The industrial production of dimethyl carbonate from methanol and carbon dioxide

Frank F.T. de Groot, Roy R.G.J. Lammerink, Casper Heidemann, Michiel P.M. van der Werff, Taiga Cafiero Garcia, Louis A.G.J. van der Ham, Henk van den Berg

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Abstract

This work discusses the design of a dimethyl carbonate (DMC) production plant based on methanol and CO2 as feed materials, which are a cheap and environment-friendly feedstock. DMC is a good alternative for methyl-tert-butyl ether (MTBE) as a fuel oxygenating agent, due to its low toxicity and fast biodegradability. Based on the MTBE demand of a general gasoline plant, the annual production capacity of the process design is stipulated to be 86 kt DMC, with a purity of 99 wt%. Three routes are proposed to form DMC: 1) direct synthesis from methanol and CO2, 2) reaction of CO2 and ammonia to urea, which can be converted to DMC with methanol, 3) reaction of ethylene oxide with CO2 to a cyclic carbonate, which can be converted to DMC by transesterification with methanol. From a black box cost analysis based on raw material prices, it is concluded that the ethylene oxide route is the least profitable. Because of higher single-pass conversions found in literature, smaller recycles and easier separations, it is concluded that the urea route would be the most feasible. The required process functions for the urea route have been determined in the conceptual design phase. A detailed design of the most important process operations is made and an overall technical and economic evaluation of the process has been carried out. In the first step of this DMC synthesis, urea is produced from carbon dioxide and ammonia with the ACES21 process. After separation and purification steps, urea is fed to a reactor with methanol (150 °C, 20 bar), where methyl carbamate (MC), an intermediate of DMC production, and ammonia are formed in the absence of a catalyst. Subsequently, MC and methanol are converted to DMC and ammonia (190 °C, 40 bar) over a ZnO-Al2O3 catalyst in a fixed-bed reactor. Methanol and DMC form an azeotrope; extractive distillation with methyl isobutyl ketone (MIBK) as entrainer is used to separate the azeotropic mixture. The reactor model for the reaction towards DMC based on kinetic rate expressions, showed that a long residence time (>10 h) and a relatively high MeOH:MC molar feed ratio of 6 are required to achieve reasonable single-pass conversions (15 %). This resulted however in an unrealistically large reactor volume and a large methanol load on the process. A feasibility study was done in order to improve the performance of the process. It was calculated that with a MeOH:MC ratio of 2 and a single-pass conversion of MC of 30 % the process would become technically feasible; the reactor volume decreased from 5,000 m3 to 600 m3 and the energy consumption of the process was decreased from 238 MW to 50 MW. A Pinch analysis showed that maximally 6 MW could be saved with heat integration, which corresponds to approximately 2 M$/y savings on energy costs. To produce 86 kt/y of DMC, the required amounts of raw materials are 80 kt/y of methanol and 58 kt/y of CO2, which results in an overall DMC yield from methanol of 38 %. The required total capital investment of the process is 110 M$. Economic feasibility depends on the DMC selling price. A price range between 800 and 1,100 $/t was assumed. For 800 $/t it is not possible to repay the capital investment within an assumed lifetime of 10 years and the process would therefore not be profitable. The break-even point is at 845 $/t. For a selling price of 1,100 $/t the gross profit becomes 22 M$/y, with a payback period of 3 years and a return on investment of 20 %.

Original languageEnglish
Pages (from-to)1561-1566
Number of pages6
JournalChemical engineering transactions
Volume39
Issue numberSpecial Issue
DOIs
Publication statusPublished - 2014

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Carbon Dioxide
Methanol
Carbonates
Carbon dioxide
Urea
Ammonia
Ethylene Oxide
methyl carbonate
Sales
Raw materials
Ethers
Ethylene
Azeotropes
Economics
Catalysts
Biodegradability
Oxides
Transesterification
Conceptual design
Distillation

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de Groot, F. F. T., Lammerink, R. R. G. J., Heidemann, C., van der Werff, M. P. M., Garcia, T. C., van der Ham, L. A. G. J., & van den Berg, H. (2014). The industrial production of dimethyl carbonate from methanol and carbon dioxide. Chemical engineering transactions, 39(Special Issue), 1561-1566. https://doi.org/10.3303/CET1439261
de Groot, Frank F.T. ; Lammerink, Roy R.G.J. ; Heidemann, Casper ; van der Werff, Michiel P.M. ; Garcia, Taiga Cafiero ; van der Ham, Louis A.G.J. ; van den Berg, Henk. / The industrial production of dimethyl carbonate from methanol and carbon dioxide. In: Chemical engineering transactions. 2014 ; Vol. 39, No. Special Issue. pp. 1561-1566.
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abstract = "This work discusses the design of a dimethyl carbonate (DMC) production plant based on methanol and CO2 as feed materials, which are a cheap and environment-friendly feedstock. DMC is a good alternative for methyl-tert-butyl ether (MTBE) as a fuel oxygenating agent, due to its low toxicity and fast biodegradability. Based on the MTBE demand of a general gasoline plant, the annual production capacity of the process design is stipulated to be 86 kt DMC, with a purity of 99 wt{\%}. Three routes are proposed to form DMC: 1) direct synthesis from methanol and CO2, 2) reaction of CO2 and ammonia to urea, which can be converted to DMC with methanol, 3) reaction of ethylene oxide with CO2 to a cyclic carbonate, which can be converted to DMC by transesterification with methanol. From a black box cost analysis based on raw material prices, it is concluded that the ethylene oxide route is the least profitable. Because of higher single-pass conversions found in literature, smaller recycles and easier separations, it is concluded that the urea route would be the most feasible. The required process functions for the urea route have been determined in the conceptual design phase. A detailed design of the most important process operations is made and an overall technical and economic evaluation of the process has been carried out. In the first step of this DMC synthesis, urea is produced from carbon dioxide and ammonia with the ACES21 process. After separation and purification steps, urea is fed to a reactor with methanol (150 °C, 20 bar), where methyl carbamate (MC), an intermediate of DMC production, and ammonia are formed in the absence of a catalyst. Subsequently, MC and methanol are converted to DMC and ammonia (190 °C, 40 bar) over a ZnO-Al2O3 catalyst in a fixed-bed reactor. Methanol and DMC form an azeotrope; extractive distillation with methyl isobutyl ketone (MIBK) as entrainer is used to separate the azeotropic mixture. The reactor model for the reaction towards DMC based on kinetic rate expressions, showed that a long residence time (>10 h) and a relatively high MeOH:MC molar feed ratio of 6 are required to achieve reasonable single-pass conversions (15 {\%}). This resulted however in an unrealistically large reactor volume and a large methanol load on the process. A feasibility study was done in order to improve the performance of the process. It was calculated that with a MeOH:MC ratio of 2 and a single-pass conversion of MC of 30 {\%} the process would become technically feasible; the reactor volume decreased from 5,000 m3 to 600 m3 and the energy consumption of the process was decreased from 238 MW to 50 MW. A Pinch analysis showed that maximally 6 MW could be saved with heat integration, which corresponds to approximately 2 M$/y savings on energy costs. To produce 86 kt/y of DMC, the required amounts of raw materials are 80 kt/y of methanol and 58 kt/y of CO2, which results in an overall DMC yield from methanol of 38 {\%}. The required total capital investment of the process is 110 M$. Economic feasibility depends on the DMC selling price. A price range between 800 and 1,100 $/t was assumed. For 800 $/t it is not possible to repay the capital investment within an assumed lifetime of 10 years and the process would therefore not be profitable. The break-even point is at 845 $/t. For a selling price of 1,100 $/t the gross profit becomes 22 M$/y, with a payback period of 3 years and a return on investment of 20 {\%}.",
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de Groot, FFT, Lammerink, RRGJ, Heidemann, C, van der Werff, MPM, Garcia, TC, van der Ham, LAGJ & van den Berg, H 2014, 'The industrial production of dimethyl carbonate from methanol and carbon dioxide', Chemical engineering transactions, vol. 39, no. Special Issue, pp. 1561-1566. https://doi.org/10.3303/CET1439261

The industrial production of dimethyl carbonate from methanol and carbon dioxide. / de Groot, Frank F.T.; Lammerink, Roy R.G.J.; Heidemann, Casper; van der Werff, Michiel P.M.; Garcia, Taiga Cafiero; van der Ham, Louis A.G.J.; van den Berg, Henk.

In: Chemical engineering transactions, Vol. 39, No. Special Issue, 2014, p. 1561-1566.

Research output: Contribution to journalArticleAcademicpeer-review

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T1 - The industrial production of dimethyl carbonate from methanol and carbon dioxide

AU - de Groot, Frank F.T.

AU - Lammerink, Roy R.G.J.

AU - Heidemann, Casper

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AU - Garcia, Taiga Cafiero

AU - van der Ham, Louis A.G.J.

AU - van den Berg, Henk

PY - 2014

Y1 - 2014

N2 - This work discusses the design of a dimethyl carbonate (DMC) production plant based on methanol and CO2 as feed materials, which are a cheap and environment-friendly feedstock. DMC is a good alternative for methyl-tert-butyl ether (MTBE) as a fuel oxygenating agent, due to its low toxicity and fast biodegradability. Based on the MTBE demand of a general gasoline plant, the annual production capacity of the process design is stipulated to be 86 kt DMC, with a purity of 99 wt%. Three routes are proposed to form DMC: 1) direct synthesis from methanol and CO2, 2) reaction of CO2 and ammonia to urea, which can be converted to DMC with methanol, 3) reaction of ethylene oxide with CO2 to a cyclic carbonate, which can be converted to DMC by transesterification with methanol. From a black box cost analysis based on raw material prices, it is concluded that the ethylene oxide route is the least profitable. Because of higher single-pass conversions found in literature, smaller recycles and easier separations, it is concluded that the urea route would be the most feasible. The required process functions for the urea route have been determined in the conceptual design phase. A detailed design of the most important process operations is made and an overall technical and economic evaluation of the process has been carried out. In the first step of this DMC synthesis, urea is produced from carbon dioxide and ammonia with the ACES21 process. After separation and purification steps, urea is fed to a reactor with methanol (150 °C, 20 bar), where methyl carbamate (MC), an intermediate of DMC production, and ammonia are formed in the absence of a catalyst. Subsequently, MC and methanol are converted to DMC and ammonia (190 °C, 40 bar) over a ZnO-Al2O3 catalyst in a fixed-bed reactor. Methanol and DMC form an azeotrope; extractive distillation with methyl isobutyl ketone (MIBK) as entrainer is used to separate the azeotropic mixture. The reactor model for the reaction towards DMC based on kinetic rate expressions, showed that a long residence time (>10 h) and a relatively high MeOH:MC molar feed ratio of 6 are required to achieve reasonable single-pass conversions (15 %). This resulted however in an unrealistically large reactor volume and a large methanol load on the process. A feasibility study was done in order to improve the performance of the process. It was calculated that with a MeOH:MC ratio of 2 and a single-pass conversion of MC of 30 % the process would become technically feasible; the reactor volume decreased from 5,000 m3 to 600 m3 and the energy consumption of the process was decreased from 238 MW to 50 MW. A Pinch analysis showed that maximally 6 MW could be saved with heat integration, which corresponds to approximately 2 M$/y savings on energy costs. To produce 86 kt/y of DMC, the required amounts of raw materials are 80 kt/y of methanol and 58 kt/y of CO2, which results in an overall DMC yield from methanol of 38 %. The required total capital investment of the process is 110 M$. Economic feasibility depends on the DMC selling price. A price range between 800 and 1,100 $/t was assumed. For 800 $/t it is not possible to repay the capital investment within an assumed lifetime of 10 years and the process would therefore not be profitable. The break-even point is at 845 $/t. For a selling price of 1,100 $/t the gross profit becomes 22 M$/y, with a payback period of 3 years and a return on investment of 20 %.

AB - This work discusses the design of a dimethyl carbonate (DMC) production plant based on methanol and CO2 as feed materials, which are a cheap and environment-friendly feedstock. DMC is a good alternative for methyl-tert-butyl ether (MTBE) as a fuel oxygenating agent, due to its low toxicity and fast biodegradability. Based on the MTBE demand of a general gasoline plant, the annual production capacity of the process design is stipulated to be 86 kt DMC, with a purity of 99 wt%. Three routes are proposed to form DMC: 1) direct synthesis from methanol and CO2, 2) reaction of CO2 and ammonia to urea, which can be converted to DMC with methanol, 3) reaction of ethylene oxide with CO2 to a cyclic carbonate, which can be converted to DMC by transesterification with methanol. From a black box cost analysis based on raw material prices, it is concluded that the ethylene oxide route is the least profitable. Because of higher single-pass conversions found in literature, smaller recycles and easier separations, it is concluded that the urea route would be the most feasible. The required process functions for the urea route have been determined in the conceptual design phase. A detailed design of the most important process operations is made and an overall technical and economic evaluation of the process has been carried out. In the first step of this DMC synthesis, urea is produced from carbon dioxide and ammonia with the ACES21 process. After separation and purification steps, urea is fed to a reactor with methanol (150 °C, 20 bar), where methyl carbamate (MC), an intermediate of DMC production, and ammonia are formed in the absence of a catalyst. Subsequently, MC and methanol are converted to DMC and ammonia (190 °C, 40 bar) over a ZnO-Al2O3 catalyst in a fixed-bed reactor. Methanol and DMC form an azeotrope; extractive distillation with methyl isobutyl ketone (MIBK) as entrainer is used to separate the azeotropic mixture. The reactor model for the reaction towards DMC based on kinetic rate expressions, showed that a long residence time (>10 h) and a relatively high MeOH:MC molar feed ratio of 6 are required to achieve reasonable single-pass conversions (15 %). This resulted however in an unrealistically large reactor volume and a large methanol load on the process. A feasibility study was done in order to improve the performance of the process. It was calculated that with a MeOH:MC ratio of 2 and a single-pass conversion of MC of 30 % the process would become technically feasible; the reactor volume decreased from 5,000 m3 to 600 m3 and the energy consumption of the process was decreased from 238 MW to 50 MW. A Pinch analysis showed that maximally 6 MW could be saved with heat integration, which corresponds to approximately 2 M$/y savings on energy costs. To produce 86 kt/y of DMC, the required amounts of raw materials are 80 kt/y of methanol and 58 kt/y of CO2, which results in an overall DMC yield from methanol of 38 %. The required total capital investment of the process is 110 M$. Economic feasibility depends on the DMC selling price. A price range between 800 and 1,100 $/t was assumed. For 800 $/t it is not possible to repay the capital investment within an assumed lifetime of 10 years and the process would therefore not be profitable. The break-even point is at 845 $/t. For a selling price of 1,100 $/t the gross profit becomes 22 M$/y, with a payback period of 3 years and a return on investment of 20 %.

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de Groot FFT, Lammerink RRGJ, Heidemann C, van der Werff MPM, Garcia TC, van der Ham LAGJ et al. The industrial production of dimethyl carbonate from methanol and carbon dioxide. Chemical engineering transactions. 2014;39(Special Issue):1561-1566. https://doi.org/10.3303/CET1439261