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2011 Refining Processes Handbook Home Processes Index Company Index

Olefins recovery
Application: Recover high-purity hydrogen (H2) and C2+ liquid products
from refinery offgases using cryogenics.
4
Description: Cryogenic separation of refinery offgases and purges con-
taining 10%– 80% H2 and 15% – 40% hydrocarbon liquids such as eth- Refinery
off gases
ylene, ethane, propylene, propane and butanes. Refinery offgases are
optionally compressed and then pretreated (1) to remove sulfur, carbon
dioxide ( CO2  ), H2 O and other trace impurities. Treated feed is partially 1 2
condensed in an integrated multi-passage exchanger system (2) against 3

returning products and refrigerant.

Separated liquids are sent to a demethanizer (3) for stabilization 5 SNG or C2 + product
while hydrogen is concentrated (4) to 90% – 95%+ purity by further fuel C2
cooling. Methane, other impurities, and unrecovered products are sent 6 C3
High-purity
C4+
to fuel or optionally split into a synthetic natural gas (SNG) product and hydrogen
low-Btu fuel. Refrigeration is provided by a closed-loop system (5). Mixed
C2+ liquids from the demethanizer can be further fractionated (6) into
finished petrochemical feeds and products such as ethane, ethylene,
propane and propylene.
Installations: Five operating refinery offgas cryogenic systems pro-
Operating conditions: Feed capacities from 10 to 150+ million scfd.
cessing FCC offgas, cat reformer offgas, hydrotreater purge gas, coker
Feed pressures as low as 150 psig. Ethylene recoveries are greater than
offgas and refinery fuel gas. Several process and refrigeration schemes
95%, with higher recoveries of ethane and heavier components. Hydro-
used since 1987 with the most recent plant startup in 2001.
gen recoveries are better than 95% recovery.
Reference: US Patents 6,266,977 and 6,560,989.
Economics: Hydrogen is economically co-produced with liquid hydro-
Trautmann, S. R. and R. A. Davis, “Refinery offgases—alternative
carbon products, especially ethylene and propylene, whose high value
sources for ethylene recovery and integration,” AIChE Spring Meeting,
can subsidize the capital investment. High hydrocarbon liquid products
New Orleans, March 14, 2002, Paper 102d.
recovery is achieved without the cost for feed compression and subse-
quent feed expansion to fuel pressure. Power consumption is a function Licensor: Air Products and Chemicals Inc.  contact
of hydrocarbon quantities in the feed and feed pressure. High-purity
hydrogen is produced without the investment for a “back-end” PSA
system. Project costs can have less than a two-year simple payback.
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2011 Refining Processes Handbook Home Processes Index Company Index

Olefins—butenes extractive distillation

Application: Separation of pure C4 olefins from olefinic/paraffinic C4 C4 paraffins
mixtures via extractive distillation using a selective solvent. BUTENEX
is the Uhde technology to separate light olefins from various C4 feed-
stocks, which include ethylene cracker and FCC sources.

Description: In the extractive distillation (ED) process, a single-com- C4 olefins

pound solvent, N-Formylmorpholine (NFM), or NFM in a mixture with Extractive
C4
further morpholine derivatives, alters the vapor pressure of the com- fraction
distillation
column
Stripper
column
ponents being separated. The vapor pressure of the olefins is lowered
more than that of the less soluble paraffins. Paraffinic vapors leave the
top of the ED column, and solvent with olefins leaves the bottom of the
ED column.
The bottom product of the ED column is fed to the stripper to
Solvent + olefins
separate pure olefins (mixtures) from the solvent. After intensive heat Solvent
exchange, the lean solvent is recycled to the ED column. The solvent,
which can be either NFM or a mixture including NFM, perfectly satisfies
the solvent properties needed for this process, including high selectivity,
thermal stability and a suitable boiling point.

Economics: Installation: Two commercial plants for the recovery of n - butenes have
Consumption per metric ton of FCC C4 fraction feedstock: been installed since 1998.
Steam, t / t 0.5 – 0.8
Licensor: Uhde GmbH  contact
Water, cooling ( DT = 10°C ), m3/ t 15.0
Electric power, kWh/t 25.0
Product purity:
n - Butene content 99.+ wt.– % min.
Solvent content 1 wt.– ppm max.

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Olefins—dehydrogenation of
light paraffins to olefins HP steam
Air

Application: The Uhde STeam Active Reforming (STAR) process produces Fuel gas
Feed
Raw gas
(a) propylene as feedstock for polypropylene, propylene oxide, cumene, preheater
compression
Star Fuel gas
acrylonitrile or other propylene derivatives, and (b) butylenes as feed- reformer
stock for methyl tertiary butyl ether (MTBE), alkylate, isooctane, polybu-
tylenes or other butylene derivatives. O2/air
Oxy Heat Gas
reactor recovery separation
Feed: Liquefied petroleum gas (LPG) from gas fields, gas condensate
fields and refineries. Hydrocarbon feed
Olefin
Boiler feed water product
Product: Propylene (polymer- or chemical-grade); isobutylene; n-butyl- Fractionation
Process condensate
enes; high-purity hydrogen (H2) may also be produced as a byproduct.
Process steam Hydrocarbon
recycle
Description: The fresh paraffin feedstock is combined with paraffin re-
cycle and internally generated steam. After preheating, the feed is sent
to the reaction section. This section consists of an externally fired tubular
fixed-bed reactor (Uhde reformer) connected in series with an adiabat-
ic fixed-bed oxyreactor (secondary reformer type). In the reformer, the After cooling and condensate separation, the product is subse-
endothermic dehydrogenation reaction takes place over a proprietary, quently compressed, light-ends are separated and the olefin product is
noble metal catalyst. separated from unconverted paraffins in the fractionation section.
In the adiabatic oxyreactor, part of the hydrogen from the interme- Apart from light-ends, which are internally used as fuel gas, the
diate product leaving the reformer is selectively converted with added olefin is the only product. High-purity H2 may optionally be recovered
oxygen or air, thereby forming steam. This is followed by further dehy- from light-ends in the gas separation section.
drogenation over the same noble-metal catalyst. Exothermic selective H2
conversion in the oxyreactor increases olefin product space-time yield Economics: Typical specific consumption figures (for polymer-grade
and supplies heat for further endothermic dehydrogenation. The reaction propylene production) are shown (per metric ton of propylene product,
takes place at temperatures between 500°C and 600°C and at 4 – 6 bar. including production of oxygen and all steam required):
The Uhde reformer is top-fired and has a proprietary “cold” out- Propane, kg/metric ton 1,200
let manifold system to enhance reliability. Heat recovery utilizes process Fuel gas, GJ/metric ton 6.4
3
Circul. cooling water, m /metric ton 170
heat for high-pressure steam generation, feed preheat and for heat re-
quired in the fractionation section. Electrical energy, kWh/metric ton 100

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Continued 
Olefins—dehydrogenation of light
paraffins to olefins, continued
Installation: Two commercial plants using the STAR process for dehydro-
genation of isobutene to isobutylene have been commissioned (in the
US and Argentina). A STAR process oxydehydrogenation plant for the
production of 350,000 tpy propylene will go onstream in Egypt in 2009.
More than 60 Uhde reformers and 25 Uhde secondary reformers have
been constructed worldwide.

References: Heinritz-Adrian, M., S. Wenzel and F. Youssef, “Advanced

propane dehydrogenation,” Petroleum Technology Quarterly, Spring
2008, pp. 83–91.
Heinritz-Adrian, M., “STAR process – Advanced propane dehydro-
genation for on-purpose propylene production,” CMT 5th Middle East
Olefins & Polyolefins Conference, Dubai, November 2007.
Wenzel, S., “STAR process—Uhde´s oxydehydrogenation technol-
ogy,“ 9th International Petrochemicals & Gas Conference and Exhibi-
tion, London, 2007.

Licensor: Uhde GmbH  contact

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Oxygen enrichment for Claus units

Liquid oxygen tank
Claus plant process
Application: Overcome bottlenecks due to limited gas throughout— Vaporizer control system
typically for capacity increase and/or decompose detrimental hazardous
materials such as ammonia Controller

Description: As “clean fuels” regulations become effective, refiners Measuring and

control unit
must recover more sulfur in their Claus plants. As a byproduct of deep 1
FLOWTRAIN
Steam
desulfurization, ammonia is generated and typically must be decom-
2 4
posed in the Claus plant. To upgrade the sulfur recovery units (SRUs) Process gas
to catalytic
accordingly, oxygen enrichment is an effcient and low-cost option. Oxy- Air reactors
Onsite ASU
gen enrichment can increase sulfur capacity substantially and is capable
3
of decomposing ammonia from sour-water stripper gas very efficiently.
Oxygen addition can be done in three levels, depending on the re- Acid gas plus sour BFW
Oxygen pipeline water stripper gas
quired capacity increase:
1. Up to approximately 28% oxygen. Oxygen is simply added to 1 Alternative oxygen sources
2 FLOWTRAIN with all required safety features
the Claus furnace air. This can raise sulfur capacity by up to 35%. 3 Oxygen injection and mixing device
4 Claus reaction furnace with burner for air and/or oxygen enriched operation
2. Up to approximately 40% oxygen. The burner of the Claus
furnace must be replaced. Up to 60% additional sulfur capacity can be
achieved by this method.
3. Beyond 40% oxygen. This option allows for 100% more capac- to the Claus plants’ process control system.
ity and beyond. Here major modification of Claus unit is necessary, e.g., An effcient mixing device ensures even oxygen distribution in the
implementing a second thermal stage. Claus air. A proprietary Claus burner was developed especially for appli-
Oxygen sources can be liquid oxygen tanks, onsite air separation cation for air- and oxygen-enriched operations. This burner provides for a
units (ASUs) or pipeline supply. Oxygen consumption in Claus plants short and highly turbulent flame, which ensures good approach toward
fluctuates widely in most cases; thus, tanks are the best choice due to equilibrium for Claus operation and for the decomposition of ammonia.
ease of operation, flexibility and economy. For oxygen addition into the
CS air duct, a number of safety rules must be observed. The oxygen Economics: As oxygen enrichment provides substantial additional
metering device FLOWTRAIN contains all of the necessary safety fea- Claus capacity, it is a low-cost alternative to building an additional Claus
tures, including flow control, low-temperature and low-pressure alarm plant. It can save investment, manpower and maintenance. Installed
and switch-off, and safe standby operation. All features are connected cost for oxygen enrichment per level 1 is typically below $250,000.

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Continued 
Oxygen enrichment for Claus units, continued
For level 2, the investment costs range from $200,000 to $500,000
and depend on the size of the Claus plant. Operating costs are varied
and depend on the duration of oxygen usage. Typically, annual costs
of oxygen enrichment are estimated as 10% to 40% of the operating
cost for a Claus plant, providing the same additional sulfur capacity.
Due to improved ammonia destruction maintenance work, as cleaning
of heat exchanger tubes from ammonium salts and the respective cor-
rosion become substantially less.

Installations: Over 10, plus numerous test installations to quantify the

effects of capacity increase and ammonia decomposition.

Contributor: Linde AG  contact