Applied Energy 90 (2012) 24–31

Contents lists available at ScienceDirect

Applied Energy
journal homepage: www.elsevier.com/locate/apenergy

Bio-refinery system in a pulp mill for methanol production with comparison

of pressurized black liquor gasification and dry gasification using direct
causticization
Muhammad Naqvi a,⇑, Jinyue Yan a,b, Erik Dahlquist b
a
Department of Chemical Engineering and Technology, Royal Institute of Technology, SE-10044 Stockholm, Sweden
b
School of Sustainable Development of Society and Technology, Mälardalen University, Box 883, SE-72123 Västerås, Sweden

a r t i c l e i n f o a b s t r a c t

Article history: Black liquor gasification (BLG) for bio-fuel or electricity production at the modern pulp mills is a field in
Received 21 September 2010 continuous evolution and the efforts are considerably driven by the climate change, fuel security, and
Received in revised form 20 December 2010 renewable energy. This paper evaluates and compares two BLG systems for methanol production: (i) oxy-
Accepted 27 December 2010
gen blown pressurized thermal BLG; and (ii) dry BLG with direct causticization, which have been
Available online 26 January 2011
regarded as the most potential technology candidates for the future deployment. A key objective is to
assess integration possibilities of BLG technologies with the reference Kraft pulp mill producing
Keywords:
1000 air dried tonnes (ADt) pulp/day replacing conventional recovery cycle. The study was performed
Bio-fuel
Bio-refinery
to compare the systems’ performance in terms of potential methanol production, energy efficiency,
Black liquor gasification and potential CO2 reductions. The results indicate larger potential of black liquor conversion to methanol
Methanol from the pressurized BLG system (about 77 million tonnes/year of methanol) than the dry BLG system
Pulp mill (about 30 million tonnes/year of methanol) utilizing identical amount of black liquor available worldwide
(220 million tDS/year). The potential CO2 emissions reduction from the transport sector is substantially
higher in pressurized BLG system (117 million tonnes/year CO2 reductions) as compared to dry BLG
system (45 million tonnes/year CO2 reductions). However, the dry BLG system with direct causticization
shows better results when considering consequences of additional biomass import. In addition,
comparison of methanol production via BLG with other bio-refinery products, e.g. hydrogen, dimethyl
ether (DME) and bio-methane, has also been discussed.
Ó 2010 Elsevier Ltd. All rights reserved.

1. Introduction for re-use in the digestion unit. The recovery boiler technology has
proven to work well but it has several major disadvantages in
Pulp and paper industry consumes a large proportion of bio- terms of low electric power generation efficiency, risk of smelt-
mass worldwide that include bark, wood residues, and black liquor water explosions and reduced-sulfur gas emissions [1,2]. There
(BL). Being a limited resource, biomass must be used as efficiently has been a significant interest in developing new technologies like
as possible. Due to the fact that modern pulp and paper industries BLG to avoid such drawbacks associated with the conventional
have established infrastructure for handling and processing bio- recovery boilers.
mass, it is possible to lay foundation for future gasification based Several concerted efforts have been made in recent years to
bio-refineries to co-produce electricity, chemicals or bio-fuels with evaluate energy consequences of the integrated BLG technology
pulp and paper products. There is potential to export electricity or in the pulp mills and to compare utilization of black liquor in the
bio-fuels by improving today’s existing pulp and paper mills. most efficient manner [3–8]. Mass and energy balances for a con-
Black liquor is a major bio-energy resource, especially in coun- ventional pulp mill with the recovery boiler are compared with a
tries having large pulp and paper industry. Black liquor is the res- pulp mill integrated BLG plant to investigate energy, environmen-
idue of lignin and spent chemicals produced during chemical tal and economic consequences [9,10]. Integration of BLG with ad-
pulping process in digesters, also known as Kraft process. In con- vanced gas turbine has been studied by Maunsbach et al. [12]
ventional pulp mills, black liquor is fired in a recovery boiler (RB) within an eco-cyclic pulp mill research program (see KAM report,
to produce steam and electricity and to recover cooking chemicals 2003 for an overview) [11], to improve the performance of the
combined heat and power. The advanced gas turbines include
⇑ Corresponding author. Tel.: +46 8 7906713. evaporative gas turbine (EvGT) [13] and externally fired gas
E-mail address: [email protected] (M. Naqvi). turbine (EFGT) [14–17]. Berglin et al. assessed the preliminary

0306-2619/$ - see front matter Ó 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.apenergy.2010.12.074
 M. Naqvi et al. / Applied Energy 90 (2012) 24–31 25

Nomenclature

ADt air dried tonnes DARS direct alkali regeneration system

ASU air separation unit DBLG dry black liquor gasification
BFW boiler feed water DME dimethyl ether
BL black liquor FAO food and agriculture organization
BLG black liquor gasification KAM kretslopps anpassad massafabrik
BLS black liquor solids LHV lower heating value
CBLG Chemrec black liquor gasification MeOH methanol
CCS carbon capture and storage RB recovery boiler
CFB circulating fluidized bed

economics of BLG with motor fuel production, e.g. methanol and the integrated pulp mill with BLG to replace conventional recovery
dimethyl ether (DME) [18]. Andersson and Harvey analyzed pulp boiler. System performance is analyzed in terms of potential meth-
mill integrated hydrogen production from BLG and compared with anol production, overall system efficiency (i.e. energy ratios and
stand-alone hydrogen production from biomass gasification black liquor to methanol efficiency), and comparison of methanol
[19,20]. Consonni et al. studied gasification based bio-refinery production route with other possible bio-refinery alternatives,
operations for bio-fuel production, e.g. DME, Fischer–Tropsch liq- e.g. H2, DME and CH4. In addition, the potential CO2 reductions
uids, and ethanol-rich mixed-alcohols [21]. Naqvi et al. investi- are estimated if methanol is used as an automotive fuel replacing
gated two different BLG technologies, i.e. pressurized gasification fossil gasoline.
for DME production and catalytic hydrothermal gasification for
methane production [22]. A number of studies presented dry BLG
technology with direct causticization. Equilibrium calculations 2. Pulping and BLG processes
were performed on direct causticization with titanium dioxide
(TiO2) using a program called FACT [23]. Zeng and Heiningen car- 2.1. Conventional pulping process
ried out experimental tests in a fluidized bed reactor processing
1 kg of dry black liquor solids (BLS) per hour [24]. Richards et al. The dominant pulp production process is chemical pulping pro-
[25] and later Nohlgren and Sinquefield [26] have done compli- cess, also known as Kraft process, in which the cellulose fibers are
mentary investigations on causticization chemistry. From the re- separated from the lignin. The process includes a major operation
sults of various studies and experiences from pilot plant, it is known as digestion where wood chips are impregnated with the
believed that if important technical issues are resolved, commer- cooking liquor. The wood chips are cooked at a temperature of
cialization of BLG technology will be reached within a decade [27]. 150–170 °C under highly alkaline conditions in the presence of sul-
The potential of electricity or bio-fuel production have been fide [11]. The produced pulp is washed to recover black liquor and
studied mostly with pressurized BLG system integrated with mod- reduce the carryover of organic component in oxygen delignifica-
ern pulp mills but there is no valuable effort made to estimate the tion unit. The pulp is then bleached with chlorine dioxide and
potential electricity or bio-fuel production from other gasification hydrogen peroxide in a sequence of acidic and alkaline stages.
technologies. The aim of the study is to investigate energy conver- The bleached pulp is dried with hot air before shipped to paper
sion performance of black liquor to methanol production compar- mills.
ing two different types of BLG technologies: (i) oxygen blown From the energy perspective, a modern Kraft pulp mill is self
pressurized entrained flow gasification (Chemrec design), and (ii) sufficient thanks to the black liquor recovery cycle: all internal
dry black liquor gasification process with direct causticization. steam and electricity demand can be met by recovering energy
The emphasis is to keep the pulping process unchanged without from the dissolved lignin in the black liquor [10]. The conventional
any major impacts and recover all cooking chemicals from black li- recovery boilers are employed for dual purposes, i.e. recover en-
quor to re-use in digestion unit. The energy withdrawn in terms of ergy and cooking chemicals from black liquor. Due to the presence
black liquor conversion to methanol must be compensated by of high organic content from the dissolved lignin; black liquor rep-
additional biomass import. Fig. 1 shows bio-refinery concept in resents a potential energy source of 250–500 MW per mill that

Wood Paper/pulp
Chemical Pulp mill

MP/LP MP/LP
Power
steam Cooking steam
Power
liquor
BL BL
Recovery BLG
Boiler Island HP steam
HP steam

Bark Power
boiler MeOH boiler

Falling Additional Falling

bark Biomass bark

Fig. 1. Concept of bio-refinery system in the integrated pulp mill with BLG replacing the recovery boiler.
26 M. Naqvi et al. / Applied Energy 90 (2012) 24–31

produces 1.7–1.8 tonnes of black liquor per tonne of pulp [4]. 2.5. BLG based MeOH production
Today, energy from black liquor is utilized to meet steam and elec-
tricity demand for the pulping operations but it is of great interest The synthesis gas leaving the gasifier (i.e. either CBLG or DBLG
to convert this energy to more valuable energy products. systems) is saturated with water vapor representing a considerable
amount of heat energy that can be recovered to generate medium
2.2. BLG systems configuration and low-pressure steam. It is also important to remove fine partic-
ulates of alkali salts in the synthesis gas. To accomplish both oper-
In a BLG process, a gasification island is used to replace the con- ations, a combined gas cooling and particulate removal unit is
ventional recovery cycle to increase potential energy efficiency and used, e.g. counter current condenser type of gas cooler [18]. To re-
also eliminating the drawbacks associated with the recovery boiler. move sulfur components in the synthesis gas, a new type of
Black liquor is gasified in the reactor at high temperatures under absorption system is used with sodium carbonate (Na2CO3) solu-
reducing conditions and synthesis gas is separated from the inor- tion as solvent, developed by Dahlquist and Jones [28]. H2S is ab-
ganic content, e.g. mainly sodium carbonate and sodium sulfate sorbed in a gas scrubber, reacting immediately with Na2CO3
[28]. The detailed description and integration of studied BLG tech- solution in a selective way; while CO2 reacts very slowly. The de-
nologies with the reference pulp mill is discussed in later sections. signed absorption system provides 20 times more absorption of
H2S than the absorption of CO2.
2.3. Chemrec BLG system After cleaning, about 50% of cleaned synthesis gas from the
CBLG system is then adjusted in composition in CO-shift unit using
The pressurized, oxygen blown thermal Chemrec system (CBLG) water gas shift reaction because the gas contains excess CO and too
gasifies black liquor at 32 bar and 950–1000 °C, using oxygen as little H2 for MeOH synthesis. See reaction (5). The shifted gas
gasifying agent [4]. The gasifier bed is composed of sodium carbon- stream is then mixed with remaining un-converted gas and sent
ate and sodium sulfide particles formed during gasification. The to MeOH synthesis loop:
high temperature gasification results in molten smelt from the
CO þ H2 O $ CO2 þ H2 þ Heat ð5Þ
inorganic constituents in the black liquor. Organics are gasified
to synthesis gas containing mainly carbon monoxide, hydrogen The synthesis gas from the DBLG system does not require shift
and methane. The synthesis gas and molten smelt flows down- conversion as it contains more H2 than CO. The product gas is then
wards after a residence time of 5–10 s to a quench dissolver where compressed to about 90 bar required for the MeOH synthesis loop.
they are simultaneously separated. The synthesis gas and the smelt The loop comprises of single MeOH reactor and a distillation sec-
are cooled from quench temperature of 220 °C to about 90 °C by tion for purification. Following reactions takes place in the MeOH
injection of condensate from the cooling unit. The smelt dissolves reactor [18]:
in the weak wash forming green liquor, which is pumped back to
the causticizing unit to produce white liquor for re-use in the CO þ 2H2 $ CH3 OH DH300 ¼ 90:77 kJ=mol ð6Þ
digestion unit.
CO2 þ 3H2 $ CH3 OH þ H2 O DH300 ¼ 49:16 kJ=mol ð7Þ
2.4. Dry BLG with direct causticization
Being exothermic, the MeOH synthesis releases a considerable
amount of heat that is utilized to preheat boiler feed water
In dry BLG (DBLG) process with direct causticization, a gasifier
(BFW) and generate low-pressure steam for the distillation section.
replaces the recovery boiler but also the conventional chemical
This decreases the net steam demand of BLG Island and fuel con-
recovery cycle is replaced by a titanate cycle for direct causticiza-
sumption in the power boiler. Small amounts of combustible
tion within the gasifier. Black liquor is introduced into a fluidized
wastes, e.g. combustible gases and liquid wastes, from the MeOH
bed of titanium dioxide (TiO2) in a circulating fluidized bed (CFB)
synthesis loop also contribute as supplementary fuel in the power
gasifier [28]. The synthesis gas constitutes H2, CO, and CO2 as main
boiler that produces steam to meet heat demand of the pulp mill.
feedstock for bio-fuel production. During the gasification, sulfates
The backpressure steam turbine is used for the electricity
in black liquor are reduced to sulfides and a major part of sulfides
generation.
are evaporated as hydrogen sulfide (H2S). The sodium carbonate is
evaporated to CO2 forming Na2OTiO2, which means direct causti-
cization in the bed. This leads to elimination of complicated and 3. Methods and assumptions
energy-intensive lime kiln for reburning of CaCO3 as is normally
the case in the conventional recovery cycle and also in other gasi- 3.1. Studied systems
fication technologies. The main reactions in the gasifier are [26]:
This section presents assumptions and methodology adapted to
7Na2 CO3 þ 5ðNa2 O  3TiO2 Þ ! 3ð4Na2 O  5TiO2 Þ þ 7CO2 ð1Þ
configure two different BLG technologies and integration with the
reference pulp mill, (i) Chemrec BLG (CBLG) system; and (ii) dry
Na2 SO4 þ 2C ! Na2 S þ 2CO2 ð2Þ
BLG (DBLG) with direct causticization. The CBLG system employs
currently most advanced oxygen blown pressurized entrained flow
Na2 S þ CO2 þ H2 O ! Na2 CO3 þ H2 S ð3Þ
gasifier and it can produce synthesis gas at a high temperature sep-
During leaching with water, the sodium pentatitanate formed in arating in-organics from black liquor in the quench section within
the gasifier is converted to sodium tri-titanate and sodium hydrox- the gasifier. The dry BLG system is a circulating fluidized bed gas-
ide (white liquor). See the following reaction: ifier using TiO2 as bed material. The two systems differ mainly in
terms of chemical recovery, i.e. the CBLG system increases causti-
3ð4NaÞ2 O  5TiO2 Þ þ 7H2 O ! 5ðNa2 O  3TiO2 Þ þ 14NaOH ð4Þ
cizing load while the DBLG system eliminates lime kiln with no
The sodium tri-titanate is separated from the white liquor and causticization requirement, and also differ in terms of synthesis
recycled to the gasifier. The sulfur-lean white liquor is sent back gas composition.
to the pulp mill for re-use in the digestion unit. The H2S in the syn- Fig. 2 compares chemical recovery cycle in dry BLG with direct
thesis gas is recovered using selective absorption and can be used causticization and Chemrec BLG integrated with the pulp mill. It is
to produce sulfur-rich aqueous stream. assumed that all cooking chemicals must be recovered from the
 M. Naqvi et al. / Applied Energy 90 (2012) 24–31 27

DBLG system CBLG system

BLG Island BLG Island
MeOH MeOH

Synthesis gas Synthesis gas

Conc. BL BLG with Chemrec

4Na2O.5TiO 2 Conc. BL
Green liquor
direct BLG
White
TiO 2 causticization liquor
Leaching of Causticizing
NaOH

White CaO CaCO3

liquor
Separation Lime kiln
washing
Na2O.3TiO 2

H2O Falling bark CO2

Fig. 2. Comparison of chemical recovery cycle in pulp mill integrated MeOH production from dry BLG with direct causticization and Chemrec BLG.

gasifier and sent back to the pulp mill for re-use in the digestion grated reference pulp mill is constant in the CBLG system. How-
unit. The integrated BLG systems with the pulp mill for MeOH pro- ever, the energy demand is reduced in the DBLG system mainly
duction require compensating process steam and electricity from due to the elimination of energy-intensive lime kiln.
black liquor by additional biomass import and combustion in the
power boiler. The demand of electricity and steam for the inte- 3.2. Reference mill characteristics

Table 1 The reference mill is an eco-cyclic pulp mill developed within

Reference pulp mill characteristic. the Swedish research program KAM (Kretslopps Anpassad Massa-
fabrik). KAM mill is a hypothetical and generic mill with commer-
Pulp production ADt pulp/day 1000
Wood consumption Tonnes/day (dry wood) 2074 cially best available technologies with better integration under
Black liquor solids (BLS) per tonne pulp Tonnes/tonne 1.7 high environmental standards. The nominal scale of the KAM refer-
BL solids flow rate Tonnes BLS/day 1700 ence mill is 2000 air dry metric tonnes (ADt) per day of pulp pro-
BL concentration % solids 80
duction [11]. Base capacity for the reference mill selected for this
BL heating value MJ/kg 12.3
BL energy content MW 243.5
study is 1000 ADt/day of pulp production that is approximately
BLS composition (wt.%) C 33 equivalent to 1700 tonnes per day of black liquor solids (BLS, as
O 36.9 dry). Table 1 shows key reference mill parameters used to config-
H 3.7 ure CBLG and DBLG systems.
S 4.27
Na 20.04
K 1.92 3.3. System modeling
Ash/chlorides 0.22
Mill steam use MW 125
Mill electricity use MW 29.7
The process flow charts of MeOH production from CBLG and
DBLG systems are shown in Figs. 3 and 4, respectively. The

MP
CO -shift reactors LP
LP
IP

Cleaned syn -gas

Na2CO3

H2 S-Absorber
Cooled syn -gas Shifted syn- gas

Chemrec MeOH
gasifier 5 86 tonnes /day
S-rich stream
Combustible wastes
LLP steam CW
BL 1.5 bar
Raw MeOH
1700 Tds/day
950 °C P= 90 bar
LP steam
32 bar
4 bar
LLP
MP steam IP
12 bar
MeOH distillation

Syn-gas MeOH reactor

cooler 250 °C

Fig. 3. Process flow sheet of MeOH production via CBLG system.

28 M. Naqvi et al. / Applied Energy 90 (2012) 24–31

Cleaned syn -gas

MeOH
Na2 CO3
227 tonnes /day
Cooled syn-gas
H2S-Absorber Combustible wastes
CW

CFB Raw MeOH

Gasifier S-rich stream
P = 90 bar
LLP steam
BL 1.5 bar IP
LLP
1700 tDS/day
720 °C LP steam MeOH distillation
1 bar 4 bar

MP steam MeOH reactor

12 bar 250 °C

Syn-gas cooler

Fig. 4. Process flow diagram of MeOH production via DBLG system.

integrated BLG systems comprise all units from black liquor con- demand of steam and electricity shall be fulfilled by employing a
version to MeOH production and a power boiler. The configuration new biomass power boiler. To compensate energy deficit due to
includes black liquor gasifier, gas cooling and cleaning unit, and black liquor conversion to MeOH, additional biomass is combusted
synthesis gas conversion to MeOH. The key input values used for in the power boiler. The key parameters of the power boiler are
energy calculations are listed in Table 2. summarized in Table 3.
The data used for energy calculations is based on previous work The power boiler is dimensioned primarily to generate as much
by Naqvi et al. [22]. A new designed H2S absorption system, using steam as produced by the recovery boiler for mill process use and
sodium carbonate (Na2CO3) as solvent, replaces the Rectisol pro- also to meet internal steam demand of the BLG Island. The steam
cess for acid gas removal and recovery [28]. The DBLG system uses turbine is working in back pressure mode producing both electric-
data from simulations with polynoms (i.e. SIMCA) made from the ity and steam for pulping process. The boiler feed water is pre-
pilot plant operations and physical relations. The composition of heated with warm water from the gas cooling unit and the boiler
the synthesis gas from pilot plant operated at a relative oxidation efficiency is assumed to be 90% at full load.
(i.e. amount of O2 per kg BL  amount of O2 needed for 100% oxi-
dation of all organics) of 35% is used. 4. Performance modeling results

3.4. Power boiler Material and energy balances are used to determine the poten-
tial electricity, steam and MeOH production based on reference
The combustion of black liquor in the recovery boiler is respon- mill capacity, i.e. 1000 ADT/day of pulp production. The additional
sible for generating steam and electricity required in the pulp mill. biomass import needed to compensate the energy withdrawn from
However in case of BLG integrated MeOH production, the total black liquor to methanol production is also estimated.

4.1. MeOH production potential

Table 2
Key operating parameters for BLG island modeling.
To compare the studied systems, the bio-refinery performance
Gasifier estimates are reported in Table 4. Methanol production potential
CBLG Pressure Bar 32 is used as a performance indicator to evaluate the optimization
Temperature °C 950
DBLG Pressure Bar 1.01
of the integrated systems, either CBLG or DBLG, estimating poten-
Temperature °C 720 tial amount of MeOH that can be produced based on the reference
BLS to gasifier % 100 unit. The results indicated that MeOH production is significantly
Gas at cooler outlet Temperature °C 30 higher in the CBLG system than the DBLG system but at a cost of
CO-shift reactor High temperature shift (HTS) °C 350
larger biomass import.
Low temperature shift (LTS) °C 190
MeOH synthesis Pressure Bar 90
Temperature °C 250 4.2. Energy ratios

The energy ratio is defined as the sum of mill process steam, net
electricity import or export, and MeOH output divided by the sum
Table 3 of all fuel energy inputs. The estimated energy ratios are used to
key parameters of the power boiler. investigate the competitiveness of integrated BLG systems replac-
Power boiler characteristics
ing the conventional recovery boilers. See Table 5 (lower heating
Load % 100 values are used). The ratio of useful energy outputs to total energy
Feed water temperature °C 160 inputs is higher in the CBLG system than for the recovery boiler
Steam pressure Bar 140 case. When comparing studied systems, the CBLG systems shows
Steam temperature °C 545
better overall energy efficiency (71%) as compared to about 53%
Boiler efficiency % 90
energy efficiency in the DBLG system.
 M. Naqvi et al. / Applied Energy 90 (2012) 24–31 29

Table 4 CO2 emissions associated with upstream processes, i.e. additional

Bio-refinery performance estimates comparing recovery boiler, CBLG and DBLG biomass cultivation and transport to mill site, but these emissions
systems.
are not included in scope of this study. About 1.5 tonnes of CO2
RB CBLG DBLG could be reduced for each tonne of MeOH produced, taking an
Pulp production ADt/day 1000 1000 1000 average value of 85% carbon in 1 tonne of gasoline [29]. Table 7
BL to gasifier, LHVa MW 243.5 243.5 243.5 shows the theoretical possible CO2 reductions from potential
Electricity balance methanol production per year based on black liquor availability
Mill electricity use MW 27.6 28.3 26.1
BL unit consumption MW 2.5 15.6 6.9
in the reference mill system, Sweden, Europe and world. Note that
Electricity production MW 52.2 21.6 24.6 the scale up is used as a simplification tool to estimate potential
Import/Export (-/+) MW 22.1 22.3 8.4 CO2 offset if black liquor available in various regions is gasified
Steam balance to produce methanol. The pulp mills with different energy balances
Steam to mill process Tonnes/hr 176.8 177.6 176.5
will result in different on-site CO2 reductions and CO2 savings
Net BLG production Tonnes/hr – 75.5 61.2
Power boiler Tonnes/hr – 102.1 115.3 replacing fossil fuels.
Bark
Existing bark MW 40.5 40.5 40.5
Bark to lime kiln MW 21.1 29.7 – 5. Discussion
Bark to power boiler MW – 70.8 80.8
Net bark available MW 19.6 60 40.3
Methanol production Tonnes/day – 585.6 226.9 The study shows a number of informative comparisons between
Energy output, LHV MW – 143 55.7 integrated BLG systems for methanol production and also with the
Petroleum equivalentb Barrels per day – 2276 886.3 conventional black liquor recovery system in terms of chemical
a
Lower heating values (LHV) of fuels, e.g. BL (12.3 MJ/kg), bark (19.4 MJ/kg), recovery and energy balances.
methanol (21.1 MJ/kg).
b
Barrels (bbl) per day of eqvt. petroleum-derived gasoline (5.43 GJ/bbl) replaced  The studied BLG systems differ in synthesis gas composition but
by methanol. mainly in terms of chemical recovery. In conventional recovery
system, sodium and sulfur as molten sodium sulfide and
sodium carbonate are recovered at the bottom of the recovery
Table 5 boiler. The smelt is then dissolved in weak wash to produce
Energy efficiency results of compared systems. green liquor. Before it can be reused for delignification, the
causticizing of green liquor is performed to produce calcium
RB CBLG DBLG
carbonate and sodium hydroxide. However in the CBLG system,
Energy inputs
a major part of sulfur in black liquor leaves the gasifier as H2S
Black liquor (dry solids) MW 243.5 243.5 243.5
Bark to lime kiln MW 21.1 29.7 – and not as sodium sulfide (Na2S). This result in conversion of
Bark to power boiler MW – 70.8 80.8 only 45% of incoming sulfur in black liquor to Na2S and an
Total inputs MW 264.6 344 324.3 increase in causticizing need to 23% (i.e. increased load on lime
Energy outputs kiln fired with bark compared to conventional recovery system).
Mill process steam MW 125 125.7 125.7
Estimated bark to lime kiln in the recovery boiler case is about
Electricity import/export (-/+) MW 22.1 22.3 8.4
Methanol production MW – 143 55.7 95 tonnes DS/day. However, in the CBLG system it is increased
Total outputs MW 147.1 246.4 172.3 to 132 tonnes DS/day. There is no direct causticization in the
Energy ratio 0.56 0.71 0.53 CBLG system due to liquid phase and it is not possible to add
TiO2 to get causticization.
 In the DBLG system, there is direct causticization in the reactor
4.3. Black liquor to methanol efficiency that eliminates the causticizing needs. Within dry BLG process,
approximately 65% of the sulfur is forming H2S and goes with
The system performance of studied BLG systems is compared in the gas phase. It is then recovered with a mixture of NaOH
terms of black liquor energy conversion to methanol energy. Note and Na2CO3 at pH 10.5, where a selective absorption of H2S
that in the reference pulp mill system, the combustion of the black can be achieved in relation to CO2, and thus a strong NaHS
liquor results in only internal steam and electricity demand of the phase formed (1 M). When the sodium oxide titanate is leached
pulping process but with no energy product output. The major en- in water we directly get NaOH, and thus a separation is made
ergy streams (i.e. black liquor and methanol) passing the system between NaOH and NaHS, which enables modified cooking
boundary of the BLG island configuration are given in Table 6. [32]. In addition, the dry BLG with direct causticization showed
several other advantages over conventional recovery cycle, such
as higher white liquor concentration, and production of white
4.4. Potential CO2 reductions liquor of varying sulfidity.
 When we compare the energy balances, the CBLG system offers
To estimate the potential CO2 offset, MeOH produced from higher methanol output (143 MW) compared to the DBLG sys-
black liquor is considered as CO2 neutral and it is assumed to re- tem (about 56 MW) but at a cost of 20 MW extra biomass
place fossil gasoline as an automotive fuel. There is some fossil fuel import, i.e. about 60 MW biomass import needed in the CBLG
system and about 40 MW in the DBLG system.
 The black liquor to methanol efficiency is used as a system per-
Table 6
formance indicator for energy conversion of the integrated BLG
Black liquor to methanol efficiency.
systems. The results show substantially higher black liquor con-
CBLG DBLG version efficiency in the CBLG system (59%) than the DBLG sys-
Black liquor to MeOH tem (23%), mainly due to better performance results in the
Black liquor (dry solids) MW 243.5 243.5 system configuration, e.g. larger methanol production and also
Methanol MW 143 55.7
net BLG steam production in the CBLG system is higher than
Conversion efficiency, LHV % 59 23
the DBLG system.
30 M. Naqvi et al. / Applied Energy 90 (2012) 24–31

Table 7 The possibilities for integrated bio-energy system for combined

Potential CO2 emissions offset from methanol production based on BLS availability in
2008.
heat and power generation with CO2 capture and storage (CCS) has
been introduced and analyzed, see [31]. The potential DME or CH4
Ref. Sweden Europe World production from thermal and catalytic hydrothermal gasification
mill
process has been compared [22,33]. Integration of BLG based poly-
CBLG system generation integrated with CO2 capture and storage (CCS) is one of
BLS availabilitya Million tDS/year 0.60 14.4 55.2 220
MeOH production Million tonnes/year 0.21 5.04 19.3 77.1
interesting topics for future studies. In addition, the synthesis gas
CO2 reductions Million tonnes/year 0.32 7.6 29.2 116.8 composition shows potential methane production via BLG with di-
DBLG system rect causticization and it will be investigated in future.
BLS availability Million tDS/year 0.60 14.4 55.2 220
MeOH production Million tonnes/year 0.08 1.92 7.5 29.7
CO2 reductions Million tonnes/year 0.12 2.9 11.3 45 6. Conclusion
a
Based on the food and agriculture organization (FAO) data base 2008 [30].
Two different black liquor gasification systems for methanol
production are compared based on chemical recovery cycle, elec-
tricity and steam balances, additional biomass import, energy ra-
Table 8
tios and CO2 emissions offset. The study has shown that there is
Comparison of BLG for MeOH production with various bio-fuels from different
studies. a potential to replace conventional black liquor recovery cycle with
the BLG systems in the pulp mills, co-producing pulp and valuable
Parameters reference Bio-refineries
energy products. There is a larger potential of black liquor conver-
Ekbom Andersson and Naqvi Present sion to methanol from the Chemrec BLG system (about 77 million
et al. [4] Harvey [19] et al. [22] study
tonnes/year of methanol) than the dry BLG system (about 30 mil-
Product DME H2 CH4 MeOH lion tonnes/year of methanol) utilizing identical amount of black
CBLG DBLG liquor available worldwide (220 million tDS/year). In addition,
Pulp, ADt/day 1000 1000 1000 1000 1000 the potential CO2 emissions reduction from the transport sector
BLS, tDS/day 1700 1700 1700 1700 1700 is substantially higher in Chemrec BLG system (117 million ton-
Steam from PBa, t/h 117.7 116 141.8 102.1 115.3
nes/year CO2 reductions) as compared to dry BLG system (45 mil-
Bark, import/export 62.5 61.8 106.5 60 40.3
(/+), MW lion tonnes/year CO2 reductions). The results are better in terms
Power, import/export 27.7 28.4 1.1 22.3 8.4 of biomass import in the dry BLG system with direct causticization
(/+), MW mainly due to elimination of the lime kiln.
Fuel production 137.5 130.5 240.2 143 55.7
(LHV), MW
a
Acknowledgement
Power boiler.

One of authors (Naqvi) would like to acknowledge the HEC/SI

Scholarship Programme, which is funded by Higher Education
 The energy ratio of the CBLG system shows substantial Commission Pakistan and managed by Swedish Institute.
improvements in the overall energy system at the pulp mill
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