Difference between revisions of "Steam explosion"
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Lignocellulosic biomass, such as wood, exists of composite materials with high mechanical strength composed of cellulose fibres, lignin polymers as a matrix and hemicelluloses in a tightly packed cellular structure of fibres that form fibre bundles. Their natural function is to bear high mechanical loads, and to resist chemical and enzymatic degradation through microorganisms. Steam explosion breaks this structure down to enable these chemical and enzymatic [[Conversion|conversions]]. It converts biomass in a steam atmosphere at elevated temperatures ranging from 140 to 240 °C. The steam pressure is rapidly reduced to atmospheric pressure, whereby a mechanical disruption of biomass occurs. In steam explosion, the lignocellulosic biomass is treated with a high-pressure, hot steam for some time and then the vessel is rapidly depressurised to atmospheric pressure. With this explosive decompression and high temperature it causes degradation of hemicellulose, which is extracted as a water-soluble fraction. The cellulose is largely preserved in its original form, and only slight depolymerisation occurs at mild reaction condition. The Lignin undergoes depolymerisation by cleavage of β–O–4 linkages, and condensation of the fragments occurs to form a more stable polymer.<ref>{{Cite web|title=Steam Explosion - an overview {{!}} ScienceDirect Topics|url=https://www.sciencedirect.com/topics/chemistry/steam-explosion|date accessed=2021-08-30}}</ref> | Lignocellulosic biomass, such as wood, exists of composite materials with high mechanical strength composed of cellulose fibres, lignin polymers as a matrix and hemicelluloses in a tightly packed cellular structure of fibres that form fibre bundles. Their natural function is to bear high mechanical loads, and to resist chemical and enzymatic degradation through microorganisms. Steam explosion breaks this structure down to enable these chemical and enzymatic [[Conversion|conversions]]. It converts biomass in a steam atmosphere at elevated temperatures ranging from 140 to 240 °C. The steam pressure is rapidly reduced to atmospheric pressure, whereby a mechanical disruption of biomass occurs. In steam explosion, the lignocellulosic biomass is treated with a high-pressure, hot steam for some time and then the vessel is rapidly depressurised to atmospheric pressure. With this explosive decompression and high temperature it causes degradation of hemicellulose, which is extracted as a water-soluble fraction. The cellulose is largely preserved in its original form, and only slight depolymerisation occurs at mild reaction condition. The Lignin undergoes depolymerisation by cleavage of β–O–4 linkages, and condensation of the fragments occurs to form a more stable polymer.<ref>{{Cite web|title=Steam Explosion - an overview {{!}} ScienceDirect Topics|url=https://www.sciencedirect.com/topics/chemistry/steam-explosion|date accessed=2021-08-30}}</ref> | ||
Steam explosion was introduced and patented as a biomass pre-treatment process in 1926 by Mason et al. (1926)<ref>W.H. Mason WH (1926): ''Process and apparatus for disintegration of wood and the like.'' US Patent: 1578609, 1926.</ref>. The patent describes a steam explosion process for the pre-treatment of wood where wood chips are fed from a bin through a screw loading valve. The chips are then steam heated at a temperature of about 285°C and a pressure of 3.5 MPa for about 2 min. The pressure is increased rapidly to about 7 MPa (70 bar) for about 5 s, and the chips are then discharged and explode at atmospheric pressure into a pulp. The sudden pressure release defibrillates the cellulose bundles, and this result in a better accessibility of the cellulose for [[hydrolysis]]<ref name=":0">David Steinbach, Andrea Kruse, Jörg Sauer, Jonas Storz (2020): ''Is Steam Explosion a Promising Pretreatment for Acid Hydrolysis of Lignocellulosic Biomass?'' Process 8, 1626;, p. 75–104. ([https://www.mdpi.com/2227-9717/8/12/1626 pdf])</ref> or [[Industrial fermentation|fermentation]].<ref name=":1">M. Tanahashi (1990): ''Characterization and degradation mechanisms of wood components by steam explosion and utilization of exploded wood.'' Wood Research 77, 1990: p. 49-117. ([https://core.ac.uk/download/pdf/39187461.pdf pdf])</ref><ref name=":2">Wolfgang Stelte: ''Steam explosion for biomass pre-treatment.'' Danish Technological Institute</ref><ref name=":3">Kun Wang, Jinghuan Chen, Shao-Ni Sun, Run-Cang Sun: ''Steam Explosion.'' In: ''Pretreatment of Biomass.'' Elsevier, 2015, p. 75–104. ([https://www.researchgate.net/publication/282595810 pdf])</ref> | Steam explosion was introduced and patented as a biomass pre-treatment process in 1926 by Mason et al. (1926)<ref>W.H. Mason WH (1926): ''Process and apparatus for disintegration of wood and the like.'' US Patent:<tcxspan tcxhref="1578609" title="Call <tcxspan tcxhref="1578609" title="Call <tcxspan tcxhref="1578609" title="Call <tcxspan tcxhref="1578609" title="Call 1578609, via 3CX"> 1578609,</tcxspan> via 3CX"><tcxspan tcxhref="1578609" title="Call 1578609, via 3CX"> 1578609,</tcxspan></tcxspan> via 3CX"><tcxspan tcxhref="1578609" title="Call <tcxspan tcxhref="1578609" title="Call 1578609, via 3CX"> 1578609,</tcxspan> via 3CX"><tcxspan tcxhref="1578609" title="Call 1578609, via 3CX"> 1578609,</tcxspan></tcxspan></tcxspan> via 3CX"><tcxspan tcxhref="1578609" title="Call <tcxspan tcxhref="1578609" title="Call <tcxspan tcxhref="1578609" title="Call 1578609, via 3CX"> 1578609,</tcxspan> via 3CX"><tcxspan tcxhref="1578609" title="Call 1578609, via 3CX"> 1578609,</tcxspan></tcxspan> via 3CX"><tcxspan tcxhref="1578609" title="Call <tcxspan tcxhref="1578609" title="Call 1578609, via 3CX"> 1578609,</tcxspan> via 3CX"><tcxspan tcxhref="1578609" title="Call 1578609, via 3CX"> 1578609,</tcxspan></tcxspan></tcxspan></tcxspan> 1926.</ref>. The patent describes a steam explosion process for the pre-treatment of wood where wood chips are fed from a bin through a screw loading valve. The chips are then steam heated at a temperature of about 285°C and a pressure of 3.5 MPa for about 2 min. The pressure is increased rapidly to about 7 MPa (70 bar) for about 5 s, and the chips are then discharged and explode at atmospheric pressure into a pulp. The sudden pressure release defibrillates the cellulose bundles, and this result in a better accessibility of the cellulose for [[hydrolysis]]<ref name=":0">David Steinbach, Andrea Kruse, Jörg Sauer, Jonas Storz (2020): ''Is Steam Explosion a Promising Pretreatment for Acid Hydrolysis of Lignocellulosic Biomass?'' Process 8, 1626;, p. 75–104. ([https://www.mdpi.com/2227-9717/8/12/1626 pdf])</ref> or [[Industrial fermentation|fermentation]].<ref name=":1">M. Tanahashi (1990): ''Characterization and degradation mechanisms of wood components by steam explosion and utilization of exploded wood.'' Wood Research 77, 1990: p. 49-117. ([https://core.ac.uk/download/pdf/39187461.pdf pdf])</ref><ref name=":2">Wolfgang Stelte: ''Steam explosion for biomass pre-treatment.'' Danish Technological Institute</ref><ref name=":3">Kun Wang, Jinghuan Chen, Shao-Ni Sun, Run-Cang Sun: ''Steam Explosion.'' In: ''Pretreatment of Biomass.'' Elsevier, 2015, p. 75–104. ([https://www.researchgate.net/publication/282595810 pdf])</ref> | ||
==Product== | ==Product== | ||
| Line 28: | Line 28: | ||
==Technology providers== | ==Technology providers== | ||
{| class="wikitable sortable mw-collapsible | {| class="wikitable sortable mw-collapsible" | ||
|+'''Technology comparison''' | |+'''Technology comparison''' | ||
! class="cd-text-darkgreen" style="vertical-align:{{{va|bottom}}}"| Company name | ! class="cd-text-darkgreen" style="vertical-align:{{{va|bottom}}}"| Company name | ||
! class="cd-text-darkgreen" style="vertical-align:{{{va|bottom}}}"| Country | ! class="cd-text-darkgreen" style="vertical-align:{{{va|bottom}}}"| Country | ||
! class="cd-text-darkgreen" style="vertical-align:{{{va|bottom}}}"| Technology | ! class="cd-text-darkgreen" style="vertical-align:{{{va|bottom}}}"| Technology subcategory | ||
! class="cd-text-darkgreen" style="vertical-align:{{{va|bottom}}}"| Technology name | ! class="cd-text-darkgreen" style="vertical-align:{{{va|bottom}}}"| Technology name | ||
! class="cd-text-darkgreen" style="vertical-align:{{{va|bottom}}}"| TRL | ! class="cd-text-darkgreen" style="vertical-align:{{{va|bottom}}}"| TRL | ||
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! | ! | ||
|- | |- | ||
| [[ | |[[Steam explosion#Biorenewables Development Centre BDC|Biorenewables Development Centre BDC]] | ||
| | |United Kingdom | ||
| | | - | ||
| | |Fibre expansion | ||
| | |4-7 | ||
| | |100 | ||
| | |12 | ||
| | |190 | ||
| class="cd-background-lightgreen cd-text-darkgreen" style="text-align:center" |● | | class="cd-background-lightgreen cd-text-darkgreen" style="text-align:center" |● | ||
| class="cd-background-lightgreen cd-text-darkgreen" style="text-align:center" |● | | class="cd-background-lightgreen cd-text-darkgreen" style="text-align:center" |● | ||
|- | |- | ||
| [[ | | [[Steam explosion#ENEA|ENEA]] | ||
| | | Italy | ||
| | | - | ||
| | |Steam Explosion | ||
| | | 5 | ||
| | |300 | ||
| | |15 | ||
| | |200 | ||
| class="cd-background-lightgreen cd-text-darkgreen" style="text-align:center" |● | | class="cd-background-lightgreen cd-text-darkgreen" style="text-align:center" |● | ||
| class="cd-background-lightgreen cd-text-darkgreen" style="text-align:center" |● | | class="cd-background-lightgreen cd-text-darkgreen" style="text-align:center" |● | ||
|} | |} | ||
=== | === Biorenewables Development Centre BDC === | ||
=== | {{Infobox provider-steam explosion|Company=Biorenewables Development Centre|Country=United Kingdom|Webpage=http://www.biorenewables.org|Technology name=Fibre expansion|Contact=Mark Gronnow, info@biorenewables.org|Feedstock=any lignocellulosic materials (straws, bagasse, willow, miscanthus etc)|Product=pre-treated biomass|TRL=4-7|Cellulose yield=up to 90|Pressure:=up to 12|Image=Cropped-logo1.png|Hemicellulose yield=up to 90|Temperature=up to 190|Other=use under alkaline and acid conditions|Capacity=100 L}} | ||
The Biorenewables Development Centre (BDC) is an open-access R&D biorefinery centre, based at the University of York, working at the interface between academia and industry to convert plants, microbes and biowastes into profitable biorenewable products. With biologists, chemists, and business development specialists the BDC team offers a unique combination of multi-disciplinary expertise coupled with pilot-scale processing capabilities in one coordinated centre. Covering a broad spectrum of biorefining technologies, from feedstock assessment to product evaluation, the team specialise in making the most out of biorenewable materials; helping ideas to survive the valley of death; and de-risking the innovation process. | |||
=== Clamper === | |||
{{Infobox provider-steam explosion|Company=Clamber|Country=Spain|Webpage=https://clamber.castillalamancha.es|Contact=Javier Mena (javier.mena@geacam.com)|Technology name=Steam Explosion|TRL=6-7|Pressure:=21|Capacity=400|Temperature=180 - 220|Other=Cellulose yield and hemicellulose removal depends on the type of lignocellulosic biomass treated.|Product=Biomass|Feedstock=Lignocellulosic biomass|Cellulose yield=not relevant|Hemicellulose yield=not relevant|Image=CLaMber2.png}} | |||
R&D&I BIORREFINERY CLaMber - A public demonstration facility dedicated to scientific research, scaling-up experiments and the development of new bioprocesses and bioproducts from the use of fermentable wet biomass or lignocellulosic biomass, both residual and cultivated. It was built in 2015 thanks to the CLaMber Project (Castilla-La Mancha Bio-Economy Region) which was developed by the Regional Institute for Agri-Food and Forestry Research and Development (I R I A F), under the Ministry of Agriculture, Livestock and Rural Development of the Regional Government of Castilla-La Mancha (JCCM). It has been financed by the JCCM itself and by ERDF funds through the Ministry of Economy and Competitiveness (MINECO). | |||
=== ENEA === | |||
{{Infobox provider-steam explosion|Company=ENEA Italian National Agency for New Technologies, Energy and Sustainable Economic Development|Country=Italy|Webpage=https://www.enea.it/en|Technology name=Steam Explosion|TRL=5|Capacity=300|Feedstock=each kind of lignocellulosic material|Product=2nd generation sugars, soluble hemicellulose, cellulose, lignin|Contact=Isabella De Bari, | |||
isabella.debari@enea.it|Image=LogoENEA.png|Cellulose yield=80-90|Pressure:=15|Hemicellulose yield=90-95|Temperature=200|Other=catalyzed by 1-2% H2SO4}} | |||
ENEA is a public Agency targeted to research, innovation technology and advanced services in the fields of energy, environment and sustainable economic development. Its activities are devoted to basic, mission oriented and industrial research, dissemination and transfer of research results, providing public and private partners with high-tech services. ENEA has approximately 2700 employees operating in ten Research Centers located across Italy. The ENEA Research Centre “La Trisaia” (south of Italy) has complete platforms for the conversion of biomass/wastes, comprising a number of bench scale, pilot and demonstrative scale plants for biomass pretreatment, gasification, pyrolysis, biotechnological conversions and downstream processing. One main research focus is the development of new technologies for pretreatment, fractionation, separation, purification and conversion of biomass into so-called biobased products of industrial interest. The final objective is to support the development of new models of biorefineries, integrated with the agro-industrial processes that generate high value materials respecting the vocation and territorial sustainability. | |||
== Open access pilot and demo facility providers == | == Open access pilot and demo facility providers == | ||
| Line 89: | Line 100: | ||
<references /> | <references /> | ||
[[Category: | [[Category:Pre-processing]] | ||
[[Category: | [[Category:Post-processing]] | ||
[[Category:Technologies]] | |||
Latest revision as of 07:11, 8 August 2023
| Technology | |
| |
| Technology details | |
| Name: | Steam explosion |
| Category: | Pre-processing (Physical processes and technologies), Post-processing (Physical processes and technologies) |
| Feedstock: | Garden and park waste |
| Product: | Lignocellulosic hydrolysate |
Steam explosion is a physicochemical method to break the lignocellulose structure by using high-pressure steam to disrupt the bonding between polymeric components (lignin, cellulose) and decompression. It can be used to pre-treat the lignocellulosic biomass to improve subsequent processes, such as enzymatic hydrolysis.
Feedstock
Origin and composition
Steam explosion is used to pre-treat lignocellulosic biomass such as wood, straw and lignocellulosic wastes for industrial processes. Normally, the material enters the steam explosion process as chips, pellets or ground material.
Pre-treatment
Process and technologies
Lignocellulosic biomass, such as wood, exists of composite materials with high mechanical strength composed of cellulose fibres, lignin polymers as a matrix and hemicelluloses in a tightly packed cellular structure of fibres that form fibre bundles. Their natural function is to bear high mechanical loads, and to resist chemical and enzymatic degradation through microorganisms. Steam explosion breaks this structure down to enable these chemical and enzymatic conversions. It converts biomass in a steam atmosphere at elevated temperatures ranging from 140 to 240 °C. The steam pressure is rapidly reduced to atmospheric pressure, whereby a mechanical disruption of biomass occurs. In steam explosion, the lignocellulosic biomass is treated with a high-pressure, hot steam for some time and then the vessel is rapidly depressurised to atmospheric pressure. With this explosive decompression and high temperature it causes degradation of hemicellulose, which is extracted as a water-soluble fraction. The cellulose is largely preserved in its original form, and only slight depolymerisation occurs at mild reaction condition. The Lignin undergoes depolymerisation by cleavage of β–O–4 linkages, and condensation of the fragments occurs to form a more stable polymer.[1]
Steam explosion was introduced and patented as a biomass pre-treatment process in 1926 by Mason et al. (1926)[2]. The patent describes a steam explosion process for the pre-treatment of wood where wood chips are fed from a bin through a screw loading valve. The chips are then steam heated at a temperature of about 285°C and a pressure of 3.5 MPa for about 2 min. The pressure is increased rapidly to about 7 MPa (70 bar) for about 5 s, and the chips are then discharged and explode at atmospheric pressure into a pulp. The sudden pressure release defibrillates the cellulose bundles, and this result in a better accessibility of the cellulose for hydrolysis[3] or fermentation.[4][5][6]
Product
Steam explosion is a pre-treatment process that makes biomass more suitable for following processes, such as enzymatic hydrolysis, acid hydrolysis[3] or fermentation. Depending on residence time and temperature, steam explosion can result in anything from small cracks in the wood structure, to total defibrillation of the wood fibers.[4][5][6]
Post-treatment
Technology providers
| Company name | Country | Technology subcategory | Technology name | TRL | Capacity [kg/h] | Pressure [bar] | Temperature [°C] | Feedstock: Food waste | Feedstock: Garden & park waste |
|---|---|---|---|---|---|---|---|---|---|
| Biorenewables Development Centre BDC | United Kingdom | - | Fibre expansion | 4-7 | 100 | 12 | 190 | ● | ● |
| ENEA | Italy | - | Steam Explosion | 5 | 300 | 15 | 200 | ● | ● |
Biorenewables Development Centre BDC
| General information | |||
| Company: | Biorenewables Development Centre | 
| |
| Country: | United Kingdom | ||
| Contact: | Mark Gronnow, info@biorenewables.org | ||
| Webpage: | http://www.biorenewables.org | ||
| Technology and process details | |||
| Technology name: | Fibre expansion | Technology category: | Pre-processing (Physical processes and technologies), Post-processing (Physical processes and technologies) |
| TRL: | 4-7 | Capacity: | 100 L kg·h-1 |
| Cellulose yield: | up to 90 % | Hemicellulose removal: | up to 90 % |
| Pressure: | up to 12 bar | Temperature: | up to 190 °C |
| Other: | use under alkaline and acid conditions | ||
| Feedstock and product details | |||
| Feedstock: | any lignocellulosic materials (straws, bagasse, willow, miscanthus etc) | Product: | pre-treated biomass |
The Biorenewables Development Centre (BDC) is an open-access R&D biorefinery centre, based at the University of York, working at the interface between academia and industry to convert plants, microbes and biowastes into profitable biorenewable products. With biologists, chemists, and business development specialists the BDC team offers a unique combination of multi-disciplinary expertise coupled with pilot-scale processing capabilities in one coordinated centre. Covering a broad spectrum of biorefining technologies, from feedstock assessment to product evaluation, the team specialise in making the most out of biorenewable materials; helping ideas to survive the valley of death; and de-risking the innovation process.
Clamper
| General information | |||
| Company: | Clamber | 
| |
| Country: | Spain | ||
| Contact: | Javier Mena (javier.mena@geacam.com) | ||
| Webpage: | https://clamber.castillalamancha.es | ||
| Technology and process details | |||
| Technology name: | Steam Explosion | Technology category: | Pre-processing (Physical processes and technologies), Post-processing (Physical processes and technologies) |
| TRL: | 6-7 | Capacity: | 400 kg·h-1 |
| Cellulose yield: | not relevant % | Hemicellulose removal: | not relevant % |
| Pressure: | 21 bar | Temperature: | 180 - 220 °C |
| Other: | Cellulose yield and hemicellulose removal depends on the type of lignocellulosic biomass treated. | ||
| Feedstock and product details | |||
| Feedstock: | Lignocellulosic biomass | Product: | Biomass |
R&D&I BIORREFINERY CLaMber - A public demonstration facility dedicated to scientific research, scaling-up experiments and the development of new bioprocesses and bioproducts from the use of fermentable wet biomass or lignocellulosic biomass, both residual and cultivated. It was built in 2015 thanks to the CLaMber Project (Castilla-La Mancha Bio-Economy Region) which was developed by the Regional Institute for Agri-Food and Forestry Research and Development (I R I A F), under the Ministry of Agriculture, Livestock and Rural Development of the Regional Government of Castilla-La Mancha (JCCM). It has been financed by the JCCM itself and by ERDF funds through the Ministry of Economy and Competitiveness (MINECO).
ENEA
| General information | |||
| Company: | ENEA Italian National Agency for New Technologies, Energy and Sustainable Economic Development | 
| |
| Country: | Italy | ||
| Contact: | Isabella De Bari,
isabella.debari@enea.it | ||
| Webpage: | https://www.enea.it/en | ||
| Technology and process details | |||
| Technology name: | Steam Explosion | Technology category: | Pre-processing (Physical processes and technologies), Post-processing (Physical processes and technologies) |
| TRL: | 5 | Capacity: | 300 kg·h-1 |
| Cellulose yield: | 80-90 % | Hemicellulose removal: | 90-95 % |
| Pressure: | 15 bar | Temperature: | 200 °C |
| Other: | catalyzed by 1-2% H2SO4 | ||
| Feedstock and product details | |||
| Feedstock: | each kind of lignocellulosic material | Product: | 2nd generation sugars, soluble hemicellulose, cellulose, lignin |
ENEA is a public Agency targeted to research, innovation technology and advanced services in the fields of energy, environment and sustainable economic development. Its activities are devoted to basic, mission oriented and industrial research, dissemination and transfer of research results, providing public and private partners with high-tech services. ENEA has approximately 2700 employees operating in ten Research Centers located across Italy. The ENEA Research Centre “La Trisaia” (south of Italy) has complete platforms for the conversion of biomass/wastes, comprising a number of bench scale, pilot and demonstrative scale plants for biomass pretreatment, gasification, pyrolysis, biotechnological conversions and downstream processing. One main research focus is the development of new technologies for pretreatment, fractionation, separation, purification and conversion of biomass into so-called biobased products of industrial interest. The final objective is to support the development of new models of biorefineries, integrated with the agro-industrial processes that generate high value materials respecting the vocation and territorial sustainability.
Open access pilot and demo facility providers
Patents
Currently no patents have been identified.
References
- ↑ , : Steam Explosion - an overview | ScienceDirect Topics , Last access 2021-08-30. https://www.sciencedirect.com/topics/chemistry/steam-explosion
- ↑ W.H. Mason WH (1926): Process and apparatus for disintegration of wood and the like. US Patent:<tcxspan tcxhref="1578609" title="Call <tcxspan tcxhref="1578609" title="Call <tcxspan tcxhref="1578609" title="Call <tcxspan tcxhref="1578609" title="Call 1578609, via 3CX"> 1578609,</tcxspan> via 3CX"><tcxspan tcxhref="1578609" title="Call 1578609, via 3CX"> 1578609,</tcxspan></tcxspan> via 3CX"><tcxspan tcxhref="1578609" title="Call <tcxspan tcxhref="1578609" title="Call 1578609, via 3CX"> 1578609,</tcxspan> via 3CX"><tcxspan tcxhref="1578609" title="Call 1578609, via 3CX"> 1578609,</tcxspan></tcxspan></tcxspan> via 3CX"><tcxspan tcxhref="1578609" title="Call <tcxspan tcxhref="1578609" title="Call <tcxspan tcxhref="1578609" title="Call 1578609, via 3CX"> 1578609,</tcxspan> via 3CX"><tcxspan tcxhref="1578609" title="Call 1578609, via 3CX"> 1578609,</tcxspan></tcxspan> via 3CX"><tcxspan tcxhref="1578609" title="Call <tcxspan tcxhref="1578609" title="Call 1578609, via 3CX"> 1578609,</tcxspan> via 3CX"><tcxspan tcxhref="1578609" title="Call 1578609, via 3CX"> 1578609,</tcxspan></tcxspan></tcxspan></tcxspan> 1926.
- ↑ a b David Steinbach, Andrea Kruse, Jörg Sauer, Jonas Storz (2020): Is Steam Explosion a Promising Pretreatment for Acid Hydrolysis of Lignocellulosic Biomass? Process 8, 1626;, p. 75–104. (pdf)
- ↑ a b M. Tanahashi (1990): Characterization and degradation mechanisms of wood components by steam explosion and utilization of exploded wood. Wood Research 77, 1990: p. 49-117. (pdf)
- ↑ a b Wolfgang Stelte: Steam explosion for biomass pre-treatment. Danish Technological Institute
- ↑ a b Kun Wang, Jinghuan Chen, Shao-Ni Sun, Run-Cang Sun: Steam Explosion. In: Pretreatment of Biomass. Elsevier, 2015, p. 75–104. (pdf)