MANUFACTURE OF ACETYLENE
BY PARAFFIN HYDROCARBONS
(WULFF PROCESS)
Raw materials
• Basis: 1000kg acetylene (100%)
• Natural gas = 262000Sef
• Steam (600psig) = 26308kg
• Electricity =140kWH
• Cooling water =25000gal
• Process water =200gal
• Solvent (make up) =2.95kg
Reaction
Manufacture
Description
• In the Wulff process acetylene may be produced by thermal decomposition of hydrocarbons
such as methane, ethane, propane, butane, ethylene etc.
• Pyrolysis is carried out in the Wulff regenerative furnace which is a rectangular steel box filled
with refractory bricks checker work. Before the hydrocarbon feed is sent to the chamber, it is
diluted with steam (up to 1:8 ratios). The feed is carried through the chamber at sub-
atmospheric pressure by virtue of a large vacuum pump. Which reduced the residence time
as little as 0.03 sec; cracked gas leaves the chamber at about 370°C. The maximum
temperature in the furnace just after the heating cycle approaches 1315°C. The furnace is
operated in four minutes cycle in which the checker work is first heated for one minute and
then feed gas pyrolyzed for one minute. The same sequence of operation is then done in
reverse direction through the furnace. To facilitate reversal of the gas flow, fuel gas burners
and hydrocarbon feed pipes are located on each side of the combustion chamber. To allow
continuous flow of cracked gases to the purification train, two furnaces are usually operated
on staggered cycles. Cooled cracked gases from the chamber are then further quenched in a
tar trap, where steam and various tars are removed. The gas is compressed to atmospheric
pressure, passed through a knock-out forum and electrostatic precipitator, and sent to the
recovery system.
Description
• Usually diacetylene and acetylene are separated by absorption in DMF (dimethyl
formamide). By proper adjustment of solvent ratio and temperature, diacetylene may be
removed in the first scrubbing column. In the acetylene absorber small quantities of
ethylene, CO2 and higher acetylenes are also absorbed. Most of the acetylene-free off-gases
used for various heat exchanging operation like used as fuel for the steam boilers, for
combustion chamber heating etc.
• Acetylene rich solution is sent to stabilizer, where less soluble components are removed by
stripping. Acetylene is then removed from the solvent in a second stripping column. The
solvent is readied for reuse by stripping out high boilers by blowing with off gas from the
acetylene absorber-followed by rectification.
• Usually, off-gas from the acetylene recovery system is used as fuel for heating the
combustion chamber. The volume of off-gas is much more than is required for fuel, so it may
be either recycled to the furnace or used as a raw material for some other operation.
• Yield of acetylene (98.5 to 99.3 % purity) varies with the hydrocarbon feed stock used.
Average yields for the once-through process are 22.5 kg per 100kg methane, 38.6 kg per
100kg ethane, and 35.5kg per 100kg propane. The off-gas is principally ethylene, carbon
Kinetics and thermodynamics
• The principal conditions which must be considered are as follows
• Energy requirement to convert hydrocarbons to acetylene is very high
and which can be supplied by very high temperature. For paraffinic
feedstock, the heat of formation for a gram atom carbon in acetylene
decreases with the increasing length of the chain and it increases in
the case of olefinic hydrocarbons. The heat of formation is of the
order of magnitude required for the dissociation of steam.
Kinetics and thermodynamics
• The formation of acetylene begins at a relatively high temperature; in the case of
methane occurs around 8150C. The temperature required decreases with the
increase in the number of carbon atoms of the hydrocarbon feed.
• The decomposition of hydrocarbons to carbon and hydrogen begins at relatively
low temperatures. E.g. decomposition of methane occurs at 4500C. Hence, the
decomposition into the elements proceeds in competition with the formation of
acetylene. However, the rate of acetylene formation is greater than that of the
decomposition reaction. There so care should be taken that the hydrocarbon
feed must reach at relatively high temperatures (above 6750C) in the shortest
possible time and then the attained equilibrium must be immediately quenched
to about 2850C in order to preserve the acetylene formed. The time interval for
the reaction should be of the order of milliseconds.
