Periodic Reporting for period 3 - GICO (Gasification Integrated with CO2 capture and conversion)
Periodo di rendicontazione: 2023-06-01 al 2024-11-30
Due to the waste, energy demand and oil/natural gas cost and related environmental impatcs increase and low use of biomass especially waste in biofuels and electricity sectors, new technologies must be found in order to use the:
1) high potential (where there is life there is biomass and so there will be always low cost biomass waste):
2) low environmental impacts (it can arrive to CO2 negative emission);
3) cross-fertilisation with many sectors (is the only renewable sourced that can produce food, materials and chemicals)
of the biomass waste. So, GICO foreseen the use of waste biomass via (see Figure 1:GICO concept):
(i) Hydrothermal Cracking (HTC) in order to allow the use of difficult to convert waste (spending less energy in drying, etc).
(ii) Sorption Enhanced Gasification (SEG) in order to convert waste in a high hydrogen content gas
(iii) Hot Gas Conditioning (HGC) in order not to generate waste and loose the heat energy as in cold gas conditioning
(iv) Plasma CO2 conversion with integrated oxygen membrane to convert CO2 in CO and Oxygen
(v) Methanol membrane reactor and SOFC to produce biofuel and electricity with high efficiency and low emissions and costs.
1) high potential (where there is life there is biomass and so there will be always low cost biomass waste):
2) low environmental impacts (it can arrive to CO2 negative emission);
3) cross-fertilisation with many sectors (is the only renewable sourced that can produce food, materials and chemicals)
of the biomass waste. So, GICO foreseen the use of waste biomass via (see Figure 1:GICO concept):
(i) Hydrothermal Cracking (HTC) in order to allow the use of difficult to convert waste (spending less energy in drying, etc).
(ii) Sorption Enhanced Gasification (SEG) in order to convert waste in a high hydrogen content gas
(iii) Hot Gas Conditioning (HGC) in order not to generate waste and loose the heat energy as in cold gas conditioning
(iv) Plasma CO2 conversion with integrated oxygen membrane to convert CO2 in CO and Oxygen
(v) Methanol membrane reactor and SOFC to produce biofuel and electricity with high efficiency and low emissions and costs.
Data concerning availability, physicochemical features of nontreated and treated with HTC biomass wastes was carried out (see D2.1) with more than 250 references of feedstock and hydrochars. 20 feedstocks have been identified, fully characterised and tested in SEG (see Figure 2 Syngas composition in SEG conditions: CaO and 600-700 °C): 10 with lower moisture (i.e. <50%) and inorganic matter (<15%) to be directly gasified and 10 with higher moisture and inorganic elements to be pretreated with HTC (produced 300 kg of hydrochar). Hydrochar yield ranged between 19 wt% for OFMSW and 72 wt% for wood waste, in line with decreasing feedstock moisture and increasing carbon content. Despite low organic matter content of whey, its positive contribution is reflected in a 5 % increase in the mass yield, when this residue replaces water as the reaction medium. The moisture content of the resulting hydrocarbons is reduced to ~ 60 wt% see D2.2. Although the results obtained for the particle that acts as sorbent and catalyst are promising, more tests and characterizations are required in order to bring the materials closer to a proof-of-concept owing to the problem in realising one-particle system with a good specific surface area (see D2.3). 40CaO-60Ca12Al14O33 & 40CaO-60CaZrO3 shown the highest carbon uptake properties. Although calcinated dolomite (c-DLM) showed a notable uptake capacity initially, about 50% of performance decreased quickly after 3 cycles. However, production cost of synthesized CO2 sorbents was estimated to be around 100 €/kg vs. 0.12 €/kg of DLM. Benchmark SER tests have also been performed for a two-particles system using the sorbent and a commercial nickel based catalyst showing satisfactory hydrogen concentrations above 95 vol% (dry basis).
Glow Discharge, Gliding Arc and Nanopulsed plasma did not meet capacity to operate stably at 1 bar pressure for long periods of time at high power operations. DBD approach was capable to operate stably in high chemical conversion or high energy efficiency regimes. High conversion requires a “high power - low flow” regime and high efficiency “low power - high flow”, this is due to two reasons: back-reaction of CO and O2 in the plasma and less homogeneous electric discharge at high power. The best OPEX is around 3 €/kg of CO in a low chemical conversion (15%), high energy efficiency (15%) see Figure 3 Plasma CO2 conversion and oxygen membrane results and Figure 4 DBD integrated with membrane during officer visit.
Rotary drum reactor was tested at different temperature, residence time, biomass and sorbents. 915-920 °C for 2h best calcining condition. Big and uniform biomass (i.e. hazelnut shell) segregates from the sorbent lowering the H2 yield over the test. HTC material converts towards syngas more easily and concentration of tar is lower (6.6 g/Nm3). At the Bubbling Fluidized Bed Reactor gasification facility several feedstocks were tested. The achievement of the 90 %-v syngas target in H2, already at the reactor outlet, appears achievable by adjusting the dolomite/olivine ratio and the biomass feed rate to the reactor. The use of the 50 %-wt calcined dolomite/olivine bed inventory turned out in a 40-75% tar reduction (based on gravimetric data in the range 40-70 g/Nm3dry) and a decrease in H2S and HCl levels to values of tens of ppm-v. Leaching is demonstrated a way of preventing the release of trace substances at combustion temperature.
High temperature catalytic ceramic hot gas filtration candles were tested at 650°C, showing that Ni impregnated AES candle has a conversion of 90% without H2Seq, with conversion is 40 %. Complete tar conversion achieved with 57-7 catalyst (at T=650°C, 20 ppm of H2S) at GHSV < 3000 h-1. HGC for gasifier is defined as: CaO (650 °C, CO2-polishing, H2S = 20 ppm) --> Aluminosilicate (650 °C, NaCl, KCl << 1 ppm) --> Filter candle (650 °C, particles) --> 57-7 catalyst (650 °C, tar removal) --> ZnO (550 °C, H2S < 5 ppm) --> AlkCO3 (400 °C – 500 °C, HCl < 1 -2.5 ppm). For combustor HGC is defined as: Aluminosilicate (920 °C, NaCl, KCl << 1 ppm) --> Filter candle (650 °C, particles) ---> AlkCO3 (400 °C – 500 °C, HCl < 1 -2.5 ppm) see Figure 5 Hot Gas Conditioning unit realised. Regarding the plasma assisted gas conditioning, tar removal efficiency was achieved (see D2.6).
Integrated gasification/carbonation – combustion/ calcination with HGC and integrated plasma CO2 conversion with oxygen membrane was tested (see D4.2). Membrane reactors for methanol production and methanol synthesis have been developped and tested (see D4.4). SOFC button cells tests with conditioned syngas to perform studies on the effect of organic and inorganic contaminants were done (see D4.5) and so BoP and P&ID of the overall system was done (see D4.6). Overall GICO simulation (D5.1 see Figure 6 GICO simulated in ASPEN) and optimisation (D5.2) techno-economic, environmental and social impact analysis (D5.3) market evaluation (D6.4) and business (D6.5) have been done taking into account 4 GICO plant schemes (wtih all, without plasma, without HTC, without plasma and HTC). Owing to the experimental (WP2, WP3, WP4) and simulative (WP5) results we did not reach the goal to demonstrate the foreseen reliability and efficiency of the overall process, e.g. 50% cost reduction, 50% energy efficiency increase, near-zero/negative emissions, but, within the best of the 4 different GICO plant schemes considered in D5.2 overall energy efficiency, emissions and costs are near to the goal.
Published/organised: 23 peer reviewed scientific articles, 3 articles, 3 conferences, 1 Workshop. Participated/produced: 20 international conferences, 16 datasets.
Glow Discharge, Gliding Arc and Nanopulsed plasma did not meet capacity to operate stably at 1 bar pressure for long periods of time at high power operations. DBD approach was capable to operate stably in high chemical conversion or high energy efficiency regimes. High conversion requires a “high power - low flow” regime and high efficiency “low power - high flow”, this is due to two reasons: back-reaction of CO and O2 in the plasma and less homogeneous electric discharge at high power. The best OPEX is around 3 €/kg of CO in a low chemical conversion (15%), high energy efficiency (15%) see Figure 3 Plasma CO2 conversion and oxygen membrane results and Figure 4 DBD integrated with membrane during officer visit.
Rotary drum reactor was tested at different temperature, residence time, biomass and sorbents. 915-920 °C for 2h best calcining condition. Big and uniform biomass (i.e. hazelnut shell) segregates from the sorbent lowering the H2 yield over the test. HTC material converts towards syngas more easily and concentration of tar is lower (6.6 g/Nm3). At the Bubbling Fluidized Bed Reactor gasification facility several feedstocks were tested. The achievement of the 90 %-v syngas target in H2, already at the reactor outlet, appears achievable by adjusting the dolomite/olivine ratio and the biomass feed rate to the reactor. The use of the 50 %-wt calcined dolomite/olivine bed inventory turned out in a 40-75% tar reduction (based on gravimetric data in the range 40-70 g/Nm3dry) and a decrease in H2S and HCl levels to values of tens of ppm-v. Leaching is demonstrated a way of preventing the release of trace substances at combustion temperature.
High temperature catalytic ceramic hot gas filtration candles were tested at 650°C, showing that Ni impregnated AES candle has a conversion of 90% without H2Seq, with conversion is 40 %. Complete tar conversion achieved with 57-7 catalyst (at T=650°C, 20 ppm of H2S) at GHSV < 3000 h-1. HGC for gasifier is defined as: CaO (650 °C, CO2-polishing, H2S = 20 ppm) --> Aluminosilicate (650 °C, NaCl, KCl << 1 ppm) --> Filter candle (650 °C, particles) --> 57-7 catalyst (650 °C, tar removal) --> ZnO (550 °C, H2S < 5 ppm) --> AlkCO3 (400 °C – 500 °C, HCl < 1 -2.5 ppm). For combustor HGC is defined as: Aluminosilicate (920 °C, NaCl, KCl << 1 ppm) --> Filter candle (650 °C, particles) ---> AlkCO3 (400 °C – 500 °C, HCl < 1 -2.5 ppm) see Figure 5 Hot Gas Conditioning unit realised. Regarding the plasma assisted gas conditioning, tar removal efficiency was achieved (see D2.6).
Integrated gasification/carbonation – combustion/ calcination with HGC and integrated plasma CO2 conversion with oxygen membrane was tested (see D4.2). Membrane reactors for methanol production and methanol synthesis have been developped and tested (see D4.4). SOFC button cells tests with conditioned syngas to perform studies on the effect of organic and inorganic contaminants were done (see D4.5) and so BoP and P&ID of the overall system was done (see D4.6). Overall GICO simulation (D5.1 see Figure 6 GICO simulated in ASPEN) and optimisation (D5.2) techno-economic, environmental and social impact analysis (D5.3) market evaluation (D6.4) and business (D6.5) have been done taking into account 4 GICO plant schemes (wtih all, without plasma, without HTC, without plasma and HTC). Owing to the experimental (WP2, WP3, WP4) and simulative (WP5) results we did not reach the goal to demonstrate the foreseen reliability and efficiency of the overall process, e.g. 50% cost reduction, 50% energy efficiency increase, near-zero/negative emissions, but, within the best of the 4 different GICO plant schemes considered in D5.2 overall energy efficiency, emissions and costs are near to the goal.
Published/organised: 23 peer reviewed scientific articles, 3 articles, 3 conferences, 1 Workshop. Participated/produced: 20 international conferences, 16 datasets.
GICO developped advanced, smart and flexible approaches to convert biowatse and RES electricity excess into biofuel and on-demand power production bringing together several socio-economic benefits:
(i) utilisation of residual biomass wastes (agricultural, industrial and municipal biomass waste with high humidity and/or ash content)
(ii) sorbents, catalysts, gasifier, plasma technologies, membrane reactors developped to increase efficiency and releability and reduce emissions and costs
(iii) potential to produce around 50% of electricity or 50% of transport EU energy demand
(i) utilisation of residual biomass wastes (agricultural, industrial and municipal biomass waste with high humidity and/or ash content)
(ii) sorbents, catalysts, gasifier, plasma technologies, membrane reactors developped to increase efficiency and releability and reduce emissions and costs
(iii) potential to produce around 50% of electricity or 50% of transport EU energy demand