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Kraft pulp production generates residues and by‐products of significant importance to the mill. Solid residues from forestry activities are commonly used to generate steam in power boilers. In the recovery cycle, black liquor generates steam (and subsequently energy) by burning in the Tomlinson boiler, while white liquor is regenerated. Well‐developed alternative technologies can use these residues and by‐products to generate different types of biofuels. This review addresses the use of such technologies integrated with Kraft mills, in the concept of biorefineries, showing advantages, disadvantages, and successful examples. Solid residues from forestry can be used to produce bio‐oil through processes such as fast pyrolysis and hydrothermal liquefaction. Bio‐oils are currently used for heating through combustion in commercial/industrial boilers, but greater appreciation occurs if used as biofuels, which is done through catalytic upgrading processes. Black liquor gasification generates synthesis gas, which can be burned for energy co‐generation, used to produce synthetic fuels, or as a hydrogenating agent for bio‐oil or crude tall oil catalytic upgrading. Kraft biorefineries are gradually being implemented, justifying efforts to improve existing and new biomass conversion technologies. [ABSTRACT FROM AUTHOR]

Abstract: The black liquor gasification based bio-fuel production at chemical pulp mill is an attractive option to replace conventional recovery boilers increasing system energy efficiency. The present paper studies circulating fluidized bed system with direct causticization using TiO2 for the gasification of the black liquor to the synthesis gas. The advantage of using direct causticization is the elimination of energy-intensive lime kiln which is an integral part of the conventional black liquor recovery system. The study evaluates the effects of gasifying medium i.e. oxygen or air, on the fluidized bed gasification system, the synthesis gas composition, and the downstream processes for the synthesis gas conversion to the synthetic natural gas (SNG). The results showed higher synthetic natural gas production potential with about 10% higher energy efficiency using oxygen blown gasification system than the air blown system. From the pulp mill integration perspective, the material and energy balance results in better integration of air blown system than the oxygen blown system, e.g. less steam required to be generated in the power boiler, less electricity import, and less additional biomass requirement. However, the air blown system still requires a significant amount of energy in terms of the synthesis gas handling and gas upgrading using the nitrogen rejection system. [Copyright &y& Elsevier]

Abstract: Membrane separation of CO2 from synthesis gas could be an energy efficient and simple alternative to other separation techniques. In this work, a membrane comprised of an about 0.7µm thick MFI film on a graded alumina support was used to separate CO2 from synthesis gas produced by pilot scale gasification of black liquor. The separation of CO2 from the synthesis gas was carried out at a feed pressure of 2.25MPa, a permeate pressure of 0.3MPa and room temperature. In the beginning of the experiment, when the H2S concentration in the feed was 0.5% and the concentration of water in the feed was 0.07%, a CO2/H2 separation factor of 10.4 and a CO2 flux of 67.0kgm−2 h−1 were observed. However, as the H2S concentration in the feed to the membrane increased to 1.7%, the CO2/H2 separation factor and the CO2 flux decreased to 5 and 61.4kgm−2 h−1, respectively. The results suggest that MFI membranes are promising candidates for the separation of CO2 from synthesis gas. [Copyright &y& Elsevier]

Abstract: The only pressurized black liquor gasifier currently in operation is located in Sweden. The composition of the main components in the gas has been reported previously. The main components are H2, CO, CO2, N2, CH4, and H2S. In the present work, trace components in the gas have been characterized and the results are hereby reported for the first time. Samples were taken at two occasions during a one year period. The benzene concentration in the gas varied only slightly and the average concentration was 158ppm. Benzene is formed by thermal cracking of the biomass. The COS concentration varied substantially and the average concentration was 47ppm. The variations may be related to how the quench is operated. A few ppm of C2-hydrocarbons were also observed in the gas and the variation was probably a result of varying oxygen to black liquor ratio. No tars were observed in the gas. However, tar compounds, such as phenanthrene, pyrene, fluoranthene and fluorene were detected in deposits found on the pipe walls after the gas cooler. The concentration of particles in the synthesis gas was very low; <0.1mg/Nm3, which is comparable to the particulate matter in ambient air. Submicron particles were comprised of elements such as C, O, Na, Si, S, Cl, K, and Ca, and these particles probably originated from the black liquor. Larger particles were comprised mainly of Fe, S and Ni and these particles probably resulted from corrosion of steel in the plant pipe-work. In summary, the concentrations of trace components and particles in the gas are quite low. [Copyright &y& Elsevier]

Abstract: Synthetic natural gas (SNG) production from dry black liquor gasification (DBLG) system is an attractive option to reduce CO2 emissions replacing natural gas. This article evaluates the energy conversion performance of SNG production from oxygen blown circulating fluidized bed (CFB) black liquor gasification process with direct causticization by investigating system integration with a reference pulp mill producing 1000 air dried tonnes (ADt) of pulp per day. The direct causticization process eliminates use of energy intensive lime kiln that is a main component required in the conventional black liquor recovery cycle with the recovery boiler. The paper has estimated SNG production potential, the process energy ratio of black liquor (BL) conversion to SNG, and quantified the potential CO2 abatement. Based on reference pulp mill capacity, the results indicate a large potential of SNG production (about 162MW) from black liquor but at a cost of additional biomass import (36.7MW) to compensate the total energy deficit. The process shows cold gas energy efficiency of about 58% considering black liquor and biomass import as major energy inputs. About 700ktonnes per year of CO2 abatement i.e. both possible CO2 capture and CO2 offset from bio-fuel use replacing natural gas, is estimated. Moreover, the SNG production offers a significant fuel replacement in transport sector especially in countries with large pulp and paper industry e.g. in Sweden, about 72% of motor gasoline and 40% of total motor fuel could be replaced. [Copyright &y& Elsevier]

This paper estimates potential hydrogen production via dry black liquor gasification system with direct causticization integrated with a reference pulp mill. The advantage of using direct causticization is elimination of energy intensive lime kiln. Pressure swing adsorption is integrated in the carbon capture process for hydrogen upgrading. The energy conversion performance of the integrated system is compared with other bio-fuel alternatives and evaluated based on system performance indicators. The results indicated a significant hydrogen production potential (about 141 MW) with an energy ratio of about 0.74 from the reference black liquor capacity (about 243.5 MW) and extra biomass import (about 50 MW) to compensate total energy deficit. About 867,000 tonnes of CO 2 abatement per year is estimated i.e. combining CO 2 capture and CO 2 offset from hydrogen replacing motor gasoline. The hydrogen production offers a substantial motor fuel replacement especially in regions with large pulp and paper industry e.g. about 63% of domestic gasoline replacement in Sweden. [ABSTRACT FROM AUTHOR]

Abstract: Biofuel production from gasified black liquor is an interesting route to decrease green house gas emissions. The only pressurised black liquor gasifier currently in pilot operation is located in Sweden. In this work, synthesis gas was taken online directly from this gasifier, purified from hydrocarbons and sulphur compounds and for the first time catalytically converted to methanol in a bench scale equipment. Methanol was successfully synthesised during 45h in total and the space time yield of methanol produced at 25bar pressure was 0.16–0.19g methanol/(g catalyst h). The spent catalyst exposed to gas from the gasifier was slightly enriched in calcium and sodium at the inlet of the reactor and in boron and nickel at the outlet of the reactor. Calcium, sodium and boron likely stem from black liquor whereas nickel probably originates from the stainless steel in the equipment. A slight deactivation, reduced surface area and mesoporosity of the catalyst exposed to gas from the gasifier were observed but it was not possible to reveal the origin of the deactivation. In addition to water, the produced methanol contained traces of hydrocarbons up to C4, ethanol and dimethyl ether. [Copyright &y& Elsevier]

Abstract: Black liquor gasification (BLG) is being developed as an alternative technology for energy and chemical recovery in kraft pulp mills. This study compares BLG – with downstream production of DME (dimethyl ether) or electricity – with recovery boiler-based pulping biorefinery concepts for different types of mills. The comparison is based on profitability as well as CO2 emissions, using different future energy market scenarios. The possibility for carbon capture and storage (CCS) is considered. The results show that, if commercialised, BLG with DME production could be profitable for both market pulp mills and integrated pulp and paper mills in all energy market scenarios considered. Recovery boiler-based biorefinery concepts including extraction of lignin or solid biomass gasification with DME production could also be profitable for market and integrated mills, respectively. If the mill is located close to an infrastructure for CO2 collection and transportation, CCS significantly improves profitability in scenarios with a high CO2 emissions charge, for both combustion- and gasification-based systems. Concepts that include CCS generally show a large potential for reduction of global CO2 emissions. Few of the concepts without CCS achieve a significant reduction of CO2 emissions, especially for integrated mills. [Copyright &y& Elsevier]

Based on KAMa pulp and paper mill, a polygeneration system integrated with a black liquor gasifier is proposed. The effects of CO2 captured by oxygen-fuel combustion and Selexol absorption on the performance of the polygeneration system are studied in terms of both thermodynamic performance and cost assessment. Using the Aspen Plus simulator, the performance of the studied polygeneration systems are analyzed from the perspectives of the first and second laws of thermodynamics. Compared with the reference system, the first law efficiency of the polygeneration system increased from 15.7% to 29.3%, with an investment increment of 17.9%. The investment incremental rates for CO2 capture by oxyfuel combustion and Selexol absorption are 15.1% and 16.7%, respectively. Energy penalty due to CO2 capture and compression is 0.61 MJ electricity/kg CO2, avoided in the oxygen-fuel method at a cost of $29.6/tonne CO2. However, energy penalty can reach 1.03 MJ product (electricity and methanol) per kg CO2, avoided in the Selexol absorption CO2 capture process at a cost of $46.0/tonne CO2. [ABSTRACT FROM AUTHOR]

Abstract: A novel technology to mitigate the climate changes and improve energy security is Pressurized Entrained flow High Temperature Black Liquor Gasification (PEHT-BLG) in combination with an efficient fuel synthesis using the resulting syngas. In order to optimise the technology for use in a pulp and paper mill based biorefinery, it is of great importance to understand how the operational parameters of the gasifier affect the product gas composition. The present paper is based on experiments where gas samples were withdrawn from the hot part of a 3MW entrained flow pressurized black liquor gasifier of semi industrial scale using a high temperature gas sampling system. Specifically, the influence of process conditions on product gas composition (CO2, CO, H2, CH4, H2S, and COS) were examined by systematically varying the operational parameters: system pressure, oxygen to black liquor equivalence ratio, black liquor flow rate to pressure ratio and black liquor pre-heat temperature. Due to the harsh environment inside the gasification reactor, gas sampling is a challenging task. However, for the purpose of the current study, a specially designed high temperature gas sampling system was successfully developed and used. The results, obtained from two separate experimental campaigns, show that all of the investigated operational parameters have a significant influence on the product gas composition and present valuable information about to the process characteristics. [Copyright &y& Elsevier]

Abstract: Black liquor gasification (BLG) has potential to replace a Tomlinson recovery boiler as an alternative technology to increase safety, flexibility and energy efficiency of pulp and paper mills. This paper presents an extensive literature review of the research and development of various BLG technologies over recent years based on low and high temperature gasification that include SCA-Billerud process, Manufacturing and Technology Conversion International (MTCI) process, direct alkali regeneration system (DARS), BLG with direct causticization, Chemrec BLG system, and catalytic hydrothermal BLG. A few technologies were tested on pilot scale but most of them were abandoned due to technical inferiority and very fewer are now at commercial stage. The drivers for the commercialization of BLG enabling bio-refinery operations at modern pulp mills, co-producing pulp and value added energy products, are discussed. In addition, the potential areas of research and development in BLG required to solve the critical issues and to fill research knowledge gaps are addressed and highlighted. [Copyright &y& Elsevier]

Abstract: There is great interest in developing black liquor gasification technology over recent years for efficient recovery of bio-based residues in chemical pulp mills. Two potential technologies of producing dimethyl ether (DME) and methane (CH4) as alternative fuels from black liquor gasification integrated with the pulp mill have been studied and compared in this paper. System performance is evaluated based on: (i) comparison with the reference pulp mill, (ii) fuel to product efficiency (FTPE) and (iii) biofuel production potential (BPP). The comparison with the reference mill shows that black liquor to biofuel route will add a highly significant new revenue stream to the pulp industry. The results indicate a large potential of DME and CH4 production globally in terms of black liquor availability. BPP and FTPE of CH4 production is higher than DME due to more optimized integration with the pulping process and elimination of evaporation unit in the pulp mill. [Copyright &y& Elsevier]

Abstract: Black liquor gasification (BLG) is currently being developed as an alternative technology for energy and chemical recovery at chemical pulp mills. This study examines how different assumptions regarding systems surrounding the pulp mill affect the CO2 emission balances for different BLG concepts. The syngas from the gasification process can be used for different applications; this study considers production of renewable motor fuels and electricity generation. Both a market pulp mill and an integrated pulp and paper mill are considered as host mill for the BLG plant. Furthermore, the consequences of limited availability of biomass are shown, i.e., increasing the use of biomass in a mill is not necessarily CO2-neutral. The results show that the potential to reduce CO2 emissions by introducing BLG is generally much higher for a market pulp mill than for an integrated pulp and paper mill. Electricity generation from the syngas is favoured when assuming high grid electricity CO2 emissions where as motor fuel production is favoured when assuming low grid electricity CO2 emissions. When considering the consequences of limited availability of biomass, the CO2 emission balances are strongly affected, in some cases changing the results from a decrease to an increase of the CO2 emissions. [Copyright &y& Elsevier]

The article discusses black liquor gasification which is a process for recovering the energy and chemicals in black liquor produced from the Kraft pulping process. The process, which can be combined with catalytic conversion of synthesis gas (syngas) into motor fuels, holds potential for the production of motor fuel from black liquor. The article focuses on the results obtained by spatially resolved measurements of the composition of gas in the DP-1 gasifier, which is a pressurized black liquor gasifier that contains a water cooled quench probe, in Sweden. Results from several detailed experiments using high-speed photography of black liquor sprays are also discussed in-depth.

Abstract: When gasified black liquor is used for hydrogen production, significant amounts of biomass must be imported. This paper compares two alternative options for producing hydrogen from biomass: (A) pulp-mill-integrated hydrogen production from gasified back liquor; and (B) stand-alone production of hydrogen from gasified biomass. The comparison assumes that the same amount of biomass that is imported in Alternative A is supplied to a stand-alone hydrogen production plant and that the gasified black liquor in Alternative B is used in a black liquor gasification combined cycle (BLGCC) CHP unit. The comparison is based upon equal amounts of black liquor fed to the gasifier, and identical steam and power requirements for the pulp mill. The two systems are compared on the basis of total CO2 emission consequences, based upon different assumptions for the reference energy system that reflect different societal CO2 emissions reduction target levels. Ambitions targets are expected to lead to a more CO2–lean reference energy system, in which case hydrogen production from gasified black liquor (Alternative A) is best from a CO2 emissions’ perspective, whereas with high CO2 emissions associated with electricity production, hydrogen from gasified biomass and electricity from gasified black liquor (Alternative B) is preferable. [Copyright &y& Elsevier]

• Black liquor gasification was coupled with calcium looping. • Calcium looping for CO 2 capture and H 2 production was compared. • CO 2 capture route (39 €/t) was less expensive than H 2 production route (48.8 €/t). • CO 2 avoided cost was highly dependent on capital cost of black liquor gasification. • Export of H 2 had the lowest CO 2 avoided cost among black liquor gasification cases. Although considered one of the major energy-intensive industries (EIIs), the pulp and paper industry has also the potential for energy production from an industrial waste, black liquor. This study proposes black liquor gasification (BLG) coupled with calcium looping (CaL) as a CO 2 capture route for the pulp and paper industry. BLG with H 2 production (BLG-CaL-H 2), BLG with gas turbine combined cycle (BLG-CaL-GT) or with solid oxide fuel cell (BLG-CaL-SOFC) were considered. The dependence of carbon capture and storage (CCS) cost on the natural gas, limestone, electricity imported and H 2 sale prices aside the expenditures related with BLG-CaL were evaluated. The CCS route, based on CaL retrofitted to the pulp and paper plant, was found to have a lower cost of CO 2 avoided (39.0 €/tCO 2) when compared with BLG-CaL (48.8–57.1 €/tCO 2). Between the BLG-CaL scenarios, BLG-CaL-H 2 presented the lowest cost of CO 2 avoided (48.8 €/tCO 2) but the highest energy penalty. Based on the thermodynamic performance, it was shown that CaL retrofit and BLG-CaL-SOFC presented the best overall performance, turning the electricity importer reference plant into electricity exporter. The economic sensitivity showed that the capital requirement of BLG-CaL has a strong effect on the cost of CO 2 avoided for all alternatives. The H 2 production is also strongly affected by the H 2 sale price while BLG-CaL-SOFC and BLG-CaL-GT are strongly dependent on natural gas price. [ABSTRACT FROM AUTHOR]