Novel eco-efficient reactive distillation process for dimethyl carbonate production by indirect alcoholysis of urea

doi:10.1007/s11705-021-2047-9

Front. Chem. Sci. Eng.

2022, Vol. 16

Issue (2) : 316-331 https://doi.org/10.1007/s11705-021-2047-9

RESEARCH ARTICLE

Novel eco-efficient reactive distillation process for dimethyl carbonate production by indirect alcoholysis of urea

Iulian Patrașcu¹, Costin S. Bîldea¹, Anton A. Kiss²(

)

¹. Department of Chemical and Biochemical Engineering, University “Politehnica” of Bucharest, 011061 Bucharest, Romania
². Department of Chemical Engineering and Analytical Science, The University of Manchester, Manchester M13 9PL, UK

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Abstract

Dimethyl carbonate is an eco-friendly essential chemical that can be sustainably produced from CO₂, which is available from carbon capture activities or can even be captured from the air. The rapid increase in dimethyl carbonate demand is driven by the fast growth of polycarbonates, solvent, pharmaceutical, and lithium-ion battery industries. Dimethyl carbonate can be produced from CO₂ through various chemical pathways, but the most convenient route reported is the indirect alcoholysis of urea. Previous research used techniques such as heat integration and reactive distillation to reduce the energy use and costs, but the use of an excess of methanol in the trans-esterification step led to an energy intensive extractive distillation required to break the dimethyl carbonate-methanol azeotrope. This work shows that the production of dimethyl carbonate by indirect alcoholysis of urea can be improved by using an excess of propylene carbonate (instead of an excess of methanol), a neat feat that we showed it requires only 2.64 kW·h·kg^–1 dimethyl carbonate in a reaction-separation-recycle process, and a reactive distillation column that effectively replaces two conventional distillation columns and the reactor for dimethyl carbonate synthesis. Therefore, less equipment is required, the methanol-dimethyl carbonate azeotrope does not need to be recycled, and the overall savings are higher. Moreover, we propose the use of a reactive distillation column in a heat integrated process to obtain high purity dimethyl carbonate (>99.8 wt-%). The energy requirement is reduced by heat integration to just 1.25 kW·h·kg^–1 dimethyl carbonate, which is about 52% lower than the reaction-separation-recycle process. To benefit from the energy savings, the dynamics and control of the process are provided for ±10% changes in the nominal rate of 32 ktpy dimethyl carbonate, and for uncertainties in reaction kinetics.

Keywords dimethyl carbonate reactive distillation process design plantwide control

Corresponding Author(s): Anton A. Kiss

Just Accepted Date: 03 March 2021 Online First Date: 28 April 2021 Issue Date: 10 January 2022

Cite this article:

Iulian Patra?cu,Costin S. Bîldea,Anton A. Kiss. Novel eco-efficient reactive distillation process for dimethyl carbonate production by indirect alcoholysis of urea[J]. Front. Chem. Sci. Eng., 2022, 16(2): 316-331.

URL:

https://academic.hep.com.cn/fcse/EN/10.1007/s11705-021-2047-9
https://academic.hep.com.cn/fcse/EN/Y2022/V16/I2/316

Tab.1 DMC production processes and the energy usage

Fig.1 DMC synthesis by indirect alcoholysis of urea (PC route).

Tab.2 Boiling points of pure components and azeotropes (1 bar)

Tab.3 Binary interaction parameters

Fig.2 Flowsheet of the DMC process (DC&RDC).

Fig.3 (a) and (b) Temperature and composition profiles of the DC C1; (c) temperature and reaction rate profiles and (d) liquid-vapour composition profiles along the RDC.

Fig.4 Optimization of the DCs (a) C1, (b) C2 and (c) RDC for the DMC process.

Fig.5 Composite curves for heat integration: (a) without side reboiler and (b) with side reboiler.

Fig.6 Flowsheet of the DMC process, proposed for heat integration.

Fig.7 Heat integrated process design for DMC production (HI-DC&RDC).

Fig.8 Temperature profiles of the heat exchangers (a) HEX1, (b) HEX2, (c) HEX3, and (d) HEX4.

Fig.9 Heat exchangers network for the heat integrated process.

Tab.4 Energy usage (heating requirements) in various scenarios for DMC synthesis and purification

Tab.5 Economic evaluation of the process

Fig.10 Process control structure of heat integrated plant for DMC production.

Controller	PV, value & range	OP, value & range	Kc/%	Time/min
FC urea	Flow rate= 2704 kg·h^–1
LC mix PGMKUP	Level= 1.875 m	Flow rate PGMKUP= 32.9 kg·h^–1	130	13.2
	0–3.75 m	0–1000 kg·h^–1
Ratio control	Flow rate urea= 2704 kg·h^–1	Flow rate propilen glicol= 3581 kg·h^–1	1.324
Concentration controller (CC) urea	Urea concentration= 1.429 wt-%	Urea:PG= 1.324	0.06	500
	0.04–0.24 wt-%	0–2.64
TC CSTR1	Temperature= 180 °C	Heat duty= 2.33 GJ·h^–1	5	6
	130 °C–230 °C	−46–46 GJ·h^–1
LC CSTR1	Level= 2.90 m	Product flow rate CSTR1= 6285 kg·h^–1	10	60
	0–4.14 m	0–12571 kg·h^–1
TC CSTR2	Temperature= 180 °C	Heating duty= 0.35 GJ·h^–1	5	6
	130 °C–230 °C	−7–7 GJ·h^–1
LC CSTR2	Level= 2.90 m	Flow rate product CSTR2= 5082 kg·h^–1	10	60
	0–4.14 m	0–10164 kg·h^–1
TC flash V-L	Temperature= 50 °C	Cooling duty= −1.8 GJ·h^–1	10	20
	40 °C–60 °C	−3.6–0 GJ·h^–1
LC flash V-L	Level= 1 m	Product flow rate= 5082 kg·h^–1	10	60
	0–2 m	0–10164 kg·h^–1
PC flash V-L	Column pressure= 0.5 bar	Vapor flow rate= 70.4 kmol·h^–1	20	12
	0–1 bar	0–140 kmol·h^–1
PC C1	Column pressure= 0.5 bar	Vapor flow rate= 20 kmol·h^–1	20	12
	0–1 bar	0–40 kmol·h^–1
LC reflux drum C1	Level= 3.35 m	Flow rate reflux= 339.8 kg·h^–1	94	2.64
	0–4.8 m	0–679 kg·h^–1
LC sump C1	Level= 0.61 m	Bottom flow rate= 4714.9 kg·h^–1	10	60
	0–1.22 m	0–9428 kg·h^–1
TC stage 1 C1	Temperature= 94.44 °C	Condenser duty= −0.301 GJ·h^–1	10	20
	84 °C–104 °C	−1.89–0 GJ·h^–1
TC stage 6 C1	Temperature= 195.2 °C	Reboiler duty= 0.944 GJ·h^–1	10	20
	185 °C–205 °C	0–1.89 GJ·h^–1
TC Cool1	Temperature= 49 °C	Cooler duty= −2.16 GJ·h^–1	5	1
	39 °C–59 °C	−4.33–0 GJ·h^–1
Ratio control	Flow rate PC= 15084.2 kg·h^–1	Flow rate metanol= 2884.38 kg·h^–1	0.1912
PC RDC	Column pressure= 1 bar	Condenser duty= −1.48 GJ·h^–1	20	12
	0–2 bar	−2.96–0 GJ·h^–1
LC reflux drum RDC	Level= 1.37 m	Distillate flow rate= 4050.7 kg·h^–1	10	60
	0–2.75 m	0–8099.8 kg·h^–1
LC sump RDC	Level= 1.43 m	Bottom flow rate= 13917.9 kg·h^–1	10	60
	0–2.85 m	0–27830 kg·h^–1
TC stage 3 RDC	Temperature= 49.7 °C	PC:urea= 0.1912	0.0488	7.92
	40 °C–60 °C	0–0.38
TC stage 33 RDC	Temperature= 149.79 °C	Reboiler duty= 4.39 GJ·h^–1	10	20
	140 °C–160 °C	0–8.78 GJ·h^–1
PC C2	Column pressure= 0.25 bar	Top vapors flow rate= 178.56 kmol·h^–1	20	12
	0–5 bar	0–357.05 kmol·h^–1
LC reflux drum C2	Level= 1.56 m	Condensate flow rate= 13665.38 kg·h^–1	10	60
	0–3.12 m	0–27325.32 kg·h^–1
LC sump C2	Level= 1.875 m	Bottom flow rate= 10369.3 kg·h^–1	10	60
	0–3.75 m	0–20734.25 kg·h^–1
TC condenser C2	Temperature= 145.97 °C	Condenser duty= −7.27 GJ·h^–1	10	20
	135 °C–155 °C	−14.53–0 GJ·h^–1
TC stage 44 C2	Temperature= 179.66 °C	Reboiler duty= 10.25 GJ·h^–1	10	20
?	170 °C–190 °C	0–20.5 GJ·h^–1

Tab.6 Controller tuning parameters

Fig.11 Dynamic results for 10% disturbances in urea feed flow rate: (a) change in flowrates and (b) change in DMC and NH₃ purities.

Fig.12 Dynamic simulation results for change of the PG+ DMC → PC+ 2MeOH reaction rate constant (ramp up from 0.0021 to 0.0038 kmol·kg^–1·s^–1, at t = 2 h): (a) change in flowrates; (b) change in DMC and NH₃ purity; (c) change in MeOH and PC flowrates; (d) change in reboiler duty and reflux rate.

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