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Title: Mill Integration-Pulping, Stream Reforming and Direct Causticization for Black Liquor Recovery

Abstract

MTCI/StoneChem developed a steam reforming, fluidized bed gasification technology for biomass. DOE supported the demonstration of this technology for gasification of spent wood pulping liquor (or 'black liquor') at Georgia-Pacific's Big Island, Virginia mill. The present pre-commercial R&D project addressed the opportunities as well as identified negative aspects when the MTCI/StoneChem gasification technology is integrated in a pulp mill production facility. The opportunities arise because black liquor gasification produces sulfur (as H{sub 2}S) and sodium (as Na{sub 2}CO{sub 3}) in separate streams which may be used beneficially for improved pulp yield and properties. The negative aspect of kraft black liquor gasification is that the amount of Na{sub 2}CO{sub 3} which must be converted to NaOH (the so called causticizing requirement) is increased. This arises because sulfur is released as Na{sub 2}S during conventional kraft black liquor recovery, while during gasification the sodium associated Na{sub 2}S is partly or fully converted to Na{sub 2}CO{sub 3}. The causticizing requirement can be eliminated by including a TiO{sub 2} based cyclic process called direct causticization. In this process black liquor is gasified in the presence of (low sodium content) titanates which convert Na{sub 2}CO{sub 3} to (high sodium content) titanates. NaOH is formed whenmore » contacting the latter titanates with water, thereby eliminating the causticizing requirement entirely. The leached and low sodium titanates are returned to the gasification process. The project team comprised the University of Maine (UM), North Carolina State University (NCSU) and MTCI/ThermoChem. NCSU and MTCI are subcontractors to UM. The principal organization for the contract is UM. NCSU investigated the techno-economics of using advanced pulping techniques which fully utilize the unique cooking liquors produced by steam reforming of black liquor (Task 1). UM studied the kinetics and agglomeration problems of the conversion of Na{sub 2}CO{sub 3} to (high sodium) titanates during gasification of black liquor in the presence of (low sodium) titanates or TiO{sub 2} (Task 2). MTCI/ThermoChem tested the performance and operability of the combined technology of steam reforming and direct causticization in their Process Development Unit (PDU) (Task 3). The specific objectives were: (1) to investigate how split sulfidity and polysulfide (+ AQ) pulping can be used to increase pulp fiber yield and properties compared to conventional kraft pulping; (2) to determine the economics of black liquor gasification combined with these pulping technologies in comparison with conventional kraft pulping and black liquor recovery; (3) to determine the effect of operating conditions on the kinetics of the titanate-based direct causticization reaction during black liquor gasification at relatively low temperatures ({le} 750 C); (4) to determine the mechanism of particle agglomeration during gasification of black liquor in the presence of titanates at relatively low temperatures ({le} 750 C); and (5) to verify performance and operability of the combined technology of steam reforming and direct causticization of black liquor in a pilot scale fluidized bed test facility.« less

Authors:
Publication Date:
Research Org.:
University Of Maine
Sponsoring Org.:
USDOE
OSTI Identifier:
1001224
DOE Contract Number:  
FC26-02NT41493
Resource Type:
Technical Report
Country of Publication:
United States
Language:
English
Subject:
09 BIOMASS FUELS; AGGLOMERATION; BIOMASS; CONTRACTORS; ECONOMICS; FIBERS; FLUIDIZED BEDS; GASIFICATION; KINETICS; PERFORMANCE; PROCESS DEVELOPMENT UNITS; PRODUCTION; SODIUM; SPENT LIQUORS; STEAM; SULFIDES; SULFUR; TITANATES; WATER; WOOD

Citation Formats

Heiningen, Adriaan van. Mill Integration-Pulping, Stream Reforming and Direct Causticization for Black Liquor Recovery. United States: N. p., 2007. Web. doi:10.2172/1001224.
Heiningen, Adriaan van. Mill Integration-Pulping, Stream Reforming and Direct Causticization for Black Liquor Recovery. United States. https://doi.org/10.2172/1001224
Heiningen, Adriaan van. Sat . "Mill Integration-Pulping, Stream Reforming and Direct Causticization for Black Liquor Recovery". United States. https://doi.org/10.2172/1001224. https://www.osti.gov/servlets/purl/1001224.
@article{osti_1001224,
title = {Mill Integration-Pulping, Stream Reforming and Direct Causticization for Black Liquor Recovery},
author = {Heiningen, Adriaan van},
abstractNote = {MTCI/StoneChem developed a steam reforming, fluidized bed gasification technology for biomass. DOE supported the demonstration of this technology for gasification of spent wood pulping liquor (or 'black liquor') at Georgia-Pacific's Big Island, Virginia mill. The present pre-commercial R&D project addressed the opportunities as well as identified negative aspects when the MTCI/StoneChem gasification technology is integrated in a pulp mill production facility. The opportunities arise because black liquor gasification produces sulfur (as H{sub 2}S) and sodium (as Na{sub 2}CO{sub 3}) in separate streams which may be used beneficially for improved pulp yield and properties. The negative aspect of kraft black liquor gasification is that the amount of Na{sub 2}CO{sub 3} which must be converted to NaOH (the so called causticizing requirement) is increased. This arises because sulfur is released as Na{sub 2}S during conventional kraft black liquor recovery, while during gasification the sodium associated Na{sub 2}S is partly or fully converted to Na{sub 2}CO{sub 3}. The causticizing requirement can be eliminated by including a TiO{sub 2} based cyclic process called direct causticization. In this process black liquor is gasified in the presence of (low sodium content) titanates which convert Na{sub 2}CO{sub 3} to (high sodium content) titanates. NaOH is formed when contacting the latter titanates with water, thereby eliminating the causticizing requirement entirely. The leached and low sodium titanates are returned to the gasification process. The project team comprised the University of Maine (UM), North Carolina State University (NCSU) and MTCI/ThermoChem. NCSU and MTCI are subcontractors to UM. The principal organization for the contract is UM. NCSU investigated the techno-economics of using advanced pulping techniques which fully utilize the unique cooking liquors produced by steam reforming of black liquor (Task 1). UM studied the kinetics and agglomeration problems of the conversion of Na{sub 2}CO{sub 3} to (high sodium) titanates during gasification of black liquor in the presence of (low sodium) titanates or TiO{sub 2} (Task 2). MTCI/ThermoChem tested the performance and operability of the combined technology of steam reforming and direct causticization in their Process Development Unit (PDU) (Task 3). The specific objectives were: (1) to investigate how split sulfidity and polysulfide (+ AQ) pulping can be used to increase pulp fiber yield and properties compared to conventional kraft pulping; (2) to determine the economics of black liquor gasification combined with these pulping technologies in comparison with conventional kraft pulping and black liquor recovery; (3) to determine the effect of operating conditions on the kinetics of the titanate-based direct causticization reaction during black liquor gasification at relatively low temperatures ({le} 750 C); (4) to determine the mechanism of particle agglomeration during gasification of black liquor in the presence of titanates at relatively low temperatures ({le} 750 C); and (5) to verify performance and operability of the combined technology of steam reforming and direct causticization of black liquor in a pilot scale fluidized bed test facility.},
doi = {10.2172/1001224},
url = {https://www.osti.gov/biblio/1001224}, journal = {},
number = ,
volume = ,
place = {United States},
year = {2007},
month = {6}
}