Synthesis of acrylic acid from methyl lactate over calcium phosphate catalysts in a fixed bed reactor: time-on-stream behavior and kinetic analysis

Atte Aho; Päivi Mäki-Arvela; Narendra Kumar; Ilari Angervo; Karl Eränen; Johan Wärnå; Tapio Salmi; Dmitry Murzin

doi:10.1080/00986445.2024.2338787

Synthesis of acrylic acid from methyl lactate over calcium phosphate catalysts in a fixed bed reactor: time-on-stream behavior and kinetic analysis

Atte Aho, Päivi Mäki-Arvela, Narendra Kumar, Ilari Angervo, Karl Eränen, Johan Wärnå, Tapio Salmi, Dmitry Murzin

Laboratory of Industrial Chemistry and Reaction Engineering

Research output: Contribution to journal › Article › Scientific › peer-review

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Abstract

Transformation of methyl lactate to acrylic acid was investigated over Ca ₃(PO ₄) ₂, Ca ₂(P ₂O ₇) and their mixture in the temperature range of 250-425 °C. The initial concentration of methyl lactate in water was varied from 2 wt% to neat methyl lactate. The results showed that these phosphate catalysts did not contain any measurable amounts of either acid sites or basic sites. The best catalyst was Ca ₃(PO ₄) ₂ giving 62% selectivity to acrylic acid at 75% conversion at 400 °C using GHSV of 95280 h ⁻¹ and 2 wt% methyl lactate in the initial feed. This catalyst exhibited larger surface area in comparison to Ca ₂(P ₂O ₇). Elemental analysis revealed that some Ca leaching occurred during reaction, while in case of Ca ₂(P ₂O ₇) the calcium leaching was 3.4 fold higher than observed for Ca ₃(PO ₄) ₂. Long-term results over Ca ₃(PO ₄) ₂ showed that extensive catalyst deactivation occurred during the first 11 h time-on-stream, after which the activity dropped only slightly. In addition to kinetic studies with different parameters, also, kinetic modeling was performed and the activation energies for formation of different products were determined over different catalysts.

Original language	American English
Pages (from-to)	1300-1318
Journal	Chemical Engineering Communications
Volume	211
Issue number	8
DOIs	https://doi.org/10.1080/00986445.2024.2338787
Publication status	Published - 10 Apr 2024
MoE publication type	A1 Journal article-refereed

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Synthesis of acrylic acid from methyl lactate over calcium phosphate catalysts in a fixed bed reactor time-on-stream behavior and kinetic analysisFinal published version, 3.33 MBLicence: CC BY

https://urn.fi/URN:NBN:fi-fe2024081264473

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title = "Synthesis of acrylic acid from methyl lactate over calcium phosphate catalysts in a fixed bed reactor: time-on-stream behavior and kinetic analysis",

abstract = "Transformation of methyl lactate to acrylic acid was investigated over Ca 3(PO 4) 2, Ca 2(P 2O 7) and their mixture in the temperature range of 250-425 °C. The initial concentration of methyl lactate in water was varied from 2 wt% to neat methyl lactate. The results showed that these phosphate catalysts did not contain any measurable amounts of either acid sites or basic sites. The best catalyst was Ca 3(PO 4) 2 giving 62% selectivity to acrylic acid at 75% conversion at 400 °C using GHSV of 95280 h −1 and 2 wt% methyl lactate in the initial feed. This catalyst exhibited larger surface area in comparison to Ca 2(P 2O 7). Elemental analysis revealed that some Ca leaching occurred during reaction, while in case of Ca 2(P 2O 7) the calcium leaching was 3.4 fold higher than observed for Ca 3(PO 4) 2. Long-term results over Ca 3(PO 4) 2 showed that extensive catalyst deactivation occurred during the first 11 h time-on-stream, after which the activity dropped only slightly. In addition to kinetic studies with different parameters, also, kinetic modeling was performed and the activation energies for formation of different products were determined over different catalysts.",

author = "Atte Aho and P{\"a}ivi M{\"a}ki-Arvela and Narendra Kumar and Ilari Angervo and Karl Er{\"a}nen and Johan W{\"a}rn{\aa} and Tapio Salmi and Dmitry Murzin",

year = "2024",

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language = "Amerikansk engelska",

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pages = "1300--1318",

journal = "Chemical Engineering Communications",

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Synthesis of acrylic acid from methyl lactate over calcium phosphate catalysts in a fixed bed reactor: time-on-stream behavior and kinetic analysis. / Aho, Atte ; Mäki-Arvela, Päivi ; Kumar, Narendra et al.
In: Chemical Engineering Communications, Vol. 211, No. 8, 10.04.2024, p. 1300-1318.

Research output: Contribution to journal › Article › Scientific › peer-review

TY - JOUR

T1 - Synthesis of acrylic acid from methyl lactate over calcium phosphate catalysts in a fixed bed reactor: time-on-stream behavior and kinetic analysis

AU - Aho, Atte

AU - Mäki-Arvela, Päivi

AU - Kumar, Narendra

AU - Angervo, Ilari

AU - Eränen, Karl

AU - Wärnå, Johan

AU - Salmi, Tapio

AU - Murzin, Dmitry

PY - 2024/4/10

Y1 - 2024/4/10

N2 - Transformation of methyl lactate to acrylic acid was investigated over Ca 3(PO 4) 2, Ca 2(P 2O 7) and their mixture in the temperature range of 250-425 °C. The initial concentration of methyl lactate in water was varied from 2 wt% to neat methyl lactate. The results showed that these phosphate catalysts did not contain any measurable amounts of either acid sites or basic sites. The best catalyst was Ca 3(PO 4) 2 giving 62% selectivity to acrylic acid at 75% conversion at 400 °C using GHSV of 95280 h −1 and 2 wt% methyl lactate in the initial feed. This catalyst exhibited larger surface area in comparison to Ca 2(P 2O 7). Elemental analysis revealed that some Ca leaching occurred during reaction, while in case of Ca 2(P 2O 7) the calcium leaching was 3.4 fold higher than observed for Ca 3(PO 4) 2. Long-term results over Ca 3(PO 4) 2 showed that extensive catalyst deactivation occurred during the first 11 h time-on-stream, after which the activity dropped only slightly. In addition to kinetic studies with different parameters, also, kinetic modeling was performed and the activation energies for formation of different products were determined over different catalysts.

AB - Transformation of methyl lactate to acrylic acid was investigated over Ca 3(PO 4) 2, Ca 2(P 2O 7) and their mixture in the temperature range of 250-425 °C. The initial concentration of methyl lactate in water was varied from 2 wt% to neat methyl lactate. The results showed that these phosphate catalysts did not contain any measurable amounts of either acid sites or basic sites. The best catalyst was Ca 3(PO 4) 2 giving 62% selectivity to acrylic acid at 75% conversion at 400 °C using GHSV of 95280 h −1 and 2 wt% methyl lactate in the initial feed. This catalyst exhibited larger surface area in comparison to Ca 2(P 2O 7). Elemental analysis revealed that some Ca leaching occurred during reaction, while in case of Ca 2(P 2O 7) the calcium leaching was 3.4 fold higher than observed for Ca 3(PO 4) 2. Long-term results over Ca 3(PO 4) 2 showed that extensive catalyst deactivation occurred during the first 11 h time-on-stream, after which the activity dropped only slightly. In addition to kinetic studies with different parameters, also, kinetic modeling was performed and the activation energies for formation of different products were determined over different catalysts.

U2 - 10.1080/00986445.2024.2338787

DO - 10.1080/00986445.2024.2338787

M3 - Artikel

SN - 0098-6445

VL - 211

SP - 1300

EP - 1318

JO - Chemical Engineering Communications

JF - Chemical Engineering Communications

IS - 8

ER -

Synthesis of acrylic acid from methyl lactate over calcium phosphate catalysts in a fixed bed reactor: time-on-stream behavior and kinetic analysis

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