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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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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.
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
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5.1. Acetaldehyde
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.
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5.7. Alkynes
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5.11. Ethanol
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5.17. Polyacetylene
5.15. Lewisite
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5.19. Resins
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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
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ACKNOWLEDGMENTS
I am pleased to thank Nita Schobert, Lee Ann Nolan, and
Arielle Forrester for their assistance with literature searching
and document retrieval.
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