Process assessment of renewable-based acrylic acid production from glycerol valorisation

The continuous growth of biodiesel production via transesterification is leading to an increase in the generation and availability of the by-product glycerol. In this study, a glycerol-based process for the production of acrylic acid has been designed and simulated. The valorisation of glycerol route includes a two-step conversion process where glycerol is first dehydrated to acrolein and acrolein is selectively oxidised to acrylic acid. This renewable-based process is then compared in terms of heat integration and techno-economic performance to the traditional petrochemical route from propylene from a techno-economic and environmental point of view. The study includes the detailed design of the separation train in which azeotropic distillation is also assessed along with the sensitivity analysis of the most relevant variables of the process. Using a production basis of approximately 10,250 kg h−1 of acrylic acid (purity>99.5 wt%), results show that the glycerol route generates 37.3% less CO2 emissions than the propylene-based. From the heat integration analysis, slightly lower heating (96.6%) but higher cooling (32.4%) energy savings can be attained in the glycerol route as opposed to heating (100%) and cooling (21.6%) energy savings available in the propylene-based route. In terms of economics, the glycerol-based route has a lower capital expenditure (£74.0 million) and operating expenditure (£171.4 million yr−1) compared to the propylene route (£91.3 million and £180.2 million yr−1, respectively). Nevertheless, considering the use of raw material and its cost, the glycerol route is more demanding (1.96 kg h−1 of pure glycerol per kg h−1 of acrylic acid amounting to £138.6 million yr−1) than the propylene route (0.92 kg h−1 of propylene per kg h−1 of acrylic acid at £117.2 million yr−1)

Investigation of heat management for CLC of syngas in packed bed reactors

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Direct route from ethanol to pure hydrogen through autothermal reforming in a membrane reactor: Experimental demonstration, reactor modelling and design

This work reports the integration of thin (∼3–4 μm thick) Pd-based membranes for H2 separation in a fluidized bed catalytic reactor for ethanol auto-thermal reforming. The performance of a fluidized bed membrane reactor has been investigated from an experimental and numerical point of view. The demonstration of the technology has been carried out over 50 h under reactive conditions using 5 thin Pd-based alumina-supported membranes and a 3 wt%Pt-10 wt%Ni catalyst deposited on a mixed CeO2/SiO2 support. The results have confirmed the feasibility of the concept, in particular the capacity to reach a hydrogen recovery factor up to 70%, while the operation at different fluidization regimes, oxygen-to-ethanol and steam-to-ethanol ratios, feed pressures and reactor temperatures have been studied. The most critical part of the system is the sealing of the membranes, where most of the gas leakage was detected. A fluidized bed membrane reactor model for ethanol reforming has been developed and validated with the obtained experimental results. The model has been subsequently used to design a small reactor unit for domestic use, showing that 0.45 m2 membrane area is needed to produce the amount of H2 required for a 5 kWe PEM fuel-cell based micro-CHP system.The presented work is funded within the FluidCELL project as part of the European Union's Seventh Framework Programme (FP7/ 2007-2013) for the Fuel Cells and Hydrogen Joint Technology Initiative under grant agreement nº 621196

Techno-economic assessment of membrane assisted fluidized bed reactors for pure H2 production with CO2 capture

This paper addresses the techno-economic assessment of two membrane-based technologies for H2 production from natural gas, fully integrated with CO2 capture. In the first configuration, a fluidized bed membrane reactor (FBMR) is integrated in the H2 plant: the natural gas reacts with steam in the catalytic bed and H2 is simultaneously separated using Pd-based membranes, and the heat of reaction is provided to the system by feeding air as reactive sweep gas in part of the membranes and by burning part of the permeated H2 (in order to avoid CO2 emissions for heat supply). In the second system, named membrane assisted chemical looping reforming (MA-CLR), natural gas is converted in the fuel rector by reaction with steam and an oxygen carrier (chemical looping reforming), and the produced H2 permeates through the membranes. The oxygen carrier is re-oxidized in a separate air reactor with air, which also provides the heat required for the endothermic reactions in the fuel reactor. The plants are optimized by varying the operating conditions of the reactors such as temperature, pressures (both at feed and permeate side), steam-to-carbon ratio and the heat recovery configuration. The plant design is carried out using Aspen Simulation, while the novel reactor concepts have been designed and their performance have been studied with a dedicated phenomenological model in Matlab. Both configurations have been designed and compared with reference technologies for H2 production based on conventional fired tubular reforming (FTR) with and without CO2 capture. The results of the analysis show that both new concepts can achieve higher H2 yields than conventional plants (12-20% higher). The high electricity consumptions of membrane-based plants are associated with the required low pressure at the retentate side. However, the low energy cost for the CO2 separation and compression makes the overall reforming efficiency from 4% to 20% higher than conventional FTR with CO2 scrubbing. FBMR and MA-CLR show better performance than FTR with CO2 capture technology in terms of costs mainly because of lower associated CAPEX. The cost of H2 production reduces from 0.28 €/NmH23 to 0.22 €/NmH23 (FBMR) and 0.19 €/NmH23 (MA-CLR)

Techno-economic assessment of membrane assisted fluidized bed reactors for pure H2 production with CO2 capture

This paper addresses the techno-economic assessment of two membrane-based technologies for H2 production from natural gas, fully integrated with CO2 capture. In the first configuration, a fluidized bed membrane reactor (FBMR) is integrated in the H2 plant: the natural gas reacts with steam in the catalytic bed and H2 is simultaneously separated using Pd-based membranes, and the heat of reaction is provided to the system by feeding air as reactive sweep gas in part of the membranes and by burning part of the permeated H2 (in order to avoid CO2 emissions for heat supply). In the second system, named membrane assisted chemical looping reforming (MA-CLR), natural gas is converted in the fuel rector by reaction with steam and an oxygen carrier (chemical looping reforming), and the produced H2 permeates through the membranes. The oxygen carrier is re-oxidized in a separate air reactor with air, which also provides the heat required for the endothermic reactions in the fuel reactor. The plants are optimized by varying the operating conditions of the reactors such as temperature, pressures (both at feed and permeate side), steam-to-carbon ratio and the heat recovery configuration. The plant design is carried out using Aspen Simulation, while the novel reactor concepts have been designed and their performance have been studied with a dedicated phenomenological model in Matlab. Both configurations have been designed and compared with reference technologies for H2 production based on conventional fired tubular reforming (FTR) with and without CO2 capture. The results of the analysis show that both new concepts can achieve higher H2 yields than conventional plants (12-20% higher). The high electricity consumptions of membrane-based plants are associated with the required low pressure at the retentate side. However, the low energy cost for the CO2 separation and compression makes the overall reforming efficiency from 4% to 20% higher than conventional FTR with CO2 scrubbing. FBMR and MA-CLR show better performance than FTR with CO2 capture technology in terms of costs mainly because of lower associated CAPEX. The cost of H2 production reduces from 0.28 €/NmH23 to 0.22 €/NmH23 (FBMR) and 0.19 €/NmH23 (MA-CLR)

SOFC-based hybrid cycle integrated with a coal gasification plant

Application of large scale high temperature fuel cells on syngas fuel produced from coal would be a turning point in the power generation sector, dramatically improving the efficiency and the environmental performance of coal-fired power plants. The purpose of this study is the assessment of a system constituted by a SOFC-based hybrid cycle integrated with a coal gasification process. In this system, syngas produced in a high efficiency, dry feed, oxygen blown, entrained flow Shell gasifier is cooled, depurated from particulate and sulfur compounds and reheated; the clean syngas feeds a pressurized SOFC together with high pressure air generated by the compressor of a gas turbine. After combustion of unconverted syngas, fuel cell exhausts are expanded and cooled, providing heat to a bottoming steam cycle for an efficient energy recovery. A high integration between gasification and power islands is necessary in order to obtain an elevated efficiency: the heat recovery system from syngas cooling is carefully arranged to provide thermal power for clean syngas reheating, air preheating and steam generation. The paper presents a preliminary analysis of literature results and a discussion of the thermodynamic implications arising from the use of different primary fuels in a fuel cell-gas turbine cycle. Then the work presents a detailed thermodynamic analysis of the proposed IGFC layout, assessing the effect of SOFC operating pressure on power balance and net plant efficiency. A sensitivity analysis on the variation of fuel and air utilization in the fuel cell is also performed. Results show that the present innovative SOFC-based power system may achieve an efficiency gain of 7-11 percentage points, with respect to an advanced IGCC based on state of the art technology