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3.6.3. Solid wastes
Catalyst
Media
Solid
Origin
Reactors
Destination
Regeneration, metal recovery
Quantity
Depends on reactor size
Composition
Contaminated catalyst
Catalyst from reforming process is regenerate every 6 to 24 months for SR process and
continuously for CCR. Catalysts used are generally very expensive so precautions are taken to
ensure a long lifetime and losses. When the
catalyst has lost its activity, metals are recovered
off-site.
3.7. Emissions reduction proposals
3.7.1. Air emissions
Air emissions from isomerization unit in normal operations arise from process heaters, vents
and fugitive emissions.
In order to reduce fugitive emissions, a leak detection and repair program can be established
(see part A of this report).
Concerning process heaters,
old furnaces that produce NOx, SOx and particulate matters
should be replaced with emission controls furnaces.
3.7.2. Solid wastes
Concerning the catalyst, source reduction methods are those that extend its life. Currently,
recycling of the spent catalyst by sending to metals reclamation is a common practice since
the catalyst is platinum and other expensive metals.
3.7.3. Spent caustic
In order to minimize spent caustic, contact between caustic and gas must be optimized.
3.8.
Dioxins emissions
According to limited testing performed in the United States, catalyst regeneration in the
reforming process is a potential source of PCDDs/PCDFs.
During the reforming process, coke formation onto the catalyst lower its activity. This coke
can be removed by regeneration via burning at temperatures around 400°C followed by a
reactivation at temperatures around 500°C using chlorine or chlorinated compounds. This
coke burning produces exhaust gases that are vented to the atmosphere or scrubbed with
caustic or water.
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Studies have been conducted in order to determinate PCDDs and PCDFs concentrations in
waste streams. However no regulation law has been emitted by European or American
legislation concerning dioxins in petroleum industry.
Once
dioxins are produced, it is difficult to eliminate them as treatment methods or disposal
systems just transfer dioxins from a medium to another (for example, to scrub a gas transfer
dioxins to liquid). Decomposition of dioxins seems to not be widely used.
A better option would be to prevent dioxins formation, which is also difficult as formation
mechanisms are not well-known and chlorinated compounds are necessary in this process.
4. Hydrogenation in olefin plants
Hydrogenations are simple and relatively similar units present in olefin plants. They are
purification steps whose aim is to selectively hydrogenate dienes, alkynes and olefins which
are unstable compounds into olefins and alkanes. These processes
generally do not produce a
lot of effluents. The main issue is basically effluents produced during the catalyst
regeneration. Axens has a strong experience with all types of hydrogenation.
4.1. Purpose of units
The C
3
hydrogenation unit is a sub-process in an olefin plant. It is designed to selectively
hydrogenate Methylacetylene (MA) and Propadiene (PD) contained in the C
3
stream from the
depropaniser overhead, before it is fed to Propylene Towers. Indeed, in addition to up to 90%
propylene, the raw C
3
cut contains a non negligible quantity of MA and PD that have to be
removed in order to meet the propylene product specification.
The reactions involved are
hydrogenations of MA and PD with hydrogen. The MAPD hydrogenation to propylene can be
carried out in either the vapour or liquid phase. All modern steam crackers for which the C
3
cut is separated before hydrogenation ("tail end hydrogenation") use liquid-phase
hydrogenation as it requires lower investment and has lower operating costs compared to gas-
phase processing.
The C
4
hydrogenation unit is a sub-process in an olefin plant. It is designed to selectively
hydrogenate butadiene contained in the C
4
stream from the debutanizer overhead, before it is
fed to isobutylene and butane-1 removal units. The reaction involved is hydrogenation of
butadiene with hydrogen.
The gasoline hydrogenation unit is a sub-process in an olefin plant.
It is designed to totally
hydrogenate raw pyrolysis gasoline (RPG) which is the bottom product of the ethylene plant
debutanizer. The purpose of this unit is to eliminate unstable components such as diolefins
and styrenics, and olefins in order to meet the product specification. Indeed cracked gasoline
typically exhibits high aromatics content, about 50% being benzene. It is an ideal feedstock
for benzene production. However, treatment steps with adequate fractionation facilities are
required upstream of the benzene process
in order to meet sulphur, olefins and diolefins
content specifications. The treatment process operates in two stages. About 90 first stages and
60 second stages of gasoline hydrogenation have been licensed by Axens.
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4.2. Raw materials and resources input characteristics
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