Catalytic Production of Methyl Lactate from Fructose‐Based Carbohydrates Using Yttrium Modified ZSM‐5 Zeolite

In recent years, numerous researchers have focused on the development of catalytic methods for processing of biomass-derived sugars into alkyl lactates, which are widely used as non-toxic solvents and are the starting material for obtaining monomeric lactide. In this work, the transformation of fructose into methyl lactate on Sn-containing catalyst in the flow reactor that may be of practical interest was studied. The supported Sn-containing catalyst was ob-tained by a simple impregnation method of granular γ-Al2O3. The catalytic ex-periments were performed in a flow reactor at temperatures of 160-190 °C and pressure of 3.0 MPa. The 1.6-9.5 wt.% fructose solutions in 80% aqueous methanol were used as a reaction mixture. It was found that addition to a reac-tion mixture of 0.03 wt.% potassium carbonate leads to the increase in selec-tivity towards methyl lactate on 15% at 100% conversion of fructose. Prod-ucts of the target reaction С6Н12О6 + 2СН3ОН = 2С4Н8О3 + 2Н2О were ana-lyzed using 13C NMR method. The following process conditions for obtaining of 65 mol% methyl lactate yield at 100% fructose conversion were found: use of 4.8 wt.% fructose solution in 80% methanol, 180 °С, 3.0 МПа and a load on catalyst 1.5 mmol C6H12O6/mlcat/h at contact time of 11 minutes. The cata-lyst productivity is 2.0 mmol C4H8O3/mlcat/h and the by-productі are 1,3-dihydroxyacetone dimethyl acetal (20%) and 5-hydroxymethylfurfural (10%). It should be noted that a racemic mixture of L- and D-methyl lactates has been obtained by conversion of D-fructose on the SnO2/Al2O3 catalyst. The SnO2/Al2O3 catalyst was found to be stable for 6 h while maintaining full fruc-tose conversion at 55–70% methyl lactate selectivity. After regeneration the catalyst completely restores the initial activity.

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Conversion of Biomass-Derived Carbohydrates to Methyl Lactate Using Sn-MCM-41 and SnO2/SiO2

CHINESE JOURNAL OF CATALYSIS (CHINESE VERSION) ◽

10.3724/sp.j.1088.2012.20533 ◽

2013 ◽

Vol 33 (10) ◽

pp. 1696-1705

Author(s):

Zhen LIU ◽

Gang FENG ◽

Chunyan PAN ◽

Wang LI ◽

Ping CHEN ◽

...

Keyword(s):

Methyl Lactate ◽

Mcm 41

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On the Spatial Design of Co-Fed Amines for Selective Dehydration of Methyl Lactate to Acrylates

ACS Catalysis ◽

10.1021/acscatal.1c00573 ◽

2021 ◽

pp. 5718-5735

Author(s):

Yutong Pang ◽

M. Alexander Ardagh ◽

Manish Shetty ◽

Anargyros Chatzidimitriou ◽

Gaurav Kumar ◽

...

Keyword(s):

Methyl Lactate ◽

Spatial Design

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Direct conversion of cellulose to high-yield methyl lactate over Ga-doped Zn/H-nanozeolite Y catalysts in supercritical methanol

Green Chemistry ◽

10.1039/c7gc00432j ◽

2017 ◽

Vol 19 (8) ◽

pp. 1969-1982 ◽

Cited By ~ 38

Author(s):

Deepak Verma ◽

Rizki Insyani ◽

Young-Woong Suh ◽

Seung Min Kim ◽

Seok Ki Kim ◽

...

Keyword(s):

Lignocellulosic Biomass ◽

Value Added ◽

Direct Conversion ◽

High Yield ◽

Supercritical Methanol ◽

Methyl Lactate ◽

High Yields

For realizing sustainable bio-based refineries, it is crucial to obtain high yields of value-added chemicalsviadirect conversion of cellulose and lignocellulosic biomass.

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Efficient dehydration of methyl lactate to acrylic acid using Ca3(PO4)2–SiO2 catalyst

Catalysis Communications ◽

10.1016/j.catcom.2010.06.013 ◽

2010 ◽

Vol 11 (15) ◽

pp. 1176-1180 ◽

Cited By ~ 27

Author(s):

Jong-Min Lee ◽

Dong-Won Hwang ◽

Young Kyu Hwang ◽

Shiva B. Halligudi ◽

Jong-San Chang ◽

...

Keyword(s):

Acrylic Acid ◽

Methyl Lactate

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Cooperative In–Sn catalyst system for efficient methyl lactate synthesis from biomass-derived sugars

Applied Catalysis B Environmental ◽

10.1016/j.apcatb.2015.10.015 ◽

2016 ◽

Vol 183 ◽

pp. 8-17 ◽

Cited By ~ 38

Author(s):

Koji Nemoto ◽

Yoshiaki Hirano ◽

Kei-ichi Hirata ◽

Tsukasa Takahashi ◽

Hideaki Tsuneki ◽

...

Keyword(s):

Catalyst System ◽

Methyl Lactate

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Vapor-phase oxidation of propylene glycol-methanol mixture to methyl lactate on CeO2/Al2O3 catalyst

Catalysis and petrochemistry ◽

10.15407/kataliz2021.31.092 ◽

2021 ◽

pp. 92-97

Author(s):

M.E. Sharanda ◽

◽

A.M. Mylin ◽

O.Yu. Zinchenko ◽

V.V. Brei ◽

...

Keyword(s):

Propylene Glycol ◽

Vapor Phase ◽

Flow Reactor ◽

Aldol Condensation ◽

Ethyl Lactate ◽

Molar Ratio ◽

Methyl Lactate ◽

Reactor Inlet ◽

Phase Oxidation ◽

Al2o3 Catalyst

The vapor-phase oxidation of mixtures of propylene glycol with methanol and ethanol to methyl and ethyl lactate, respectively, on supported CeO2/Al2O3 catalyst with 10 wt.% CeO2 content was studied. The steel flow reactor with a fixed catalyst bed (4 cm3) was used. 20 wt.% solution of propylene glycol in alcohol was fed to the reactor inlet by Waters 950 pump at LHSV= 0.5-0.8 h-1. Reaction temperature and pressure were varied in the interval of 190-250 0C and 1.3-1.8 bars respectively. Compressed air was given to the reactor inlet at the molar ratio of propylene glycol/O2 = 1. The reaction products were analyzed using gas chromatography (Agilent 7820A) and 3C NMR (Bruker Avance 400) methods. Studied oxidation of propylene glycol in the presence of methanol describes by total reaction CH3CHOHCH2OH +O2 + СН3OH = CH3CHOHCOOСН3 +2H2O At first, hydroxyacetone is formed that is further oxidized to pyruvic aldehyde, which attaches alcohol to form hemiacetal. Then, hemiacetal of methyl glyoxal rearranges into methyl lactate by Cannizzaro. At 220 0C and load on a catalyst of < 2 mmol PG/gcat/h, the selectivity towards methyl lactate reaches 70 wt.% at 100 % propylene glycol conversion. The main by-products are formed as the result of acetaldehyde transformation. Acetaldehyde could be formed at hydroxyacetone aldol decondensation. In the presence of ethanol, the formation of a significant amount of acetaldehyde and its aldol condensation products as well as the formation of diethoxyethane are observed. Therefore, ethyl lactate selectivity at 100 % propylene glycol conversion does not exceed 45 %. Supported CeO2/SiO2 contact was tested in this oxidation reaction also. However, CeO2/SiO2 provides the low, up to 25%, selectivity towards methyl lactate at full propylene glycol conversion. It was shown that at the same conditions methyl lactate is formed with higher selectivity then ethyl lactate. The high methyl lactate yield up to 70 wt.% could be obtained via vapor-phase oxidation of 20% mixture of propylene glycol with methanol by air oxygen on supported CeO2/Al2O3 catalyst at 210 - 220°С and at time contact of 3-4 seconds.

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