Sulfonic acid functionalized hydrophobic mesoporous biochar: Design, preparation and acid-catalytic properties

Yao Zhong, Qiang Deng, Peixin Zhang, Jun Wang, Rong Wang, Zheling Zeng, Shuguang Deng

Research output: Contribution to journalArticle

9 Citations (Scopus)

Abstract

Sulfonic acid functional strong acidic catalysts are largely used in various chemical reactions. However, in many reactions with water as product, the catalytic activity and selectivity are unsatisfactory, because hydrophilic acid sites of SO3H would suffer from acidity decreasing and some hydrolysis side reactions would occur via water adsorption. Herein, a novel hydrophobic arenesulfonic acid functionalized biochar was successfully prepared for the first time by one-pot diazo reduction method of biochar with amino-arenesulfonic acid (such as, 4-aminbenzenesulfonic acid, 4-amino-1-naphthalenesulfonic acid, 8-amino-1-naphthalenesulfonic acid, 4-amino-3-hydroxy-1-naphthalenesulphonic acid). It has a large specific surface area of 200–400 m2/g, a hydrophobic network with water contact angle higher than 120° and a higher concentration of sulfonic acid over 1.0 mmol/g. Moreover, the hydrophobicity-oleophilicity and acidity are increased with the arene length and grafting amount of arenesulfonic acid. In the esterification reaction of fatty acid with methanol as well as the transesterification reaction of glycerol trioleate with methanol for the production of biodiesel, the sulfonated biochar shows a higher conversion of 96.7% for esterification and 86.3% for transesterification compared with amberlyst-15 (86.7%, 39.9%) and traditional sulfonation biochar-SO3H (27.4%, 32.6%). In the alkylation reaction of 2-methylfuran with cyclopentanone for the production of high-density biofuel, its catalytic efficiency with target product yield of 76.1% is higher than that of amberlyst-15 (50.2%) and traditional sulfonation biochar-SO3H (13.2%), because of its hydrophobicity and strong acidity. Furthermore, the catalyst is stable and shows an excellent cycle performance after 6 runs. The successful preparation of hydrophobic biochar-based acidic catalysts not only provides a new way for high-value utilization of biochar, but also eliminates the negative effect of water on many catalytic reactions.

Original languageEnglish (US)
Pages (from-to)270-277
Number of pages8
JournalFuel
Volume240
DOIs
StatePublished - Mar 15 2019

Fingerprint

Sulfonic Acids
Acids
Acidity
Sulfonation
Biofuels
Water
Transesterification
Esterification
Hydrophobicity
Catalysts
Methanol
Triolein
Catalyst selectivity
Alkylation
biochar
Specific surface area
Contact angle
Chemical reactions
Hydrolysis
Catalyst activity

Keywords

  • Alkylation
  • Esterification
  • Hydrophobicity-oleophilicity
  • Sulfonic acid functionalized biochar
  • Transesterification

ASJC Scopus subject areas

  • Chemical Engineering(all)
  • Fuel Technology
  • Energy Engineering and Power Technology
  • Organic Chemistry

Cite this

Sulfonic acid functionalized hydrophobic mesoporous biochar : Design, preparation and acid-catalytic properties. / Zhong, Yao; Deng, Qiang; Zhang, Peixin; Wang, Jun; Wang, Rong; Zeng, Zheling; Deng, Shuguang.

In: Fuel, Vol. 240, 15.03.2019, p. 270-277.

Research output: Contribution to journalArticle

Zhong, Yao ; Deng, Qiang ; Zhang, Peixin ; Wang, Jun ; Wang, Rong ; Zeng, Zheling ; Deng, Shuguang. / Sulfonic acid functionalized hydrophobic mesoporous biochar : Design, preparation and acid-catalytic properties. In: Fuel. 2019 ; Vol. 240. pp. 270-277.
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abstract = "Sulfonic acid functional strong acidic catalysts are largely used in various chemical reactions. However, in many reactions with water as product, the catalytic activity and selectivity are unsatisfactory, because hydrophilic acid sites of SO3H would suffer from acidity decreasing and some hydrolysis side reactions would occur via water adsorption. Herein, a novel hydrophobic arenesulfonic acid functionalized biochar was successfully prepared for the first time by one-pot diazo reduction method of biochar with amino-arenesulfonic acid (such as, 4-aminbenzenesulfonic acid, 4-amino-1-naphthalenesulfonic acid, 8-amino-1-naphthalenesulfonic acid, 4-amino-3-hydroxy-1-naphthalenesulphonic acid). It has a large specific surface area of 200–400 m2/g, a hydrophobic network with water contact angle higher than 120° and a higher concentration of sulfonic acid over 1.0 mmol/g. Moreover, the hydrophobicity-oleophilicity and acidity are increased with the arene length and grafting amount of arenesulfonic acid. In the esterification reaction of fatty acid with methanol as well as the transesterification reaction of glycerol trioleate with methanol for the production of biodiesel, the sulfonated biochar shows a higher conversion of 96.7{\%} for esterification and 86.3{\%} for transesterification compared with amberlyst-15 (86.7{\%}, 39.9{\%}) and traditional sulfonation biochar-SO3H (27.4{\%}, 32.6{\%}). In the alkylation reaction of 2-methylfuran with cyclopentanone for the production of high-density biofuel, its catalytic efficiency with target product yield of 76.1{\%} is higher than that of amberlyst-15 (50.2{\%}) and traditional sulfonation biochar-SO3H (13.2{\%}), because of its hydrophobicity and strong acidity. Furthermore, the catalyst is stable and shows an excellent cycle performance after 6 runs. The successful preparation of hydrophobic biochar-based acidic catalysts not only provides a new way for high-value utilization of biochar, but also eliminates the negative effect of water on many catalytic reactions.",
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T2 - Design, preparation and acid-catalytic properties

AU - Zhong, Yao

AU - Deng, Qiang

AU - Zhang, Peixin

AU - Wang, Jun

AU - Wang, Rong

AU - Zeng, Zheling

AU - Deng, Shuguang

PY - 2019/3/15

Y1 - 2019/3/15

N2 - Sulfonic acid functional strong acidic catalysts are largely used in various chemical reactions. However, in many reactions with water as product, the catalytic activity and selectivity are unsatisfactory, because hydrophilic acid sites of SO3H would suffer from acidity decreasing and some hydrolysis side reactions would occur via water adsorption. Herein, a novel hydrophobic arenesulfonic acid functionalized biochar was successfully prepared for the first time by one-pot diazo reduction method of biochar with amino-arenesulfonic acid (such as, 4-aminbenzenesulfonic acid, 4-amino-1-naphthalenesulfonic acid, 8-amino-1-naphthalenesulfonic acid, 4-amino-3-hydroxy-1-naphthalenesulphonic acid). It has a large specific surface area of 200–400 m2/g, a hydrophobic network with water contact angle higher than 120° and a higher concentration of sulfonic acid over 1.0 mmol/g. Moreover, the hydrophobicity-oleophilicity and acidity are increased with the arene length and grafting amount of arenesulfonic acid. In the esterification reaction of fatty acid with methanol as well as the transesterification reaction of glycerol trioleate with methanol for the production of biodiesel, the sulfonated biochar shows a higher conversion of 96.7% for esterification and 86.3% for transesterification compared with amberlyst-15 (86.7%, 39.9%) and traditional sulfonation biochar-SO3H (27.4%, 32.6%). In the alkylation reaction of 2-methylfuran with cyclopentanone for the production of high-density biofuel, its catalytic efficiency with target product yield of 76.1% is higher than that of amberlyst-15 (50.2%) and traditional sulfonation biochar-SO3H (13.2%), because of its hydrophobicity and strong acidity. Furthermore, the catalyst is stable and shows an excellent cycle performance after 6 runs. The successful preparation of hydrophobic biochar-based acidic catalysts not only provides a new way for high-value utilization of biochar, but also eliminates the negative effect of water on many catalytic reactions.

AB - Sulfonic acid functional strong acidic catalysts are largely used in various chemical reactions. However, in many reactions with water as product, the catalytic activity and selectivity are unsatisfactory, because hydrophilic acid sites of SO3H would suffer from acidity decreasing and some hydrolysis side reactions would occur via water adsorption. Herein, a novel hydrophobic arenesulfonic acid functionalized biochar was successfully prepared for the first time by one-pot diazo reduction method of biochar with amino-arenesulfonic acid (such as, 4-aminbenzenesulfonic acid, 4-amino-1-naphthalenesulfonic acid, 8-amino-1-naphthalenesulfonic acid, 4-amino-3-hydroxy-1-naphthalenesulphonic acid). It has a large specific surface area of 200–400 m2/g, a hydrophobic network with water contact angle higher than 120° and a higher concentration of sulfonic acid over 1.0 mmol/g. Moreover, the hydrophobicity-oleophilicity and acidity are increased with the arene length and grafting amount of arenesulfonic acid. In the esterification reaction of fatty acid with methanol as well as the transesterification reaction of glycerol trioleate with methanol for the production of biodiesel, the sulfonated biochar shows a higher conversion of 96.7% for esterification and 86.3% for transesterification compared with amberlyst-15 (86.7%, 39.9%) and traditional sulfonation biochar-SO3H (27.4%, 32.6%). In the alkylation reaction of 2-methylfuran with cyclopentanone for the production of high-density biofuel, its catalytic efficiency with target product yield of 76.1% is higher than that of amberlyst-15 (50.2%) and traditional sulfonation biochar-SO3H (13.2%), because of its hydrophobicity and strong acidity. Furthermore, the catalyst is stable and shows an excellent cycle performance after 6 runs. The successful preparation of hydrophobic biochar-based acidic catalysts not only provides a new way for high-value utilization of biochar, but also eliminates the negative effect of water on many catalytic reactions.

KW - Alkylation

KW - Esterification

KW - Hydrophobicity-oleophilicity

KW - Sulfonic acid functionalized biochar

KW - Transesterification

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