固体磷酸铁催化纤维素液化制备乙酰丙酸及乙酰丙酸甲酯

doi:10.3969/j.issn.0253-2417.2020.05.010

Abstract

Abstract:

Levulinic acid and methyl levulinate were synthesized from cellulose with using solid FePO₄ as catalyst in water/methanol medium. By comparing the catalytic results of liquid acid, metal chloride, metal sulfate and FePO₄, the results showed that FePO₄ displayed a nearly result in both conversion efficiency of cellulose and yields of levulinic acid and methyl levulinate as comparable to the catalytic effects of H₂SO₄ and Al₂(SO₄)₃.The catalytic effect of solid FePO₄ was mainly attributed to form Brønsted and Lewis acidic sites, which provide catalytic activity for cellulose hydrolysis, glucose isomerization and dehydration to form levulinic acid/ester. The total yield of levulinic acid and methyl levulinatewas 62.2% under optimal the best technological conditions of reaction temperature at 220℃, reaction time for 2 h, 2 g of microcrystalline cellulose, water/methanol volume ratio of 1:19 (total solvent volume 40 mL) and 1.5 g of catalyst dosage. The characterization of cellulose, solid residue and FePO₄ catalyst were conducted by FT-IR, XRD and TG/DTG techniques, and the results indicated that the cellulose was efficiently liquefied and then the catalyst was recycled by recrystallization. The formation of levulinates was conducted by the methanolysis and hydrolysis of cellulose, while methyl glucoside (MLG) was an important intermediate and its conversion was affected by the reaction time and the catalyst dosage. Further systematical research of this new technique is further required before the process could be industrialized considering the excellent catalytic activity and recycling characteristic of FePO₄.

Key words: cellulose, levulinic acid/levulinates, catalyze, solid iron phosphate

CLC Number:

TQ35

Linshan WEI,Jiaping ZHAO,Jun YE,Kui WANG,Jianchun JIANG. Preparation of Levulinic Acid and Methyl Levulinate from Cellulose Catalyzed by Solid Iron Phosphate[J]. Chemistry and Industry of Forest Products, 2020, 40(5): 69-74.

Figures/Tables 5

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References 24

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催化剂 catalyst	转化率/% conversion rate	产物产率yield of products/%
催化剂 catalyst	转化率/% conversion rate	糠醛 furfural	甲基葡萄糖苷 methylglucoside	乙酰丙酸 levulinic acid	乙酰丙酸甲酯 methyl levulinate
H₂SO₄	85.2	8.3	3.3	17.1	43.9
H₃PO₄	71.2	11.8	3.3	9.7	25.9
FeCl₃	68.2	1.3	0.3	3.8	13.4
CrCl₃	63.1	1.1	0.6	5.3	12.3
SnCl₄	64.3	1.9	0.7	4.6	14.2
InCl₃	61.5	1.7	0.4	3.8	13.5
Fe₂(SO₄)₃	80.3	8.3	2.8	5.3	42.3
CuSO₄	74.3	6.6	3.8	7.4	38.7
Al₂(SO₄)₃	82.6	8.6	4.4	7.6	58.3
FePO₄	82.5	7.6	5.8	9.3	52.9

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Preparation of Levulinic Acid and Methyl Levulinate from Cellulose Catalyzed by Solid Iron Phosphate

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