PSA-Based Recovery Systems for Purge

Column Off-gas in Polyolefin Plants

Air Products and Chemicals, Inc.; Allentown, PA USA -
Philip J. Cook, Robert Curzi, Keith A. Ludwig, and Lonnie W. Smith

ATOFINA Petrochemicals Inc.; La Porte, TX USA -

Tom Cushman, Nelson Black, Mark Douglas, and Kevin McGovern

PRESENTED at the POLYPROPYLENE 2004

GLOBAL TECHNOLOGY & BUSINESS FORUM
13-16 September 2004 - Zurich, Switzerland

• ABSTRACT: Air Products has commercialized recovery systems combining

pressure swing adsorption (PSA) and partial condensation to reclaim valued
hydrocarbons and nitrogen for polypropylene (PP) and polyethylene (PE)
plants. The systems achieve essentially complete recovery, and provide
producers the lowest cost for polymer degassing operations. The recovery
plant equipment is supplied in pre-packaged or skidded units to minimize
installation costs. The projects deliver very attractive economic returns, and
large reductions in emissions if the gases were being flared. A system
recovering purge gases from multiple polypropylene trains at ATOFINA’s
LaPorte, TX site started up in March 2004. This is the second Air Products
system to start-up within a year serving the polypropylene and polyethylene
(PE) industries. The technology is well positioned to help other producers
lower their operating costs, and satisfy more stringent environmental
regulations.

For more information about Air Products’ gas separation solutions and technologies
click on http://www.airproducts.com/hydrocarbon, or contact

Keith A. Ludwig Philip J. Cook Horia Gavrilescu (Brussels)

Phone: 610 481 5700 (US) Phone: 610 481 6331 (US) Phone: 32 (2) 674 9583
[email protected] [email protected] [email protected]

Lonnie Smith
Phone: 281 874 7149 (US)
[email protected]

1
 PSA-BASED RECOVERY SYSTEMS
FOR PURGE COLUMN OFF-GAS IN POLYOLEFIN PLANTS

INTRODUCTION
Many polyolefin plants use a degassing step to remove un-reacted olefin,
additives and solvents from the raw polymer before entering downstream
extrusion operations. As shown in Figure 1, nitrogen is commonly used as the
stripping gas. Nitrogen can also be used for polymer transfer and downstream
processing. These operations produce low-pressure off-gas that contain N2 and
valuable hydrocarbons. Directly disposing of this stream in a flare, or processing
for only partial recovery of the hydrocarbons results in lost value to the operator,
and unnecessary emissions of HRVOC, NOx, CO, and CO2.

Air Products has commercialized recovery systems for the low pressure streams
associated with both Polypropylene (PP) and Polyethylene (PE) plants. The
systems use Pressure Swing Adsorption (PSA) and partial condensation
technology, and reclaim essentially 100% of the materials for reuse. With a high
performance recovery unit, owners can achieve the lowest costs for their polymer
degassing operations, and near zero emissions rates.

Figre 1:

2
Until recently, the most common designs for recovery systems focused on
hydrocarbons recovery, as shown in Figure 2. In the monomer recovery step, the
feed gas is typically compressed and cooled to sub-ambient temperatures using
mechanical refrigeration. Most of the hydrocarbons condense out of the gas and
are recovered for re-use. The nitrogen and remaining hydrocarbons are disposed
in a flare or waste gas incinerator. Natural gas or some other fuel is often added
to the nitrogen-rich waste stream to assure complete combustion. Figure 2
highlights the four major costs using this method of recovery: N2, lost
hydrocarbons, power, and fuel. As environmental regulations progress,
purchasing emissions credits may emerge as a fifth cost.

Air Products has developed a model that quantifies the direct costs and the
emissions associated with the degassing and flaring steps. Working with
producers, we have demonstrated significant savings in operating costs can be
realized by using an Air Products high recovery system. Partial recovery systems
that recover hydrocarbons only may reduce degassing system costs compared to
simple flaring, but the costs are still significant, and the problem of emissions
remains.

Figure 2:

Degassing Costs for the Producer

Off-
Off-gas Monomer $ NOx,CO2,
NOx,CO
Flare
Recovery CO and VOC
Only Lost Emissions
Purge Monomer
Column $ $
Power
Fuel

X
Recovered
$ Monomer / HC
Nitrogen

3
AIR PRODUCTS HIGH RECOVERY HYBRID PSA PROCESS

The hybrid process commercialized by Air Products uses partial condensation and
Pressure Swing Adsorption (PSA) to produce a high purity nitrogen product and
the recovered hydrocarbons product (see Figure 3).

Figure 3:

A IR P R O D U C T S P O L Y O L E F IN
PLAN T RECO VERY SYSTEM

The Process

P artial
CW C ondensation PSA
E q u ip m ent

P ro d u ct
N2

Feed R ecovered
H ydrocarbons
(V apor or Liquid)

The gas stream coming off the polymer de-gassing stage is compressed and
cooled in the partial condensation section. We design the recovery unit to operate
at temperatures high enough to avoid water freezing, and formation of hydrides.
On a single pass, most of the hydrocarbons are liquefied within the condensation
unit and separated from the nitrogen gas stream. The recovered hydrocarbons
can be recycled back into the polymerization process. Some lighter
hydrocarbons (C1 to C4 compounds) are not fully condensed at the operating
conditions of the partial condensation unit and flow with the nitrogen into the PSA
unit.

The PSA step produces a high purity N2 product. For example, C2+ impurities
can be limited to 50 to 1000 ppm (by weight) in the N2. The hydrocarbons
removed from the nitrogen in the PSA are recovered in a low-pressure tail gas
stream and recycled back to the feed compressor, completing the process.

4
 The hybrid process achieves near 100% recovery of both the nitrogen and
hydrocarbons. Essentially, all hydrocarbons in the feed stream exit the process in
the condensed liquid stream from the partial condensation step. Nitrogen is
produced from the PSA. No gas is sent to flare, waste heat boilers, or incinerators
so emissions are completely eliminated. This performance translates into
significant cost savings and reduced environmental impacts especially in today’s
focus on eliminating highly reactive Volatile Organic Compounds (HRVOC’s),
Nitrous Oxides (NOx), Carbon Monoxide (CO) and Carbon Dioxide (CO2). The
only utilities required by the hybrid process are cooling water and electric power
for the compressor.

HOW PRESSURE SWING ADSORPTION (PSA) WORKS

Pressure swing adsorption (PSA) enables the production of a very pure single
component from a multi-component gas mixture. The process has existed since
the late 1960s, being used most often for the production of hydrogen in steam
methane reforming (SMR) plants, for recovery of hydrogen from streams in
ethylene plants and refineries, and for production of N2 from air. Development of
improved adsorbents and equipment used in the control and sequencing of the
process steps has greatly enabled wide industry uses. Air Products recognized
the technology could be used for separating hydrocarbons from the N2 found in
the PP and PE plant vent gas streams.

The PSA unit uses adsorbent material that selectively adsorbs hydrocarbons over
nitrogen through greater surface attraction and physical adsorption mechanisms.
When different pressures are applied, the adsorbent’s holding capacity for the
attracted material changes. PSA’s, as the name implies, cycles the operating
pressure over a packed bed of adsorbents through a predetermined sequence.
Hydrocarbons are gathered on the adsorbent materials while processing the feed
gas mixture at high pressure. When the adsorbent materials in the bed become
saturated, they are “regenerated” by lowering the pressure, which releases the
hydrocarbons. The hydrocarbons are recovered in a low-pressure tail gas stream.
Effective adsorbents used in PSA’s have relatively high capacity for the targeted
components (this results in economic bed sizes), and they exhibit good selectivity
so the desired separation is accomplished.

PSA systems use multiple beds, usually arranged in parallel as illustrated in

Figure 4. Each bed operates in a cyclic mode, alternating between the adsorption
and desorption phases. A continuous flow PSA process is created by staggering
the cycles imposed on the parallel beds.

One feature of the Air Products recovery systems using PSA is the ability to
produce very high purity N2, even down to 50 ppm C2+ impurities if required. The

5
 recovered N2 is suitable for reuse in polymer degassing operations. Some
producers could even evaluate releasing N2 directly to the atmosphere, if site
conditions prevent full use of recoverable N2 (still more cost effective than flaring).

Figure 4:

How PSA Works

On-stream REGNERATION Steps

HC
HC
HC

Adsorption Depress / Purge Re-pressure

Provide
Purge
PSA materials selectively remove (adsorb) hydrocarbons from N2
Capacity to hold hydrocarbons influenced by operating pressure
Multiple beds deliver steady flow process

COMMERCIALIZATION for 320 MTPA PE PLANT - USA - 2003

Air Products first recovery system started in June 2003 as part of commissioning a
320,000 Metric Tons Per Annum HDPE grassroots plant in the United States. The
recovery unit achieves complete recovery of purge gas components so no material
is sent to flare. This project was summarized in a paper at the MBS
POLYETHYLENE 2004 conference. This Air Products recovery system recaptures
primarily nitrogen, and hydrocarbons valued at more than $12 million annually. In
addition, the recovery process will help the site avoid annual emissions estimated at
3,750 metric tons of CO2, 1.7 metric tons of NOX, 15 metric tons of CO, and 20
metric tons of VOC (estimates of emissions if a conventional, partial recovery
system had been used).

6
COMMERCIALIZATION for ATOFINA’s 1MM MTPA Polypropylene Facility

ATOFINA selected an Air Products PSA Based Recovery System to process

offgas from multiple production units at their LaPorte Texas, USA facility.
ATOFINA’s Polypropylene facility is the world’s largest Polypropylene production
facility producing in excess of 1MM MTPA of Polypropylene.

Air Products technology was selected because it readily handles fluctuations in

flow and composition for gases from multiple units, and in part, because it
achieved essentially 100% Hydrocarbons and Nitrogen recoveries. The high
purity products can be recycled directly to the facility’s processing units.

Propylene Nitrogen Recovery Process.

Figure 5 is a simple process flow diagram (PFD) for the propylene nitrogen
recovery unit (PNRU). All equipment shown was included in Air Products scope
of supply.
Figure 5

Air Products Recovery System

PSA Nitrogen

CW
Water
Wash
Scrubber

Ref

Ref

Feed Water Discharge

Propylene
to TSA Product
Water Wash
Drier
Scrubber

to
Water to
DCAC
Water Wash
Scrubber

7
Partial Condensation Section:
The feed gas enters the process and contacts chilled water in the scrub column
to remove the bulk of the moisture in the feed. The cooled feed gas then mixes
with PSA tail-gas. This combined stream is compressed in an oil-flooded screw
compressor and cooled using cooling water. The effluent from the aftercooler is
pre-cooled in economizing heat exchangers while warming vapor feeding the
PSA and the liquid hydrocarbon condensate. The partially condensed stream is
re-combined and chilled further by refrigerant to drop out more hydrocarbon
liquid. This partial condensation section uses a mechanical refrigeration
system. (This is not required for all projects.)

The N2-rich vapor from the PSA feed separator is warmed against part of the
compressor discharge flow and then flows to the PSA for further purification.

Condensed liquid from the PSA Feed Separator warms against part of
compressor discharge flow and flashes to an intermediate pressure in the HC
Product separator. This flash step removes dissolved nitrogen from the liquid
to meet customer specifications. The vapor from the HC Product separator
recycles back to the compressor. The hydrocarbon product is raised to the
required delivery pressure using a liquid pump. The pumping step has an
added benefit of avoiding vapor formation from the product liquid in
subsequent processing steps. The final step before returning the liquid to the
polypropylene production unit is removing any remaining dissolved water from
the hydrocarbon in the liquid-phase product drier.

PSA Section:
The N2-rich vapor from the PSA Feed Separator is fed to the PSA. The PSA
extracts the remaining hydrocarbons from the gas producing a N2 product
with less than 50 ppmw of C3+ hydrocarbons. The hydrocarbons are
recovered in a low-pressure tail gas stream, and recycled to the feed
compressor.

The design feed to the PSA for this unit contains nominally 55 to 60 volume%
N2, and 30 to 40 volume % propylene.

8
The ATOFINA PNRU started in the Spring of 2004. Figure 6a is a view showing the
4 bed PSA (on the right), and the process equipment skid (on the left). Also on the
left, near the back is the feed direct contact scrubber.

Figure 6a Air Products PNRU for ATOFINA

Four (4) beds

Partial Condensation PSA System
Skid

9
Figure 6b is a view showing the process equipment skid (on the right), the propylene
drier, and the direct contact scrubber.

Figure 6b

Direct Contact
Scrubber

C3= Drier Condensation

Skid

10
Figure 6c shows the oil-flooded screw compressor skid, and the four bed PSA
system.

Figure 6c

Four (4) Beds

PSA System
Oil flooded Screw
Compressor
Skid

PNRU Operations Assessment

As mentioned earlier the recovery system started in March 2004. The recovery
system has achieved the project objectives:

¾ No vents to flare – all HC and N2 reused

¾ Free the Waste Heat Boiler to Handle other facility wastes streams
¾ N2 Product purity better than design; at times C3+ not detected
¾ Demonstrated Operational Flexibility respect to turndown, and feed gas
compositions
¾ Recovered Product Values
¾ More stable Polypropylene Degassing Operations

11
PNRU Flexibility and Payback

The design feed rate for the ATOFINA PNRU was set to process purge gas from up
to 8 PP units at site. Due to improvements in upstream processing, the average
feed rates for the recovery unit have been lower than design values. The PNRU has
run smoothly through all turndown conditions, and when processing variations or
swings in feed composition (feeds leaner than design to feeds richer than design).

Even when using averages of the reduced feed rates, the project economic returns
are computed to be less than 24 months.

ATOFINA PNRU Features

Design Actuals

40 to 60 %
Feed Flow 100% of design
Feed Composition Mole % Mole%
Nitrogen 79 70 - 88
Propylene 17 - 18 9 - 31
Propane 3 ca 3
Ethane and ethylene < 0.1 < 0.1

Project Payback months < 24

Propylene Value - Fuel Value $ /MT 485

Expanded Industry Use

The accomplishment of the two demonstrated commercialization projects allow
users to consider Air Products High Recovery Hybrid PSA Systems in future
grassroots plants and retrofits of existing Polyolefin plants to capture otherwise
lost hydrocarbons and eliminate harmful environmental emissions.

Typical Scope of Supply

Air Products supply for the recovery equipment includes design and packaging
of skidded modules for cost effective installation. The system uses oil flooded
screw compression, the Air Products PSA, and employs a special process cycle
that uses the hydrocarbon contained in the purge gas as the refrigerant to drive
the partial condensation section.

Air Products can supply the recovery equipment as a straight sale of equipment
offering, where others install the equipment; or we can offer “turnkey” systems,
where Air Products will handle all aspects of the project. With both offerings, we

12
 provide performance guarantees for utilities consumption and product
recoveries. Figure 7 provides a typical Scope of Supply breakdown for projects.

Figure 7

S c o p e o f S u p p ly
z E q u ip m e n t S u p p ly
– C o m p le te S k id d e d S y s te m s fo r L o w e r
In s ta lla tio n C o s ts
– T u rn k e y S y s te m s
z E n g in e e rin g S e rv ic e s
– In s ta lla tio n S u p p o rt
– C o n tro l In te g ra tio n
– P ro c e s s H a z a rd A n a ly s is
– S ta rt-u p
z A fte rm a rk e t S e rv ic e s
– S p a re P a rts
– O p e ra to r T ra in in g
p p t00 10

CONCLUSIONS
• Air Products has successfully commercialized polyolefin plant vent gas
recovery systems using PSA and partial condensation technology.
o Atofina LaPorte, TX PP plant
o Grassroots - 320,000 MTA PE plant

• The Atofina unit, for a PP plant, started up in March 2004. This system is
retrofitted at an existing plant. It processes purge gas from multiple PP units,
and meets or exceeds its design goals for performance and operation.

• The first unit, for a grassroots PE plant, started in June 2003, and has met or
exceeded operation goals. The PSA has been run at higher than design
rates, and at times, with no detectable C2+ in the N2 product.

• Air Products has developed a model so producers can assess major

operating costs for polymer degassing and vent gas flaring steps.

• Full recovery systems deliver the lowest operating costs from polymer
degassing operations.

13
• Recovery systems capture the entire vent gas stream as valuable products
available for re-use.

• The systems are scalable for individual polyolefin units or for site-wide vent
gas processing.

14