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The Reclaimer

A News Publication by CCR Technologies Volume 4

Focus on CCR’s Engineering Department


CCR Technologies believes in the Terry was quick to add that, for the
importance of our customers’ ability to customer, one of the greatest
have completely open access to all of environmental and economic
our resources and, of course, the key advantages of our equipment is not
people who are the gatekeepers of what it can do, but what it does not do.
CCR’s technology and innovation. Meaning . . . the CCR reclamation
Terry Trofimuk, CCR’s Vice President process does not generate large
of Engineering & Technology, has volumes of waste material, but rather, a
assembled a dedicated team of relatively small, concentrated volume of
individuals who must constantly waste material that is very manageable.
redefine theirmultitasking roles for the
benefit of maintaining CCR’s high level Terry and his department have several
of service-orientation. As no one projects running concurrently that
knows CCR’s vacuum distillation consume the bulk of their time. But
technology better than him, he was when asked about the number one
very candid regarding the value of this priority, he responds: “Our on-going
Terry Trofimuk, P.Eng., VP - Engineering & Technology
proprietary technology: “For any given focus is to continuously improve the
reclamation project, the range of performance and operating efficiencies
contaminants that we are challenged of our processing equipment”. CCR’s
with removing can be very broad – not engineering department is constantly and ARU installations in existence
only in the types – but in the volumes looking to design distillation equipment around the globe.
as well. CCR’s proprietary vacuum with fewer moving parts, smaller
distillation process is robust enough to footprints, fewer processing stages, The CCR engineering team works well
handle the degrees of difficultly that we better reliability, and less dependency together as some of its members have
often must face because we are often on manpower. With some carefully collaborated together for years. At the
presented with unknowns and a few planned adaptations in progress, CCR very least, the engineering team brings
surprises. Thus, you could say that we could soon be expanding the breadth of to our table a wide variety of
have the best technology and the most products that we would process professional experiences in the oil & gas
appropriate equipment for the projects beyond our customary amine and glycol industry which include systems design,
that our customers present to us.” reclaiming businesses. process engineering, automation, and
project management. Our engineering
Inside this issue: In addition to processing and equipment group works closely with our chemist
Focus on CCR’s Engineering 1 improvements, the CCR engineering Ray Abry. He is not only knowledgeable of
Department team spends a considerable amount of oil & gas production and refining
time for and with our clients developing systems that can help clients to
Frequently asked customer questions 2 FEL-1 (front end loaded conceptual) interpret anomalies based upon bench
studies, FEL-2 (front end loaded lab tests and the nature of solvent
The Benefits of Great 4 preliminary) studies, and FEED (front contaminants, but he has been a
Environmental Performance end engineering & design) studies. In mainstay at CCR for more than 20
these areas, CCR’s focuses on our large years.
Technology: CO2 Recovery Using 5 MEG reclaiming systems or fixed ARU’s
Monoethanolamine
(amine reclaiming units) for specific site Continue on page 2
requirements. At the same time,
Chemistry: DEA Reclaiming 8
Terry’s group is also responsible for
providing full customer support for
Meet the CCR Business Development 9 technical issues regarding CCR’s MEG
Team
Page 2
Th e R e c l a i m e r

Continued., Engineering Department

Recently, Terry and his team have


spent time onsite at customer locations
to collect data and better understand
the unique requirements of customers
who are looking for new equipment
alternatives or who desire to improve
the efficiency and adaptability of
equipment not purchased from CCR.
In some cases, depending upon the
nature and incursion rates of the
contaminants, batch processing could be
preferable and adequate for a given
system. From Terry’s perspective,
“CCR’s aim is to provide the best Raymond G.F.Abry, Chemist (left),
options that will reap the best Steve Ayres, EIT, Process Engineer
Shaun Hill, P. Eng., Project Manager (right)
economics, performance and savings for
the customer.” Last, but not least, define operating conditions before we
Terry and his staff have done their part Technologies) at Heriot-Watt
University, in Edinburgh, Scotland, and go into a design phase.”
to foster better awareness of the
advantages and capabilities of CCR by IFE (Institute for Energy Technology) in
reaching out to key global engineering Oslo, Norway. Terry says: “These
firms by hosting educational seminars. firms can offer CCR new perspectives
on very complex process models that
As an extension of own engineering enable us to optimize our design
resources, Terry frequently and openly features. Having open access to our
consults with several well established partners’ research, services and lab
research organizations such as capabilities allows us to test different
HYDRAFACT Ltd. (Hydrate and Flow compositions and components to better
Assurance Consulting and

Frequently Asked Customer Questions


Q. What are the implications of liquid is flowing to the absorber, hammer and slug-type flow into
amine contamination? thereby altering the gas/liquid ratio and downstream equipment. These problems
changing the H2S and CO2 removal not only affect the plant operation but
characteristics. The temperature profile in may also cause mechanical damage.
A. Contamination can severely affect the absorber also tends to change with
an amine unit’s capacity, operational circulation rate. Quite often, operators
stability and mechanical integrity. have to reduce the raw gas flow to the Stability of Plant Operation:
plant to ensure satisfactory operation. Higher contaminant levels usually
increase the viscosity of amine
Plant Capacity: As solvents become solutions, which reduce the mass
contaminated with non-regenerable If operators do not compensate for the transfer rates in the absorber and
impurities, they lose their effectiveness presence of contaminants in the amine, stripper. These viscosity increases
because the amine concentration is there is a danger of overloading the ultimately lead to the product gas no
reduced. To compensate for this effect, solution with H2S and CO2. Excessive longer meeting specifications. This is
the solvent circulation rate can be amine loadings can lead to unexpectedly particularly detrimental in tail gas
increased. However, the increased high corrosion rates in some parts of treating units, where reportable
circulation rate affects other parts of the amine unit, particularly where environmental excursions can result.
the process such as the heat duty in there are rapid changes in pressure,
the reboiler. It may also change the temperature and/or velocity. Two
product gas composition because more phase flow may arise resulting in pipe
Continued on page 3
Page 3 Th e R e c l a i m e r

Continued., customer questions


More viscous solutions also have a higher tendency to
foam. Hydrocarbons and particulates can also contribute to
foaming problems. In extreme cases, foaming can cause
significant pressure drops across the absorber and amine
regenerator. Activated carbon filtration is often used to
contain the hydrocarbon problems, but heavier hydrocarbons
can be costly to remove in this manner.
In addition to promoting foaming, particulates may also
reduce heat transfer efficiencies by fouling exchanger surfaces.
These fines may be introduced with the raw gas or they may
be generated in the amine unit itself. Iron sulfide fines are
"washed" off vessel walls by sudden changes in operating
conditions or by foaming. Mechanical filtration can be used to
deal with most of the fines. However, some fines are so small
that conventional filtration media cannot capture them.
CCR’s Unit 3 on location in the Gulf Coast

Corrosion: Various types of corrosion can result from Most contaminants can be categorized into three basic groups
contaminated amine solutions. Increased circulation rates can Amine Degradation Products: Amine degradation
cause erosion corrosion, the physical wearing away of metals products are compounds which are formed either by the
by the abrasive action of the solution. This is of greatest direct reaction of the amine and constituents of the feed gas
concern where restrictions or changes in direction of flow (such as carbon dioxide, carbonyl sulfide, carbon monoxide,
are encountered. Corrosion rates increase with velocity and oxygen, carbon disulfide) or by thermal decomposition of the
even mildly corrosive solutions can produce extremely high amine. Conversion of the amine, irrespective of the
mechanism, represents a loss of active and valuable
corrosion rates if erosive conditions are present. amine. Furthermore, some of these degradation products
Amines may be degraded through excessive heat or contact may cause foaming, corrosion and reduced gas treating
with oxygen, CO2, or other contaminants. The resulting capacity.
degradation products may increase the tendency for fouling
and corrosion to occur in the system. Concentration cells
can be set up beneath fouling deposits or scale, leading to Heat Stable Salts: During the normal absorption/
high localized corrosion rates. Chlorides entering the amine regeneration process, the amine solution, which is basic,
plant via poor inlet filtration or cooling water exchanger leaks reacts with acid gases entering with the raw feed gas. In the
can accelerate general and pitting corrosion, and can induce case of H2S and CO2, the amine salts are thermally
stress corrosion cracking in stainless steel components. High regenerable. If other anionic species and/or stronger acidic
levels of other inorganic and organic acid salts can also components are present in the raw feed gas, they too form
contribute significantly to corrosion. amine salts. However, these compounds are not thermally
regenerable and are hence designated as “heat stable
All types of corrosion reduce the life expectancy of amine salts”. Both inorganic and organic heat stable salts
processing units and can result in major financial losses. occur. Heat stable salts can reduce plant throughput and
increase corrosion rates.

Q. What contaminants should I be concerned about?


Non-Volatile Contaminants: Non-volatile contaminants
arise from diverse sources such as gas wells, make-up water,
A. The primary contaminants of concern are: anti-foaming agents, sealants, lubricants and anti-corrosion
agents. Another common type of non-volatile contaminants
• Heat Stable Salts / Ash are particulates which may be carried into the amine solution
• Degradation Products by the raw feed gas. Iron sulfide is very common and
undesirable, usually because of its potential to stabilize foams
• Chlorides or enhance foaming tendencies. Solid contaminants of any
type can decrease the efficiency of the absorber and stripper
• Metals by plugging contactor trays, contactor packing and process
piping.
• Particulates
• Hydrocarbons
Page 4 Th e R e c l a i m e r

The Benefits of Great Environmental Performance


One of the unpleasant facts of life is Percentage of Population Citing Environmental Issues as a Top Global Threat**
knowing that decisions made with
Country 2002 2007
imperfect foresight will be judged (by
some) with the benefit of perfect Brazil 20% 49%
hindsight. Sometimes, clear trends make Canada 43% 54%
the right decision obvious. More often,
substantial uncertainties require the use United States 23% 37%
of human judgment. When it comes to France 29% 52%
the environment, there is mounting Germany 27% 45%
evidence that major changes are
underway, creating new risks and Italy 39% 51%
opportunities. The extent and implications of United Kingdom 30% 46%
these changes are still uncertain, making China 69% 71%
related corporate decisions difficult.
India 32% 49%
Japan 55% 70%
Consider how public attitudes changed
between 2002 and 2007. The following **source Pew Global Attitudes Project (http://pewglobal.org)
table comes from the Pew Global
Attitudes Survey, and shows the percentage of explicit price on carbon. In turn, the the Cleantech Venture Network.
people in various countries who cited combination of significant changes in
In light of these trends, companies are
pollution and environmental issues as a public attitudes and greater pressure for
beginning to take action, both to limit
top global threat. government action has caused the
the downside risk associated with
investment community to take notice of
concern about the environment, and
the potential impact of these trends on
to pursue the upside opportunities it
It is clear that the attitudes of our clients financial risk and return. As early as
creates. Broadly speaking, the theme
and customers are changing. Surely their 1997, Konar and Cohen (in “Does the
that links all these initiatives together,
perceptions of the companies they work Market Value Environmental and often connects them back to the
for and buy from will not be far
Performance?”) found that the level of new shareholder value measures, is a
behind. Behind these attitude changes
toxic chemical emissions negatively focus on minimizing emissions and
are a growing number of widely
affected firms’ intangible asset value. In waste, both directly (e.g., through
publicized studies that have called for
2002, King and Lenox (“Exploring the recycling or installation of solar cells)
substantial changes in environmental
Locus of Profitable Pollution Reduction”) and indirectly (e.g., through reduced
policies. A number of them have
found strong evidence linking waste energy demand and better industrial
concluded that, in order to limit the risk
prevention to better financial results. process designs).
of a substantial rise in planetary
Systematic attempts have been made to
temperature (and its associated rate environmental performance and
At CCR, we are pleased to play a role
consequences), the amount of carbon show its linkage to shareholder value
in our clients’ efforts in these
dioxide in the earth’s atmosphere should creation. Some examples are “The
areas. Here are three examples. Our
be limited to 450 to 550 parts per Economic Value of Corporate patented continuous vacuum distillation
million (ppm). In 2006, the level of
Eco-Efficiency”, by Derwall et al, technology removes more contaminants
atmospheric CO2 was 381 ppm (35%
“TRUEVA: A New Integrated Financial from amines than any other approach,
above the estimated pre-industrial era
Measure of Environmental Exposure”, by and allows more of them to be
level), but the rate of increase had
Repetto and Dias, and the “carbon beta” recycled. At the same time, the
accelerated, to 1.9 ppm/year between
ratings recently initiated by Strategic superior amine quality that results
2000 and 2006, versus 1.5 ppm/year
Value Advisors. In light of these studies, minimizes refinery process upsets
between 1970 and 2000. multiple institutional investor groups (which generate waste), energy usage
have been formed to focus on (since temperatures and circulation
rates don’t have to be increased to
These studies, and the attention they environmental issues, including CERES,
offset declining amine quality), and
have received, have generated increasing the Investor Network on Climate Risk,
very expensive reductions in throughput
pressure for government action, including the Institutional Investor Group on (due to regulatory constraints on flaring
stricter limits on emissions, demands for
Climate Change, the London Accord, and acid gas).
greater recycling, and some type of
Continued on page 5
Page 5 Th e R e c l a i m e r

Continued., Environmental Performance


A second example is the use of CCR’s
amine reclaiming technology in power
plant post-combustion CO2 capture
pilot projects. Multiple studies have
found that the economics of CO2
capture are challenging, for a variety of
reasons. One of these is the loss of
the amine used in the process. Efficient
reclamation can minimize these losses purpose, while larger projects have the other end of the decision spectrum, it
and reduce electricity prices by $.002/ designed CCR’s patented technology is still sometimes hard to make the
kilowatt hour. into their permanent installations. business case for
Given uncertainty about the future reclaiming amines when a refinery’s
implications of current environmental ERP system does not capture the full
A final example is the increasing trends, some client decisions in this benefits of this strategy (e.g., the
demand for reclaiming contaminated area are easier to make than others. On avoided costs of fewer upsets, lower
monoethylene glycol that is used for the easy end of the spectrum, it isn’t throughput, and reduced emissions
hydrate inhibition in the growing hard to justify reclaiming and recycling and waste generation). However, with
number of deep offshore gas field monoethylene glycol when it can be rising public, government and investor
developments. Clients with seasonal done for $750/cubic meter and new concern with environmental performance,
needs have used CCR’s mobile product costs at least twice that. At and its demonstrated linkage to
vacuum distillation units for this

Technology: CO2 Recovery Using Monoethanolamine


Carbon dioxide (CO2) is one of several Being a primary amine, MEA reacts
greenhouse gases that is associated with Since the introduction in the 1930’s of more rapidly with CO2 than other
global warming. With CO2 being most the Gerbitol Process, that used amines typically used in natural gas
frequently the end product of diethanolamine to remove hydrogen treating such as diethanolamine (DEA),
combustion processes, the volumes sulphide and carbon dioxide from diisopropanolamine (DIPA) or
released to the atmosphere are easier natural gas, a variety of liquid methyldiethanolamine (MDEA). Flue gas
to estimate than most. This is generally absorption chemicals have been used, MEA systems are also being operated at
done by estimating the energy with monoethanolamine being one. higher amine concentrations than found
consumption at the large, point sources The use of the liquid absorption in natural gas treating. While typical
outlets such as industrial plants chemicals from the natural gas industry monoethanolamine concentrations range
(refineries, chemical plants, etc.) as well has been adapted for carbon dioxide from 18 wt% to 20 wt% MEA in water
as determining the amount of fuel (coal, capture from flue gas vent streams for natural gas facilities, this has been
natural gas, etc.) needed to generate a since the 1950’s. increased to 30 wt% MEA with the in-
given amount of power at large utility clusion of proprietary corrosion inhibi-
power facilities. This adaptation was necessary due to tors for flue gas applications. The higher
the very low operating pressures amine concentrations allow for more
With the advent of carbon dioxide inherent to the flue gas streams relative CO2 capture per unit volume of
trading and, more recently in North to natural gas streams. While the flue solution, so equipment sizes can be
America, penalties for emitting carbon gases are being vented at near decreased, which directly impact the
dioxide into the atmosphere, atmospheric pressure, natural gas capital cost of the MEA unit.
considerable effort is being expended streams can range from pounds to over
to remove CO2 from process vent a thousand pounds operating pressure.
streams. The goal is to produce a The low partial pressure of carbon
concentrated stream of CO2 that can dioxide in the flue gas makes the Continued on page 6
be transported for use as a feedstock selection of the appropriate liquid
for urea fertilizer production, absorbent more challenging.
sequestering in deep brine reservoirs Historically, carbon dioxide capture has
or into declining oil reservoirs to relied on Monoethanolamine (MEA) as
provide improved oil recovery. Coastal the solvent of choice to meet this
region sources could consider deep challenge.
ocean sequestration as well.
Page 6 Th e R e c l a i m e r

Example of a MEA Unit Layout

Continued., Using Monoethanolamine as much CO2 per unit volume as a Carbamate are in solution, heat is
virgin solution would, reasonable applied in the stripper to shift the
By the very nature of the chemistry levels of CO2 removal ranging from equilibrium to the left, back towards
of MEA, it is susceptible to 75% to 90% of its initial MEA and CO2. The regenerated
degradation through the introduction of concentration in the flue gas, are MEA is recycled to the absorber
sulphur oxides, nitrogen oxides and being achieved with these systems. where it picks up more carbon
oxygen. At present, it is common The advantage to operating these dioxide, while the CO2 liberated in
place to have pretreatment of the semi-lean units is related to the the stripper column is sent on to
flue gas in upstream units to lower energy requirement to drive dehydration and compression. The
lower the SOx and NOx down to the bulk of the CO2 from the sol- compressed CO2 can then be
acceptable levels of 10 ppmv and 20 vent. directed to an end use as mentioned
ppmv, respectively. Proprietary previously.
corrosion inhibitors that are added
to the high concentration MEA units As seen in the following primary
also utilize oxygen in their activation, reactions associated with CO2
so not only is the equipment removal with MEA, two moles of
protected but the effect of oxygen MEA are needed for every mole of
on degrading the MEA is lowered as carbon dioxide that is captured: Continued on page 7
well. Even with such safe guards in Once the Protonated MEA and MEA
place, degradation products will build
up over time and require removal to
regain solvent processing capacity.
Long term operating advantages and
cost savings can be achieved by
integrating a CCR Reclaimer with the
regeneration loop thereby keeping the
solvent at peak operating
performance at all times.

Further energy savings and


operational optimizations are
centered on the partial stripping of
CO2 out of the rich MEA. Even
though it is well recognized that
sending a semi-lean MEA solution
back to the absorber will not pick up
Page 7 Th e R e c l a i m e r

Continued., Using Monoethanolamine customer’s specific requirements determining which layout is


finally selected. An example of one such reclaimer design is
Further improvements are being evaluated with other illustrated in the layout example. By working closely with
solvents under investigation to either supplement the MEA the system provider, the optimum unit fit for purpose can be
or to replace it. Blended amines such as MEA / MDEA included in the base design.
blends are being investigated by university researchers. Ab-
sorption of CO2 in aqueous 2-amino-2-methyl-1-propanaol Our North American based mobile units also offer a unique
(AMP) is also under investigation. In addition to these, other opportunity for utilities to try the technology on a short
solvents being considered are aqueous DIPA/MDEA (ADIP) term basis at their existing amine based Flue Gas CO2
blends, hindered amines such as Flexsorb or new proprie- removal system. Data gathered during these runs then can
tary solvents called KS-1, KS-2 & KS-3 from Mitsubishi be utilized by CCR to offer a tailor-made stationary
Heavy Industries (MHI) and Kansai Electric Power Co. reclaiming unit for that application.
(KEPCO). Given the wide suite of existing deep cut CO2
solvents, it will not be surprising to see these enter the Flue
Gas CO2 arena in the future.

As with MEA, all of these new solvents will have the need to
remove degradation products from the solution over time.
CCR Technologies Ltd. (CCR) is uniquely qualified to
provide a built-to-order, integrated solvent reclaimer for
your MEA or alternative solvent Flue Gas CO2 capture
system. There are multiple configurations possible, with the
Page 8 Th e R e c l a i m e r

Chemistry: DEA Reclaiming

rates < 10 mils per year) are:

Aqueous diethanolamine (DEA) has been traditionally used Oxalate 250 ppm
in both refinery and natural gas sweetening processes. It is a
preferred amine to use in refineries where sulfur compounds Chloride 500 ppm
such as carbonyl sulfide and carbon disulfide are present Formate 500 ppm
because DEA will react minimally with these compounds to
form degradation products. DEA is more of a non-selective Glycolate 500 ppm
amine that will remove both H2S and CO2 acid gases Malonate 500 ppm
effectively vs. the more selective MDEA or specialty-MDEA
formulas. DEA is generally used in the 10 to 30 percent by Sulfate 500 ppm
weight range in the aqueous solution. Sulfite 500 ppm
Just like all amines, DEA does degrade over time in gas Acetate 1,000 ppm
sweetening duty. Factors which will influence the rate of Succinate 1,000 ppm
DEA degradation are temperatures, CO2 partial pressures,
and higher concentrations of DEA in solution nearing 30 Ammonia 10,000 ppm
wt%. Some of the major degradation products of DEA are: Thiocyanate 10,000 ppm
Thiosulfate 10,000 ppm
BHEP – N,N’-bis(2-hydroxyethyl) piperazine Sodium 2,000 ppm
HEOD – 3-(2-hydroxyethyl) oxazolidone All Other Metals 100 ppm
THEED – N,N,N’-tris(2-hydroxyethyl)ethylene-diamine
Formyl DEA (Formamides) – reaction of formate anions CCR’s Overall Solvent Quality Guidelines for DEA are:
(when present) and DEA
Bicine – Bis-(hydroxyethyl) glycine;
Free DEA 30 wt% max
Water 60 wt% min
Studies have shown that DEA degradation appears to limit
itself once BHEP equilibrium is established. The presence of Total HSS Anions < 1.2 wt% solution – or –
H2S also appears to inhibit DEA degradation. But it should < 2.5 wt% DEA
also be noted that in the presence of CO2, DEA is more
likely to degrade than other amines like MEA or MDEA. Bicine 250 ppm max
Formyl DEA (DEA-F) < 3.0 wt% solution max
DEA solution corrosivity is directly affected by an increase in
THEED < 1.5 wt% solution max
the levels of DEA degradation products, heat stable salt
anions, and CO2 absorption. All of these factors will lower
the DEA solution pH. Some studies also claim that DEA Ion Exchange and electrodialysis are not able to remove
degradation products and the presence of metals together non-ionic compounds such as the DEA degradation products
will act as chelating agents, further contributing to listed above, certain metals, hydrocarbons and particulates.
corrosivity and adversely affecting solvent performance. Only distillation is able to remove these undesirable
contaminants. Bicine, in particular, is a degradation product
The good news is that DEA can be used successfully, with formed in the presence of DEA and unstable chemical
low degradation and low corrosivity, if the proper CO2 intermediates. It is considered corrosive and can be
loadings, solvent strength and heat stable salt guidelines are removed by vacuum distillation. It has been shown that ion
maintained. Individual HSS anion contaminant guidelines exchange is not very effective in removing this compound
most commonly reported by amine suppliers for DEA since it is dipolar or a zwitterion (meaning that it may
behave as an anion or a cation depending on the pH of the
solutions (based upon maintaining carbon steel corrosion solution).
Page 9 Th e R e c l a i m e r

Meet the CCR Business Development Team Contact Us

With over 600 reclamation projects for over Business Development Managers
80 customers, CCR Technologies has Donald Aromando
demonstrated its unique ability to offer Phone: (281) 988-5800
custom-tailored solutions to reclaiming Fax: (281) 988-5858
challenges anywhere in the world – on-land Mobile: (830) 832-8497
or off-shore. E-mail: daromando@reclaim.com CCR Technologies Ltd. – CANADA
10655 Southport Road SW , Suite 440
Calgary, Alberta T2W 4Y1
If you have any needs, questions or Julie Fox
Main Toll Free: 800-820-4682
comments regarding CCR‘s mobile Phone: (281) 988-5800
Main Local: 403-543-6699
reclaiming services or our engineered Fax: (281) 988-5858 Main Fax: 403-252-2941
reclaiming systems, please contact any of our Mobile: (713) 252-1585
business development managers. E-mail: jfox@reclaim.com CCR Technologies, Inc. – USA
1500 CityWest Boulevard, Suite 550
John Sczesny Houston, TX 77042
Main Toll Free: 866-280-3073
Phone: (281) 988-5800
Main Local: 281-988-5800
Fax: (281) 988-5858
Main Fax: 281-988-5858
Mobile: (713) 818-8226
E-mail: jsczesny@reclaim.com Visit Our Website: www.reclaim.com
Email: info@reclaim.com

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