
via thermal decomposition of a hydrocarbon feed, producing
the thermal blacks. Thermal black and furnace blacks represent
about 95% of total carbon black production, of which furnace
black is 90%. Acetylene black is made by thermal
decomposition of acetylene. In the Shawinigan process,
acetylene is fed to a cylindrical reactor preheated to 800
C.132 Commercial acetylene black is not the same material as
the black sooty substance formed during production of
acetylene in arc or other high-temperature processes.
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likely explains the selectivity of the catalyst.143 Various


treatments that decrease the amount of surface hydrogen on
this catalyst decrease its activity but increase its selectivity.141
Higher selectivity can be achieved by alloying palladium with
silver.144 Oligomerization on the catalyst surface decreases
activity and selectivity.145 Deactivation appears to be due to the
build-up of acetylenic species that are permanently retained on
the catalyst surface.146 Acetylene can also be eective at
carburizing the surfaces of palladium catalysts.147 Palladium
supported on multiwalled carbon nanotubes allows for selective
hydrogenation of acetylene even in acetyleneethylene
mixtures;148 gold on cerium(IV) oxide also gives excellent
selectivity for hydrogenation.149

human health eects has led to trichloroethylene and


tetrachloroethane being replaced by alternative solvents in
many countries, including the United States.
1,1,2,2-Tetrachloroethylene (also known as perchloroethylene, or perc) was produced by reacting trichloroethylene
with chlorine, to produce pentachloroethane (also known as
pentachlor). Pentachloroethane was then converted, via
dehydrochlorination, to tetrachloroethylene. This reaction
could also be done by use of calcium hydroxide or via a
vapor-phase catalytic process.23 This compound has been used
widely as a dry cleaning solvent, in which application it has the
virtues of being volatile and nonammable. A related
application is as a spot remover from clothing, fabrics, and
upholstery. It is also used in some paint strippers. Tetrachloroethylene is also of concern for its environmental and health
impacts. Some countries, such as Canada, no longer allow its
production.

5.13. Heterocyclic Compounds

1,4-Butanediol can be converted to -butyrolactone, which then


can be used to synthesize a series of useful compounds, such as
pyrrolidone and its derivatives N-methylpyrrolidone and Nvinylpyrrolidone, and poly(vinylpyrrolidone).19 N-Methylpyrrolidone is a versatile solvent that has advantages, compared to
many other organic solvents, of relatively low toxicity and
ammability. Poly(vinylpyrrolidone), or polyvidone, is another
discovery attributed to Reppe. It is a water-soluble polymer
with many medical applications, such as a blood plasma
expander, as well as more prosaic applications, such as the
binder in glue sticks.
Pyridine is produced at about 30 kt/year, and is used in the
synthesis of pharmaceuticals and agrochemicals (herbicides and
insecticides), as well as a solvent. -Picoline is used to make
fungicides and herbicides, as well as vinyl pyridine latex, used as
an adhesive for tire cords. -Picoline is a starting material for
the synthesis of vitamin B3. The -isomer is used in synthesis of
pharmaceuticals. Pyridine and its three monomethylated
derivatives (-, -, and -picolines) can be made by reaction
of acetylene with ammonia at high temperatures;90,122 the
product is also referred to as a complex mixture of heterocyclic,
basic nitrogen compounds.30,150 Reaction conditions are rather
severe for acetylene chemistry: 120140 C, 1.31.5 MPa, and
3574 h reaction time in the presence of zinc and cadmium
acetates.30 Diazomethane adds to acetylene to produce
pyrazole;90,111 this is the only nitrogen compound that will
add readily to acetylene at ambient temperatures and without a
catalyst.90 Pyrazole is used in the synthesis of a variety of
medicinal compounds.
Acetylene reacts with carbazole to produce N-vinylcarbazole.19 Subsequent polymerization yields a photoconducting
material, poly(vinylcarbazole), used in photocopying machines.
Oxygenated compounds do not appear to form heterocyclic
derivatives on reaction with acetylene.90 Acetylene reacts with
pyrite at 280310 C to produce thiophene.32 The same
product forms upon passing acetylene through boiling sulfur.90
At least 2000 t of thiophene is produced annually. It is used as a
starting material in making various medicinal compounds and
agrochemicals.

5.11. Ethanol

Ethanol is an excellent and versatile solvent. It is well-known as


a motor vehicle fuel and as an oxygenated additive and octane
booster in gasoline. Ethanol can be produced from acetylene in
a sequence of reactions involving hydrogenation to ethylene
with nascent hydrogen; dissolution of the ethylene in sulfuric
acid to form ethylsulfuric acid, C2H5SO4H; addition of water;
and recovery of the ethanol by distillation.6 In principle, this
oers a route for producing ethanol from coal, though it is
dicult to see any advantage to this process relative to the
hydration of petrochemical ethylene or fermentation of sugars.
5.12. Ethylene

Under the strained economic situation of the Second World


War, there was interest in making ethylene from acetylene. In
todays industry, there is no reason to contemplate producing
acetylene for the purpose of making ethylene, especially since
ethylene is less costly than acetylene. However, the selective
hydrogenation of only one of the two double bonds in
acetylene provides insight into catalytic hydrogenation
processes that might be useful with other alkynes.
A good review of early (pre-1945) studies of hydrogenation
catalysts is given by Nieuwland and Vogt.90 Useful thermodynamic data are available to indicate the temperature ranges in
which ethane, ethylene, and acetylene are stable in the presence
of hydrogen.138 Reaction of a mixture of calcium carbide and
metallic zinc with aqueous sulfuric acid produces acetylene and
nascent hydrogen, which is said to combine readily with the
acetylene.6
Selective hydrogenation of acetylene to ethylene, not all the
way to ethane, can be eected over Lindlars catalyst, palladium
on calcium carbonate treated with lead acetate and
quinolone.126 Palladium appears to be both the most active
and the most selective hydrogenation catalyst, based on a
survey of 10 candidate metals (all of the metals of groups 8, 9,
and 10, plus copper).139 Palladium on silica gel shows good
selectivity for hydrogenation of acetylene to ethylene without
over-hydrogenation.140 Such a catalyst was used during World
War II to produce ethylene from acetylene in 90% yield at
200300 C.30 Only the rst bond, which is the more
reactive of the two bonds in acetylene, is hydrogenated. Such
a reaction provides a way for countries decient in petroleum
but possessing abundant coal reserves to produce ethylene.
Palladium on alumina is also an eective catalyst,141,142 as are
rhodium or/ium on silica gel or alumina.143 Acetylene and
ethylene adsorb on dierent sites on the catalyst surface, which

5.14. Isoprene and Chloroprene

Isoprene and chloroprene are important in the production of


synthetic rubber. 1,4-cis-Polyisoprene has properties very
similar to those of natural rubber. Annual production of
isoprene is 0.8 Mt.
Acetone adds to acetylene at 1040 C and 2 MPa in liquid
ammonia, with potassium hydroxide catalyst.2,8 The initial
product of this reaction is 2-methyl-3-butyn-2-ol, in yield of
about 96 mol %.8 Selective partial hydrogenation of the primary
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densities of 39.5 MJ/m3, compared to 35 MJ/m3 for fuels


such as JP-8 or Jet A.

product yields methylbutenol; the reaction is carried out at 30


80 C and 0.51 MPa over a palladium catalyst.8 Subsequent
dehydration of this alcohol at 250300 C over alumina111
gives the desired isoprene2 with complete conversion.8 This
process was developed by Snamprogetti and operated
commercially until the early 1980s; it is sometimes referred
to as the SNAM process.8
For chloroprene production, acetylene is dimerized to
vinylacetylene in aqueous hydrochloric acid with copper(I)
chloride catalyst.2,110,151 Acetylene conversion is about 18% but
with selectivity to vinylacetylene of 90%.2 A second stage of
reaction adds hydrogen chloride across the remaining triple
bond to produce the chloroprene. The reaction occurs in the
presence of copper(I) chloride in hydrochloric acid, at 60 C.2
Chloromethylallene, CH2ClCH=C=CH2, has been proposed
as an intermediate.110 Selectivity of vinylacetylene conversion
to chloroprene is 92%.2 Acetylene has largely been displaced as
feedstock for this process by butadiene. The rst step of
reaction, addition of acetylene to itself in dimerization, is
chemically similar to the addition of hydrogen cyanide,
mentioned below. 106 Thus HCCH + HCCH
H2C=CHCCH and HCCH + HCN H2C=CHC
N are formally the same reaction. The intermediate vinylacetylene forms explosive peroxides in contact with air,
requiring special safety precautions for running this process.23
Chloroprene can then be polymerized via a free-radical process
to form one of the rst synthetic rubbers, generally called
neoprene, originally available in the United States under the
trade name Duprene,110 and in the former Soviet Union as
Sovprene.90

5.17. Polyacetylene

The rst polymerization of acetylene was eected over


titanium(IV) n-butoxide and triethylaluminum catalyst.30,158
Polyacetylene can also be made by a ring-opening polymerization of cyclooctatetraene.159 The cyclooctatetraene can be
made from acetylene.160 The early literature on the physics,
chemistry, and material properties of polyacetylene is
summarized in the monograph by Chien.158
Alternative catalyst systems include nickel halides mixed with
borohydrides or with phospines.30,161 All other metals from
groups 810 work as well, except compounds of iron.162
Polyacetylene can exist in four dierent structures.30 Chain
lengths are estimated to be 50500 nm.163 trans-Polyacetylene
is a semiconductor, whereas cis-polyacetylene is an insulator. If
the cis form is treated with strong oxidizing or reducing agents,
its conductivity increases by 10 orders of magnitude.30
Formation of the cis product is favored at low reaction
temperatures, 78 C, whereas reactions at higher temperatures, 150 C, favors the trans product.164 Catalysts
containing nickel halide complexes with tributylphosphine
also favor the trans form.165 Room-temperature synthesis is
reported to form a polymer with approximately equal
contributions from the cis and trans forms, which is similar
to copper in electrical conductivity.30 Potential applications
abound in engineering organic molecules with desired electrical
properties for use in various solid-state devices.166
Polyacetylene can be produced as lms,163,167 but these
polymers are not able to be processed either in melt phase or
solution. Films having Youngs modulus of 100 GPa and tensile
strength of 0.9 GPa have been reported; these values are
roughly comparable to those of Kevlar. Polyacetylene is also a
conducting polymer.168 Maximum conductivity was about 2.2
104 S/cm,167 comparable to other values obtained for iodinedoped polyacetylene.169 cis-Rich polyacetylene has a tensile
strength of 150 MPa.170
Transparent polyacetylene lm has been prepared with a
conductivity of 5000 S/cm after doping with iodine;171
depending on catalyst, preparation method, and doping, values
to 16 000 S/cm have been observed.172 Values in excess of 100
000 S/cm have been claimed.173 Other oxidizing agents such as
antimony(V) uoride, or electron donors such as lithium, also
cause orders-of-magnitude improvement in the conductivity of
polyacetylene.174 Treatment of polyacetylene with uorine
leads to material useful in making gas-separation membranes.19

5.15. Lewisite

Arsenic(III) chloride adds to acetylene to form the compound


ClCH=CHAsCl2, the basis of the poison gas lewisite, intended
to be an even more horric replacement for so-called mustard
gas [(ClCH2CH2)2S], used in the trench warfare of World War
I.90,106,122 Fortunately, lewisite was never actually used in
warfare. Lewisite, mustard gas, and related compounds are
vesicants, or compounds whose action includes the extreme
blistering of exposed skin. The last global supplies of lewisite
were supposedly destroyed in 2012.
5.16. Norbornadiene

At elevated pressure, acetylene condenses with cyclopentadiene


in a DielsAlder reaction to produce norbornadiene.30,122,152
Other reaction conditions favor the formation of bicycloheptadiene compounds, some of which may have use as
insecticides.153 Norbornadiene has been used in synthesizing
complexes for formulating homogeneous catalysts. Dimerization of norbornadiene leads to a compound with the trivial
name of Binor-S.154 Hydrogenation of the dimer leads to highdensity aviation fuels. Polynorbornene acts as a solid binder for
liquid fuels, for example, gasoline and advanced aviation fuels
such as JP-10 and RJ-5.155 The polymer can contain up to 80%
of the liquid fuel and still remain as a rubbery solid, useful as a
solid fuel for ramjets.155 Cyclopentadiene can be produced by
reaction of acetylene with propylene.156 Further, cyclopentadiene can also be recovered from the light fraction of
coal tar.157 This suggests the possibility of a route, albeit a long
one, from coal to premium aviation fuels such as JP-10, which is
pure exo-tetrahydrodicyclopentadiene, and JP-9, a mixture of
methylcyclohexane, perhydronorbornadiene, and exo-tetrahydrodicyclopentadiene. These fuels have volumetric energy

5.18. Propargyl Alcohol

Propargyl alcohol nds applications in various chemical


products such as corrosion inhibitors. This compound is a
useful intermediate in producing various compounds having use
as bactericides, fungicides, and for treating infestations of
mites.1 Propargyl alcohol is useful in producing vitamins A and
E and 2-aminopyrimidine, which is used in the synthesis of
sulfadiazine.19 If the reaction of acetylene with formaldehyde,
mentioned above, is run at lower pressures, only one molecule
of formaldehyde is incorporated, giving propargyl alcohol.116
(Propargyl alcohol that forms as a byproduct in the synthesis of
1,4-butynediol is recycled to the reactor.)2 Propargyl alcohol
can also be hydrogenated in a subsequent step to allyl
alcohol.111
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5.19. Resins

impurities from the acetylene, the hydrogen chloride must be


free of chlorine, and no water can be present, since water would
immediately hydrolyze the vinyl chloride to acetaldehyde.30 A
vapor-phase reaction is run at 100170 C and 0.3 MPa119 in
xed-bed reactors.30,119 Mercury(II) chloride supported on
granular activated charcoal is used as catalyst.40,119 The xedbed reactors are basically shell-and-tube heat exchangers, which
are packed with the catalyst. Hydrochlorination is highly
exothermic, necessitating relatively small reactor size due to the
large amounts of excess heat.
Recent work indicates process improvements attainable in a
two-stage uidized-bed reactor.40,177 The conversion is up to
99%, with selectivity to vinyl chloride being about 98%.23,177
Recent catalyst formulations are designed to eliminate the use
of mercury. A catalyst based on gold, lanthanum, and cobalt on
activated carbon provides conversions >90% and selectivity
>98%.40 Potassium tetrachloropalladinate catalyzes the hydrochlorination of acetylene in quantitative yield.178
Although the conversion of acetylene to vinyl chloride is
itself a relatively inexpensive process in terms of capital and
operating costs, the acetylene feedstock is more expensive than
ethylene, so ethylene-based routes to vinyl chloride now
dominate in most countries. However, China is interested in
coal-based acetylene for vinyl chloride production.179 Some
9597% of poly(vinyl chloride) produced in China originates
from acetylene made from calcium carbide.21
The most important application of vinyl chloride is in
production of the ubiquitous poly(vinyl chloride) (PVC),18
along with various copolymers, including PVCA. PVC is used
to make pipes, so-called vinyl siding for buildings, and
insulation on electrical cables. When formulated with
plasticizers, such as phthalate esters, PVC can also be used in
clothing and furniture upholstery.
In many parts of the world, acetylene-based processes have
been displaced entirely by those using the cheaper ethylene
feedstock. However, production of vinyl chloride monomer
from acetylene would still make economic sense in countries
with abundant supplies of cheap coal, such as South Africa or
China. About 7080% of the PVC production in China, some
10 million metric tons/year,40 begins with acetylene,15,40 of
which 90% is produced from calcium carbide.40

Acetylene reacts with alkylphenols to produce various resinous


materials.98,175 One such, originally made by Reppe, was known
as Koresin and served as a very eective tackier for synthetic
rubber. These compounds have molecular masses in the range
8001100 Da. The starting material for Koresin itself was ptert-butylphenol.175
Matrix resins for graphite-reinforced composite materials can
be formulated from polyphenylsulfone and a reactive plasticizer
with an acetylenic terminal group.176 The specic compound
used in this work was 4,4-bis(3-ethynylphenoxy)diphenyl
sulfone. The purpose of the acetylenic groups is to provide
sites for facile cross-linking reactions.
5.20. Vinyl Acetate

Annual production of vinyl acetate exceeds 7 million metric


tons. Virtually all is made currently from ethylene. Most
production from acetylene ended some 30 years ago.19 Vinyl
acetate can be made by vapor-phase reaction of acetylene with
acetic acid at 170250 C and atmospheric pressure with a zinc
acetate catalyst supported on granular activated carbon.2,23,119,122 The reactor is a shell-and-tube heat exchanger
packed with the catalyst. Yield is up to 98% based on
acetylene.23 In the liquid phase, this reaction occurs at 6080
C and 0.10.2 MPa, with mercury(II) acetate used as
catalyst;18,90,116,119 zinc amalgam has also been used.91 As is
the case with other acetylene-based routes to vinyl monomers,
this process has been almost completely supplanted by ones
using ethylene as feedstock, because of the lower cost of
ethylene and the storage and handling issues associated with
acetylene. Vinyl acetate production data provide remarkable
testimony to the swing away from acetylene-based processes. In
1969, 90% of vinyl acetate was produced from acetylene; that
gure had dropped to 10% only six years later, in 1975, and
within another ve years there was no signicant production
from acetylene.91
Vinyl propionate can be produced in an analogous reaction,
starting with propionic acid.2 Formation of vinyl esters of larger
acids, including such fatty acids as stearic and oleic acid, can be
eected by similar reaction with acetylene with zinc or mercury
catalysts. Vinylation of the larger acids is done in the liquid
phase, for example, at 11.5 MPa and 165 C in the presence
of zinc stearate.2 Acid conversions of 9597% and selectivities
to the vinyl ester of 97% can be achieved.2 This reaction is
sometimes referred to as Reppe vinylation, discussed in an
extensive review by Reppe himself.108
Poly(vinyl acetate) is used in formulation of latex paints, as
well as in adhesives and coatings. Products such as wood glue
or carpenters glue, and the white glue used in schools, are
made with poly(vinyl acetate). Copolymers of vinyl acetate and
vinyl chloride, called poly(vinyl chloride acetate), PVCA, nd
use in the manufacture of ooring, and, in the past, of
phonograph records. The copolymer with ethylene, ethylene
vinyl acetate (EVA), is also used in some adhesives, particularly
hot glue sticks. EVA also forms the material commonly known
as foam rubber, used as padding in sports equipment.

5.22. Vinyl Esters and Ethers

Acetylene reacts with carboxylic acids to produce vinyl


esters.1,90 These compounds have use as plasticizers in
poly(vinyl chloride) or poly(vinyl acetate) formulations. They
also can be used to produce materials that serve as substitutes
for epoxy resins.
Vinyl ethers can be made by reacting acetylene with alcohols
in the presence of an acidic catalyst, such as boron
triuoride.90,107 Ether formation can also be run with basic
catalysts, of which potassium hydroxide gives the best
results.98,103 Reaction conditions are 160185 C and 0.7
2.1 MPa.98 Selectivities up to 95% can be achieved.2 Divinyl
ether nds use as an anesthetic. Methyl vinyl ether,
copolymerized with maleic anhydride, yields a material useful
in formulating hair sprays.19
Phenols are also reactive; phenol itself produces phenyl vinyl
ether, which rearranges to o-vinylphenol.103 As noted above, the
analogous reaction with isobutylphenol produces a useful
adhesive for synthetic rubber products, Koresin.103

5.21. Vinyl Chloride

Annual production of vinyl chloride is over 30 million metric


tons, the majority from ethylene. Acetylene reacts with
hydrogen chloride in the presence of a mercury(II) chloride
catalyst on activated charcoal support.2,18,22,23,25,90,112,119 The
conversion of acetylene is about 97%, with selectivity to vinyl
chloride of 98%.2 In addition to removing catalyst-poisoning
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5.23. Vinyl Fluoride

continued development of the electric-arc process or on the


appearance of some new, signicant technological breakthroughs.19 The recent work in China, which is richly endowed
with coal, suggests a continuing investment in improving the
arc process. The many studies of acetylene chemistry in
research laboratories worldwide may lead to exciting new
developments in producing useful chemicals from acetylene.
Pine29 has indicated that, When world petroleum resources
decline, the carbide process based upon coal might become
important for the petrochemical industry. A similar concern
was voiced by Vollhardt,126 who also pointed out that there
were no convenient routes directly to ethylene, propylene, or
butadiene from coal but that coal (or coke) can readily be
converted to calcium carbide for acetylene production. Julius
Nieuwland, one of the great gures of acetylene chemistry in
the early twentieth century, has stated that the possibilities of
further research in acetylene derivatives promise great and
varied possibilities. Even in the investigation of acetylene itself,
we are far from having covered the eld in an adequate
manner.90

Addition of hydrogen uoride to acetylene produces vinyl


uoride,2 the precursor to poly(vinyl uoride), a polymer
desirable because of excellent resistance to weathering. Various
catalysts have been used. Supported mercury compounds
operate at temperatures 150 C but deactivate relatively
quickly; aluminum, tin, or zinc uorides catalyze the reaction at
higher temperatures, 250400 C. Poly(vinyl uoride) is sold
under the trade name Tedlar, a product of Dupont. One
application of this polymer is a surface protectant for
photovoltaic cells.

6. CONCLUSIONS
This review has focused on production of acetylene from coal,
via the classic calcium carbide route and the emerging arc
pyrolysis process, and on production of commodity chemicals
from acetylene. There has been, and continues to be, extensive
work on the use of acetylene in the synthesis of specialty
chemicals or interesting new compounds emerging from
laboratory research. Specialty chemicals from acetylene are
treated in the useful monograph by Tedeschi,23 the earlier
review by Reppe,108 and the even earlier monograph by
Nieuwland and Vogt.90 Although much has changed in the
intervening three decades, particularly with respect to economic
and environmental considerations (for example, the hope that it
might be possible to utilize excess heat from nuclear breeder
reactors for making acetylene directly from coal), the basic
chemistry has not changed.
There does not appear to have been a detailed economic
analysis of chemicals production via coal-derived acetylene at
least in many decades. Even 30 years ago it was suggested that
such economics would be particularly speculative and
convoluted.82 The issues include the ability of coal to compete
with other hydrocarbon feedstocks for acetylene production,
then the issue of which route to acetylene from coal would be
preferred, and nally the larger question of the competition
between acetylene and ethylene as precursors to chemical
production.82 For large-scale commodity chemical production,
a change in the relative prices of ethylene and acetylene would
be needed for acetylene even to be considered as returning to
its former importance. Economic issues regarding the
competition between ethylene and acetylene are covered in
detail in the monograph by Stokes,109 albeit with focus on the
postwar German chemical industry, and covered more generally
by Szmant.19 Possibly, the coal to calcium carbide to acetylene
route may oer some advantages in small or niche markets,
especially where electricity is inexpensive and byproduct sales
of calcium hydroxide would be feasible.
There is no question that technologies for the production of
acetylene from coal, and for production of an extensive variety
of commodity chemicals from acetylene, are well-known and, in
many cases, have been demonstrated at commercial scale.
There are no technical barriers to making chemicals from coalbased acetylene. The issues are primarily economic, especially
the price competition with ethylene and the high energy costs
for calcium carbide or direct acetylene production, and various
environmental concerns. Stokes109 points out that the choice
among coal, biomass, or petroleum for chemical production
must be made on a country-by-country basis according to the
availability of raw materials and various nancial and technical
aspects. The future of acetylene from coal as a large-scale
source of materials of industrial importance depends on

AUTHOR INFORMATION
Corresponding Author

*E-mail schobert@ems.psu.edu.
Notes

The authors declare no competing nancial interest.


Biography

Harold Schobert is Professor Emeritus of Fuel Science at The


Pennsylvania State University, University Park, PA. He also has an
appointment as Extraordinary Professor in the Coal Research Section,
School of Physical and Chemical Sciences, North-West University,
Potchefstroom, South Africa. He has nearly 40 years experience in
energy and fuel research, mainly in the conversion of coal to clean
synthetic fuels and value-added chemicals or carbon materials.
Professor Schobert is the author of about 140 articles in peerreviewed journals, 12 books, and several hundred short papers in
conference proceedings or preprints. He has served on numerous
energy-related advisory boards or committees at state, national, and
international levels. Professor Schobert is a Fellow of the American
Chemical Society and a recipient of the Henry H. Storch Award for
excellence in fuel chemistry from the ACS Division of Energy and
Fuels.
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I am pleased to thank Nita Schobert, Lee Ann Nolan, and
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