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Biodiesel Colombia Cardona
Biodiesel Colombia Cardona
Bioresource Technology
journal homepage: www.elsevier.com/locate/biortech
a r t i c l e
i n f o
Article history:
Received 7 October 2011
Received in revised form 20 January 2012
Accepted 25 January 2012
Available online 6 February 2012
Keywords:
Glycerol conversion
Process design
Process simulation
Process assessment
Glycerol-based bioreneries
a b s t r a c t
Glycerol as a low-cost by-product of the biodiesel industry can be considered a renewable building block
for bioreneries. In this work, the conversion of raw glycerol to nine added-value products obtained by
chemical (syn-gas, acrolein, and 1,2-propanediol) or bio-chemical (ethanol, 1,3-propanediol, D-lactic acid,
succinic acid, propionic acid, and poly-3-hydroxybutyrate) routes were considered. The technological
schemes for these synthesis routes were designed, simulated, and economically assessed using Aspen
Plus and Aspen Icarus Process Evaluator, respectively. The techno-economic potential of a glycerol-based
biorenery system for the production of fuels, chemicals, and plastics was analyzed using the commercial
Commercial Sale Price/Production Cost ratio criteria, under different production scenarios. More income
can be earned from 1,3-propanediol and 1,2-propanediol production, while less income would be
obtained from hydrogen and succinic acid. This analysis may be useful mainly for biodiesel producers
since several protable alternatives are presented and discussed.
2012 Elsevier Ltd. All rights reserved.
1. Introduction
A key aspect of the manufacture of biodiesel is the co-production of glycerol, which is obtained at a weight ratio of 1/10 (glycerol/biodiesel). Currently, glycerol does no longer represent a
signicant benet for the biodiesel industry due to its low price
as consequence of the growing market of biodiesel. For example,
glycerol production increased 400% between 2004 and 2006, and
its price fell nearly 10-fold (Posada and Cardona, 2010a). Therefore,
economic exploitation of glycerol as raw material for its transformation to added-value products seems economically necessary.
In the present study, the production of nine added-value products
from glycerol by chemical or biochemical conversion routes were
analyzed based on techno-economic criteria. In addition, different
reaction conditions, strains and downstream processes were considered. The results obtained may be especially useful for biodiesel
producers since several protable transformations of raw glycerol
into added-value products are presented and discussed.
2. Chemical conversion of glycerol
Glycerol can be transformed to added-value products by
oxidation, reduction, decomposition, gasication and pyrolysis.
For example, the main oxygenated products from glycerol are glyceric acid, dihydroxyacetone, hydroxypyruvic acid, tartaric acid,
mesoxalic acid and oxalic acid, besides some intermediates (e.g.,
Corresponding author. Tel.: +57 6 8879300x50199; fax: +57 6 8879300x50452.
E-mail address: ccardonaal@unal.edu.co (C.A. Cardona).
0960-8524/$ - see front matter 2012 Elsevier Ltd. All rights reserved.
doi:10.1016/j.biortech.2012.01.151
283
Fig. 1. Process ow diagrams for raw glycerol purication ((a) purication up to 88 and 98 wt.%, and (b) purication up to 99.7 wt.%) and study cases IIII for chemical
conversion of glycerol ((c) dehydration of glycerol, (d) steam gasication of glycerol, (e) hydrogenolysis of glycerol). E, Evaporation column, R: Reactor, Cen: Centrifuge, D:
Decanter, DC: Distillation Column, IER: Ionic Exchange Resin, HE: Heat Exchanger, H: Heater, Con: Condenser, D: Divisor, M: Mixer, Comp: Compressor, Sep: Separator.
284
4. Methodology
Initially, 13 chemical routes and nine fermentative products were
identied as possible transformation ways for glycerol conversion to
added-value products. Based on technical, economic and environmental criteria (i.e., temperature and pressure of reaction, levels of
conversion/selectivity/productivity, requirements of energy, price
and market of the main product and wastes production), three
chemical and six fermentative products were chosen to be analyzed.
The processes design followed a previously described strategy (Cardona and Snchez, 2007; Quintero et al., 2008) which combines the
hierarchical decomposition methodology with the process design
method known as breadth-rst. This strategy allows systematic generation of alternatives that consider specic characteristics of each
process and simultaneous comparison of different process alternatives. In this way, it is possible to screen different process alternatives and to evaluate them at the next level of the hierarchical
decomposition using process simulators. Therefore, the process simulator Aspen Plus (Aspen Technology, Inc., USA) was used for dening, structuring, specifying, and simulating the technological
schemes for either chemical or biochemical conversion of glycerol
to added-value components. The most complex and detailed technological schemes were obtained by means of rigorous simulations,
which involved sensitivity analyses and search of optimal operation
conditions. Since not only pure, but also raw glycerol has been used
as feedstock, a typical composition of a glycerol-rich stream obtained during the biodiesel production from IdaGold mustard
(Thompson and He, 2006) was considered as the feedstock. Since this
raw glycerol stream contains low concentration of glycerol, a purication process was analyzed in order to obtain the three most important qualities of commercially available glycerol (crude glycerol at
88 wt.%, technical glycerol at 98 wt.% and USP glycerol at
99.7 wt.%). In addition, specic compounds not available on the Aspen Plus Database (i.e., free fatty acids, alkyl esters, proteins, salts,
cell mass strains, enzymes and other complex molecules produced
by reactive-extractive processes) were incorporated to the database
for each simulation. For components and properties not included in
the Aspen Plus database, subroutines and special software were designed to predict the component properties needed for simulation.
For conventional molecules, the group contribution method was
used, while biomass and enzyme were considered as solids and nonconventional compounds, respectively. All results from software calculations are presented using an accuracy value of 0.01 (0.0001 is
used recurrently for comparison purposes in some cases).
The reactive systems were analyzed as follows. For the highly
exothermic dehydration of glycerol to acrolein, an acid catalyzed
process was considered and the reaction scheme reported by
Tsukuda et al., (2007) was used. The gasication process of glycerol
was modeled according to the molar distribution of the reaction
products reported by (Mozaffarian et al., 2004). A two-steps process for the selective production of 1,2-propanediol from glycerol
was developed according to the model proposed by Akiyama et
al. (2009). Subsequently, for biochemical conversion of glycerol
(i.e., glycerol fermentation), six main products were considered.
Also, it is important to note that, although several possibilities
for glycerol fermentation to added-value products have been reported, just a few publications describe accurate kinetic models.
Consequently, for the production of ethanol, poly-3-hydroxybutyrate, lactic acid, succinic acid and propionic acid, a yield approach
was used. Moreover, a stoichiometric approach was considered as
a valid and relevant approach for analyzing the reaction stage of
different technological schemes.
With respect to the economic assessment, capital and operating
costs were calculated using the software, Aspen Icarus Process
Evaluator (Aspen Technologies, Inc., USA). The economic parameters considered were those from Colombia, in US dollars for a 10year period at an annual interest rate of 16%, considering the
straight line depreciation method with a 33% income tax (Posada
et al., 2010). The Colombian labor cost used for operatives and
supervisors was US$2.14/h and US$4.29/h, respectively. Also, the
prices used for electricity, water and low pressure vapor were
US$0.03044/kWh, US$1.252/m3 and US$8.18/ton, respectively.
Table 1
Composition of fed raw glycerol, mass ow of puried glycerol and purication costs.
Materials (kg/h)
Raw glycerol (triglycerides 2%, methanol 32.59%,
glycerol 60.05%, NaOCH3 2.62%,
proteins 0.13%, fats 1.94%) (wt.%)
Products
Methanol
Glycerol at 88% (option 1)
Glycerol at 98% (option 2)
Glycerol at 99.7% (option 3)
Purication costs-Scenario I*
Glycerol at 88%
Glycerol at 98%
Glycerol at 99.7%
Purication costs-Scenario II**
Glycerol at 88%
Glycerol at 98%
Glycerol at 99.7%
*
Mass ow (kg/h)
973.30
Mass ow (kg/h)
301.98
665.25
596.60
586.18
(US$/L)
0.22
0.26
0.35
(US$/L)
0.16
0.20
0.28
**
285
Since the feedstock for all the processes is a raw glycerol stream
obtained from a typical biodiesel plant, the rst step of consideration was purication. Fig. 1a shows the simplied owsheet for
raw glycerol purication to obtain 88 wt.% (crude glycerol) and
98 wt.% (technical glycerol). Production of glycerol at 99.7 wt.%
(glycerol USP grade) required a further rening process using an
ion exchange resin which removes the triglycerides still contained
in the mixture, as shown in Fig. 1b (Posada and Cardona, 2010b). In
addition to the purication analysis, two different scenarios were
considered due to the high concentration of methanol (32.6 wt.%)
in the glycerol stream. In the rst scenario, the methanol obtained
during the evaporation stage was considered as a waste, while in
the second scenario this stream was recycled and reused for
transesterication to produce biodiesel (methanol at 99 wt.%). In
other words, methanol was considered as a by-product with an
economical value in the last scenario. Therefore, the purication
costs of raw glycerol up to 88 wt.% were 0.1574 US$/L (scenario
I) and 0.0984 US$/L (scenario II), and 98 wt.% were 0.1782 US$/L
(scenario I) and 0.1124 US$/L (scenario II). It is important to note
that these purication costs were always lower than their
Table 2
Main processes streams and molar yields for cases of study IIV. Production of acrolein, hydrogen, 1,2-propanediol and D-lactic acid from glycerol with different qualities.
Case study
Scenario
I:
II:
III: 1,2IV: D-Lactic acid
Acrolein Hydrogen Propanediol
(1) Pure glycerol
diluted at 20 g/l
Main reactives
(kg/h)
Raw glycerol at
88 wt.%
Pure glycerol at
98 wt.%
100.0
Glycerol
directly
diluted at
10 wt.%
Water
Hydrogen
579
579
579
27,996
27,996
13,780
581
581
13,821
9041
100.0
30
23,333
374,765
Strain
Cell mass
Residues (kg/h)
94
General
aqueous
residues
Main products (kg/h)
Acrolein at
5.2
98.5 wt.%
Acrolein at
5.6
92 wt.%
Hydrogen at
91 wt.%
Syngas
1,2Propanediol
at 99 wt.%
10000.0
1.0
20.7
7997
D-Lactic
acid at
99 wt.%
Molar yield
85.20%
78.20%
85.00%
27,531
27,536
13,308
13,333
8577
420
416
422
442
433
82.00%
81.20%
83.30%
85.90%
93.40%
286
Fig. 2. Commercial Sale Price/Production Cost ratio for study cases IVI ((a) study cases IIII, and (b) study cases IVVI) and share of product purication costs ((c) study cases
IIII, and (d) study cases IVVI).
Table 3
Main processes streams and molar yields for cases of study V and VI. Production of succinic acid and propionic acid from glycerol with different qualities.
Case study
V: Succinic acid
Scenario
579
579
579
579
579
27,996
11,008
358
11,988
838
12,037
904
13,493
533
Propionibacterium
acidipropionici ACKTet
29.6
Immobilized P,
acidipropionici
ACK-Tet
53.4
Main
reactives
(kg/h)
Raw
glycerol
at
88 wt.%
Pure
glycerol
at
98 wt.%
Water
Tri-n795
1-Octanol
579
579
579
27,996
octylamine
58,803
67,945
1369
2738
2555
3103
456
Strain
Escherichia coli
Mannheimia sp,
Pasteurellaceae
Mannheimia sp,
Pasteurellaceae
Mannheimia sp,
Pasteurellaceae
Anaerobiospirillum
succiniciproducens
Propionibacterium
acidipropionici
Propionibacterium
acidipropionici
Cell mass
10.3
6.8
6.8
6.8
5.0
54.1
43.8
Propionibacterium
acidipropionici ACKTet
53.4
Residues
(kg/h)
General
aqueous
residues
27,415
58,146
58,093
59,806
86,920
27,763
10,725
11,709
11,757
13,218
380
453
464
435
373
285
266
348
288
98.21%
70.86%
67.13%
88.26%
73.34%
579
54.4%
52.0%
71.4%
579
60,675
63.4%
87,083
58.8%
287
288
Fig. 3. Process ow diagrams for biochemical conversion of glycerol to: (a) D-lactic acid (case study IV), (b) succinic acid (case study V), (c) propionic acid (case study VI), (d)
PHB (case study VII), and (e) 1,3-propanediol (case study IX). H: Heater, HE: Heat Exchanger, R: Reactor, F: Fermentor, C: Centrifuge, Con: Condenser, DC: Distillation Column,
D: Divisor, Dec: Decanter, M: Mixer, Comp: Compressor, IER: Ionic Exchange Resin, RDC: Reactive Distillation Column, RE: Reactor Extractor, Sep: Separator.
was found for the production of D-lactic acid. While the lowest production cost was 1.015 US$/kg (Scenario 4), the highest one was
1.2 US$/kg (Scenario 2) and the increasing order for the total production costs was: Scenario 4 < Scenario 5 < Scenario 3 < Scenario
1 < Scenario 2. In addition, the ratio of Commercial Sale Price/Production Cost was higher than unity for all scenarios (Fig. 2c), and
was 1.53 for the Scenario 4. These results indicate that D-lactic acid
production from raw glycerol by mean of engineered E. coli could
be a protable alternative for glycerol usage. The lowest total production cost of D-lactic acid from raw glycerol was obtained for the
Scenario 4 in which three fermentative advantages were present:
(i) use of crude glycerol (85 wt.%), (ii) high glycerol concentration
in the fermentation media (40 g/l), and (iii) total consumption of
glycerol (Fig. 2c, D-lactic acid). Succinic acid production costs varied from 2.008 to 2.949 US$/kg. Although these differences are
mainly due to purication costs, they can be explained by complex
relationships between fermentation variables (e.g., strain, glycerol
concentration, glycerol purity, glycerol consumption, etc.) and succinic acid yields affecting the global performance of the process.
Table 4
Main processes streams and molar yields for cases of study VII and IX. Production of PHB, ethanol and 1,3-propanediol from glycerol with different qualities.
VII: PHB
Scenario
Raw glycerol
Down
stream
process I
Raw glycerol
Down
stream
process II
Raw glycerol
Down stream
process III
1000
1000
1000
C. necator
JMP 134
45.6
VIII: Ethanol
C. necator
JMP 135
45.6
C. necator
JMP 136
45.6
Pure
glycerol
Down
stream
process I
Pure glycerol
Down
stream
process II
Pure glycerol
Down stream
process III
1000
1000
1000
C. necator
JMP 137
37.9
C. necator
JMP 138
37.9
C. necator
JMP 139
37.9
Residues (kg/h)
General aqueous
residues
Main products (kg/h)
25.0
Poly hydroxy
butirate at
99.9 wt.%
Ethanol at
99.5 wt.%
1,3-Propanediol at
99 wt.%
Molar yield
98%
25.4
98%
25.1
98%
48.3
98%
48.7
98%
IX: 1,3-Propanediol
Raw
glycerol
Diluted at
10 g/l
Raw
glycerol
Diluted at
20 g/l
576
578
Raw
glycerol
Diluted at
10 g/l
579
579
579
575
57.057
28.318
56.955
8536
6187
7952
Escherichia
coli
23.0
Escherichia
coli
17.3
Escherichia
coli
23.0
Klebsiella
pneumoniae
27.2
Klebsiella
pneumoniae
20.3
Klebsiella
pneumoniae
23.7
57.348
28.584
57.234
9270
6848
8688
273.07
290.51
293.38
252.70
238.40
248.40
52.38%
40.69%
48.34%
48.5
98%
92%
92%
92%
Case study
289
290
Fig. 4. Commercial Sale Price/Production Cost ratio for study cases VIIIX. (a) PHB production downstream process IIII for raw (88 wt.%) and pure (98 wt.%) glycerol, (b)
ethanol production (from: sugar cane, corn and crude glycerol), (c) ethanol production from: crude glycerol (at 10 and 20 g/l) and pure glycerol (at 10 g/l), and (d) 1,3propanediol production (Scenarios 13).
Fig. 5. Processing stages required for ethanol production from sugar cane, corn, and crude glycerol.
The order for succinic acid recovery and purication costs, and total production costs of succinic acid from raw glycerol were identical: Scenario 1 < Scenario 3 < Scenario 4 < Scenario 2 < Scenario 5.
The ratio of Commercial Sale Price/Production Cost was only higher than unity for the Scenario 1, but this value was still too close to
the unity. Thus, succinic acid production from glycerol still requires efforts to make this process more protable (Fig. 2c). The total production costs of propionic acid from raw glycerol ranged
from 1.683 to 1.942 US$/kg of propionic acid. The order for total
production costs was: Scenario 2 < Scenario 3 < Scenario 5 < Scenario 1 < Scenario 4. The ratio between Commercial Sale Price/Production Cost was calculated for the ve scenarios, and this ratio
was higher than the unity for: Scenarios 2, 3, and 5. Thus, this process could be protable only when high concentrations of glycerol
were used in the fermentation media and high yields of propionic
acid were obtained (Fig. 2c). Overall, the biotechnological route depends highly on fermentation performance, which depends on the
use of crude feedstock, high concentrations of feedstock in the fermentation media, and total consumption of feedstock. Consequently, one of the main goals of metabolic engineering should
be to develop specic strains able to completely consume the glycerol in raw substrates.
5.3.2. Case study VII: PHB
Polyhydroxy butyrate production from glycerol by C. necator
JMP 134 was simulated considering two fermentation stages, and
three extraction methods were analyzed for downstream processes
(named DSP-I, DSP-II and DSP-III, Fig. 3d). The rst downstream
process used a thermal treatment at 85 C, and then an enzymatic
digestion with pancreatin from Burkholdeira sp. PTU9 to cause cell
disruption and PHB is release. The second method used a highpressure homogenizer followed by a solvent extraction process
which modies the cell membrane permeability and causes the
PHB dissolution. The third process used an alkaline pretreatment
with a NaOH solution; then a digestion process using NaOCl and
sodium dodecyl sulfate (SDS). In all downstream processes, PHB
at 99.9 wt.% was obtained by spray drying. Additionally, two substrate qualities were used for these simulations, i.e., crude glycerol
(88 wt.%) and pure glycerol (98 wt.%) (Table 4). In all cases, the cost
of raw material was represented by the glycerol purication cost
described in Section 5.1. The glycerol purication process represents only between 4.8% and 5.6% of the total production cost of
PHB when glycerol at 88 wt.% was used, but this value increased
to between 6.3% and 7.7% when glycerol at 98 wt.% was used. In
general, lower production costs were obtained when glycerol at
98 wt.% was used in the fermentation process, due to the higher
PHB yield in the fermentation stage and the lower energy requirements in the spray drying process. The total PHB production costs
obtained were between 2.11 and 2.44 US$/kg when glycerol at
88 wt.% was used, and between 1.94 and 2.38 US$/kg for glycerol
at 98 wt.%. The comparison between the PHB Production Costs
and the Commercial Sale Price of PHB (i.e., Commercial Sale Price/
Production Cost ratio) is presented in Fig. 4a. In both cases (i.e.,
88 and 98 wt.%), a lower benet was obtained for Downstream Process II, which used a solvent extraction stage. This extraction required heating the expensive chemical solvent to 110 C, which
increased utility costs. The highest benet was achieved when
the three following conditions were met: (i) purication of raw
glycerol to a 98 wt.% level, (ii) two continuous fermentation stages,
and (iii) recovery of PHB with Downstream Process I.
5.3.3. Case study VIII: ethanol
Three different scenarios for ethanol production were considered and utilization of raw glycerol and traditional feedstocks
(i.e., sugar cane and corn) was compared from an economic point
of view. The main production stages for these three raw materials
291
are compared in Fig. 5. All possibilities used a standard conguration consisting of raw material conditioning, fermentation, separation and dehydration, and waste treatment. Three fermentative
scenarios were analyzed: crude glycerol diluted to 10 g/L, crude
glycerol at 20 g/L, and pure glycerol at 10 g/L. The main simulation
results are summarized in Table 4. Similarly to the PHB production
process, the cost of raw material was represented by the glycerol
purication cost (Section 5.1). In all cases, utilities and capital costs
represented the highest cost of the purication process, i.e., around
20% and 30%, respectively. As a result, the lowest bioconversion
cost was obtained when crude glycerol (88 wt.%) diluted to 20 g/
L was used as feedstock, since it used a lower quantity of water
than the other two processes. Higher amounts of water were necessary when pure glycerol (98 wt.%) was used, increasing the
equipments size and the utility requirements. The global production costs for raw glycerol bioconversion to fuel ethanol were obtained by adding purication and bioconversion costs. In all
cases, the purication costs represented almost 35% of the total
production costs, while the bioconversion costs were near 65%.
These global production costs from raw glycerol were lower than
those reported by Quintero et al. (2008) for fuel ethanol production
from corn (0.3381 US$/L). Thus, using raw glycerol at 10 g/L and
20 g/L could represent a saving of 15% and 20%, respectively. The
global production costs were higher than those reported by Quintero et al. (2008) for fuel ethanol production from sugar cane
(0.2153 US$/L), but lower than the international prices for fuel ethanol ranging from (0.4552 US$/L (ICIS pricing, 2011) to 0.6057 US$/
L (Johnson and Taconi, 2007). The comparison of Commercial Sale
Price/Production Cost ratio for ethanol production from both sugar
cane and corn (Fig. 4b), and from glycerol (Fig. 4c), indicates that
the production process of fuel ethanol from raw glycerol by
E. coli could also be a protable alternative.
5.3.4. Case study IX: 1,3-propanediol production
Three production scenarios were considered based on previous
optimization work on glycerol fermentation in two continuous
stages. Three different operational congurations were available
depending on the desired process objective, namely global yield,
1,3-propanediol outlet concentration, or high simultaneous productivity (Posada, 2011). Under this framework, the rst scenario considered optimal conditions of volumetric productivity in the rst
fermentation stage and optimal nal concentration of 1,3-propanediol. The second scenario considered both conditions, the highest nal concentration of 1,3-propanediol and the highest productivity in
the second fermentation stage. Finally, the third scenario consid-
292
ered the optimal global productivity and taking into account both
fermentation stages. Additionally, an integrated reactor-extraction
scheme was proposed to recover and purify the 1,3-propanediol
from the fermentation broth to avoid the problems caused by the
high hydrophilicity of 1,3-propanediol and its high boiling point
(Fig. 3e). The nal production of 1,3-propanediol was mainly related
to the fermentation yield of both fermentation stages. Thus, the order for the nal concentration of 1,3-propanediol after the second
fermentation stage was: Scenario 2 (511.4 mmol/l) > Scenario 1
(419.7 mmol/l) > Scenario 3 (412.2 mmol/l). And the order for the
fermentative yield of glycerol to 1,3-propanediol was: Scenario
1 > Scenario 3 > Scenario 2; the order for the actual production of
1,3-propanediol was: Scenario 1 > Scenario 3 > Scenario 2 (Table 4).
For the economic assessment of 1,3-propanediol production
from raw glycerol, the total production cost can be divided into
glycerol purication plus glycerol fermentation and 1,3-propanediol recovery and purication. The rst set of costs accounted for
29.432.4% of the total costs and the second set for 67.670.6%.
The 1,3-propanediol purication cost was estimated to be between
0.652 and 0.758 US$/kg. Among the three scenarios, the Commercial Sale Price/Production Cost ratio was higher than unity for all
scenarios, and for the Scenario 3 this ratio was 1.832. These results
indicate that 1,3-propanediol production from raw glycerol by K.
pneumoniae could be a protable alternative for glycerol usage
(Fig. 4d).
Finally, the results for the economic assessment (Commercial
Sale Price/Total Production ratio), as primary feasibility indicator
for the production of added-value products derived from glycerol,
are summarized in Fig. 6. The glycerol purication process (glycerol USP) was also included as an additional high valued derivative.
Initially, all products may generate income because all of them
have a ratio higher than one. More income can be earned from
1,3 propanediol and 1,2 propanediol production, while less income
would be obtained from hydrogen and succinic acid synthesis because of their low production rates and high purication costs. An
interesting fact revealed by Fig. 6 is that purifying glycerol to USP
grade can be more protable than its transformation into products
such as ethanol or acrolein. However, this situation may change in
the near future with higher technological maturity represented by
higher conversion levels, improved selectivities and better downstream technologies.
6. Conclusions
Results obtained for glycerol purication and nine added-value
products generated from glycerol showed that not only quality
requirements were successfully reached, but that all the processes
were protable. In this rst process design approach, glycerol has
been demonstrated to be a renewable and non-expensive feedstock for a system of bioreneries. Moreover, given the fact that
the quality of the glycerol analyzed in this work does not depend
directly on the country where it is produced these results can be
potentially applied to other glycerol conversion facilities in the
world.
Acknowledgement
To the Universidad Nacional de Colombia and Colombian Institute for Development of Science and Technology (COLCIENCIAS),
for the nancial support of this work.
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