Page 6 - Academic Press Encyclopedia of Physical Science and Technology 3rd Organic Chemistry

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Encyclopedia of Physical Science and Technology EN001F-4 May 7, 2001 16:19

58 Acetylene

TABLE III World Acetylene Usage a A. Acrylates and Acrylic Acid
Location Chemical Industrial Total 1. Reppe Carbonylation
United States 282 114 396
Western Europe 814 200 b 1014 b 4C 2 H 2 + Ni(CO) 4 + 4C 2 H 5 OH + 2HCl −→
Japan 106 b 100 b 206 CH 2 CHCO 2 C 2 H 5 + H 2 + NiCl 2
Others 200 b 150 b 350 b 
Total 1402 b 564 b 1966 b H 2 O
CH 2 CHCO 2 H + C 2 H 5 OH
a In millions of pounds.
b Estimated value. t = 30–40 C; atmospheric pressure.
◦
acetylenics is expected to increase. Worldwide acetylene
2. Replacement Process: Two-Stage Propylene
capacity is spread over a wide geographic area, as shown
Oxidation
in Table IV. The calcium carbide (CaC 2 ) process, based
on coal and limestone, is still extensively practiced or is 1 A
CH 3 CH CH 2 + O 2 −−−−−→
present as a backup capacity. In Russia there is probably a 2 300−450 C
◦
large calcium carbide capacity that has not been reported.
B
The large-scale use of acetylene for the manufacture CH 2 CHCHO −−−−−→ CH 2 CHCO 2 H
◦
of commodity chemicals will be dependent on the cost 275−365 C ROH
differencebetweencoalandoilandnaturalgas.Itiscertain
Acrylate esters
that sometime in the future oil and natural gas reserves will
become limited and more expensive than coal. The target A and B = fixed or fluidized-bed reactors.
date is the early 21st century. Coal-based technologies
such as the calcium carbide and AVCO (coal–hydrogen
B. Acrylonitrile
plasma arc) processes are prime candidates for large-scale
acetylene production. The AVCO process (Section VIII) 1. Acetylene–Hydrogen Cyanide
has been studied successfully at the pilot-plant level.
C 2 H 2 + HCN −−−−−→ H 2 C CHCN
40−600 C
◦
IV. ACETYLENE-BASED PROCESSES Fixed-bed process; catalyst, Ca(CN) 2 .
FOR LARGE-VOLUME CHEMICALS
2. Replacement Process: Ammoxidation
The processes summarized in the equations below were
of Propylene
important in 1940–1965 for producing commodity chem-
icals. Below each acetylene-based process is shown its 3
replacement process. H 3 C CH CH 2 + O 2 + NH 3 → H 2 C CHCN + 3H 2 O
2

TABLE IV Worldwide Acetylene Capacity
Capacity
Country (Company, Location) (millions of pounds) Acetylene process

West Germany (BASF, Ludwigshaven) 176 Partial oxidation of natural gas
West Germany (Chem. Werke Huels, Marl) 264 Arc process–refinery gas
West Germany (BASF, Ludwigshaven) 13 By-product C 2 H 2 from ethylene
Italy (Anic, Ravenna) 132 Naphtha cracking
Italy (Montedison, Porto Marghera) 154 Partial oxidation of natural gas
Japan (Denki Kagaku Kagyo, Ohmi) 200 Calcium carbide process
Japan (Igegana Electric Co., Ogaki) 616 Calcium carbide process
South Africa (African Explosives) 110 Calcium carbide process
Russia (Lissit Chansk) 77 Partial oxidation of natural gas
United States (Kentucky, Texas) 384 Calcium carbide, cracking by-product,
partial oxidation