Elsevier

Catalysis Today

Volume 375, 1 September 2021, Pages 197-203
Catalysis Today

Sulfonated graphene oxide from petrochemical waste oil for efficient conversion of fructose into levulinic acid

https://doi.org/10.1016/j.cattod.2020.02.036Get rights and content

Highlights

  • Sulfonated graphene oxide was successfully synthesized from petrochemical waste oil.

  • sGO has high surface area (246 m2 g−1) due to mesoporosity and many sulfonic groups.

  • Recyclable sGO was successfully used for fructose conversion to levulinic acid.

  • Highest yield of levulinic acid (61 %) was obtained at 160 °C, 1 h, and F:C = 6 g g−1.

  • The sGO derived from petrochemical waste oil is an environmentally benign catalyst.

Abstract

Handling of petrochemical waste oil (PWO) is costly, tedious, and risky to human health and environment. Hence, upcycling of PWO for biomass conversion to platform chemicals would be very advantageous. Herein, a highly porous sheet-like structure of sulfonated graphene oxide (sGO) catalyst was synthesized from PWO. The synthesized sGO possessed high surface area (246.2 m2 g1) due to its mesoporosity and high content of sulfonic groups (2.4 mmol g−1) grafted onto its surface. As its application, the synthesized sGO was employed to convert fructose to levulinic acid (LA) within deionized water. The high yield (61.2 mol %) of LA was obtained under a condition of 160 °C, 1 h, and 6 g g−1 fructose to sGO weight ratio. It can be reused several times (5 runs) with no severe degradation of catalytic activity. Therefore, the sGO derived from petrochemical waste oil would be considered as an environmentally benign catalyst for producing platform chemicals, i.e. LA from fructose and other biomass derivatives.

Graphical abstract

Transformation of petrochemical waste oil to sulfonated graphene oxide for efficient conversion of fructose into levulinic acid

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Introduction

Heavy reliance on depleting fossil resources to produce platform chemicals and fuels contributes to the economic dilemma and rising emission of greenhouse gases [[1], [2], [3]]. Hence, alternative ways including utilization of biomass in integrated biorefineries have been explored to compete with fossil-based refineries [4]. Biomass is a renewable resource that can be exploited to produce many high value-added products, i.e. alcohol, 5-hydroxymethylfurfural (5-HMF), furfural, formic acid (FA) and levulinic acid (LA) [5,6]. LA is considered as top ten platform chemicals, which could be further utilized to produce succinic acid, resins, polymers, herbicides, pharmaceuticals, flavoring agents, solvents, plasticizers, anti-freeze agents and biofuels/oxygenated fuel additives [3,7]. Generally, conversion of biomass into LA involves multiple steps, which are (1) hydrolysis of cellulose to glucose, (2) isomerization of glucose to fructose, (3) dehydration of fructose to HMF, and (4) further hydrolysis to form equimolar LA and FA [2,8]. These processes are often realized through chemical or enzymatic routes. Nevertheless, the chemical route has been recognized as high potential for commercially viable LA production [9,10].

In the past, homogeneous acid catalysts (e.g. H2SO4, HCl, H3PO4) were used to ensure a high conversion of reactants because of lower mass transfer resistance [11]. However, those acidic catalysts are corrosive, detrimental to the environment, and non-recyclable [8,10,12]. Hence, heterogeneous solid acid catalysts, such as ion-exchange resins, sulfated metal oxides, modified mesoporous silica, zeolites, and natural clays, have been developed to overcome the disadvantages of those homogeneous acid catalysts [13,14]. Recently, several of these types of catalysts have been used for conversion of fructose to LA from actual biomass [[15], [16], [17]]. It should be noted that the acidity of heterogeneous catalysts plays a critical role in the hydrothermal conversion of fructose to LA [[18], [19], [20]]. In addition, grafting of sulfonic groups has been most widely used due to high catalytic activity and LA yield [6,8,21]. However, the accessibility of active sites available on the surface of such heterogeneous catalysts could probably be hindered by the mass transfer resistance, resulting in poor catalytic performance [4,11].

Novel carbon nanomaterials including graphene oxide (GO) has been recognized as a promising catalyst when compared to conventional porous catalysts due to its high surface area and the presence of active functional groups (COOH, OH) [13,22,23]. Sulfonated GO (sGO) is recognized as a powerful acid catalyst for biomass conversion [6,22]. Grafting of sulfonic acid onto the two-dimensional structure of GO could lead to a large number of accessible active sites beneficial for the conversion of biomass and derivatives to high value-added platform chemicals, i.e. LA and its derivatives. Instead of using conventional disposal, which can be a cause of environmental and health threats, petroleum waste oil (PWO) was utilized to produce GO prior to its subsequent functionalization to produce sGO [24]. The as-prepared sGO was then utilized for converting fructose to LA within a high-pressure stainless-steel reactor. A systematic study was conducted to explore the effect of time, temperature, catalyst loading, and initial concentration of fructose on the catalytic performance of the synthesized sGO.

Section snippets

Materials

Heavy fuel oil (HFO) supplied from PTT Oil and Retail Business Public Company Ltd (Batch No. TA 01/19/0004) was utilized as a representative of PWO. Sulfuric acid (98 % H2SO4, QReC New Zealand) was used for partial carbonization of HFO. Manganese nitrate (≥99 % Mn(NO3)2, Sigma-Aldrich, USA) and ethanol (99 %, Aldrich USA) were used for the graphitization of carbonized solid product (CSP). Hydrochloric acid (37 % HCl, QReC New Zealand), potassium permanganate (99.0 % KMnO4, Ajax Finechem,

Characterization of sGO catalyst

Fig. 1(a) and (b) exhibit the microscopic appearance of CSP and GSP, respectively. CSP is a conglomeration of porous carbonaceous solid with mainly graphitic and amorphous carbon content. After graphitization, the resultant GSP exhibited a particulate form with high graphitic carbon content and higher porosity. Then graphene oxide (GO), which was prepared from GSP by the modified Hammer’s method, displayed a fine powdery appearance. Similarly, the resultant sGO, which was prepared from the GO

Conclusions

The porous sheet-like sGO catalyst with very high surface area of 246.2 m2 g−1 could be synthesized from petrochemical waste oil. The high content of sulfonic group (2.4 mmol g−1) could be grafted onto the surface of GO, resulting in the formation of sGO which could provide a high yield to LA converted from fructose. Effective catalytic performance of the synthesized sGO catalyst could be confirmed with ∼100 % conversion of fructose and the highest yield of LA (61.2 %) with the reaction

Credit author statement

All of our coauthoring team members who meet authorship criteria are listed. All authors certify that they have participated sufficiently in this work to take public responsibility for the content, including participation in the concept, design, analysis, writing, or revision of the manuscript. Furthermore, each author certifies that this material or similar material has not been and will not be submitted to or published in any other publication before its appearance in Catalysis Today.

Declaration of Competing Interest

The authors declare that they have no conflict of interest.

Acknowldgement

This research was supported by Ratchadapisek Sompoch Endowment Fund of Chulalongkorn University for Postdoctoral Fellowship (CL). Also, partial supports of Ratchadapisek Sompoch Endowment Fund (2015) for CEPT (CU-58-064−CC) and the National Nanotechnology Center (NANOTEC), NSTDA, the Ministry of Science and Technology of Thailand through the program of Research Network of NANOTEC (RNN) were gratefully acknowledged.

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