Yield Of Gaseous Products Research Articles

Design, instrumentation, and operation of a standard downdraft, laboratory-scale gasification testbed utilising novel seed-propagated hybrid Miscanthus pellets

Biomass gasification remains an attractive option to impact climate chaos; however, the technology presents challenges in tolerance to feedstock variability and tar production, which can limit the overall process efficiency, gasifier performance, durability and downstream syngas utilisation. The primary objectives of this study were to compare two gasifier design approaches using different reaction kinetics, based on multiple or singular oxidation and gasification reactions, and build and test a novel, flexible, laboratory-scale downdraft gasifier to convert pellets from UK hybrid Miscanthus into syngas, whilst deploying inexpensive instrumentation methods. The experimental gasification parameters studied were carbon conversion efficiency, gas yield, cold gas efficiency and gas heating values. The performance study shows that the system achieved good average temperature (842–866 °C) in the reduction zones for equivalence ratios between 0.25 and 0.35. The optimum values for carbon conversion efficiency, cold gas efficiency, heating values (HHV) of product gas and gas yield were 74%, 32%, 4.17 MJ/m3 and 1.32 m3/kg(biomass), respectively. The reported performance parameters for the new seed-propagated hybrid Miscanthus in the present study were comparable to those from conventional Miscanthus pellet gasification in downdraft gasifiers but these new hybrid varieties offer advantages in productivity over broader climatic regions compared to conventional varieties.

Decomposition of benzene as a biomass gasification tar in CH4 carrier gas using non-thermal plasma: Parametric and kinetic study

In this work, the decomposition of benzene was studied with CH4 using a dielectric barrier discharge (DBD) reactor. The experimental conditions such as input power, residence time, and concentration were varied to investigate the decomposition of benzene. The decomposition of benzene increased with increasing input power and residence time. The highest decomposition of benzene at 40 W and 2.86 s was 82.9%. The major gaseous products were H2 and lower hydrocarbons (LHC) and the yield of these products also increases with input power and residence time. The percentage yield of H2 increases from 0.65 to 5.18% by increasing input power from 5 to 40 W at 2.86 s. Similarly, the yield of LHC increases from 0.78 to 8.86% for benzene under the same reaction conditions. Hence, input power promoted the decomposition of tar compounds and enhanced the yield of gaseous products. However, at higher concentrations of the tar compound, decomposition efficiency and product yield decreased. The modified first-order kinetic model was used for the decomposition of tar model compound and methane carrier gas.

Epoxy-POSS/silicone rubber nanocomposites with excellent thermal stability and radiation resistance

Due to the rigid Si-O-Si backbone, silicone rubber (SR) have a widespread application in extreme environment such as high temperature and high-level radiation. However, the radiation stability of SR still does not meet the practical needs in special radiation environments. Herein we prepared epoxy POSS(ePOSS)/SR nanocomposites with excellent thermal stability and radiation resistance. As a physical crosslinking point in the SR, addition of small amount of ePOSS not only enhanced the mechanical properties of the matrix, but also improved its thermal stability greatly due to their good compatibility. ePOSS/SR had higher radiation stability in air than SR owing to the inhibition of radiation oxidation by ePOSS, and the yield of main gaseous radiolysis products (CH4, H2, CO and CO2) of SR and ePOSS/SR nanocomposites was determined. By analyzing the changes of chemical structure, thermal properties and mechanical properties of the ePOSS/SR nanocomposite, combined with the characteristics of gas products after γ-irradiation, the radiation induced crosslinking and degradation mechanism of the nanocomposites was proposed comprehensively.

Prediction of gas product yield from packaging waste pyrolysis: support vector and Gaussian process regression models

Prediction of gas product yield from packaging waste pyrolysis: support vector and Gaussian process regression models

Pyrolysis of COVID-19 disposable masks and catalytic cracking of the volatiles

The disposable masks generated in the battle against COVID-19 has attracted wide attention in the world. Pyrolysis can convert the masks into useful chemicals and fuels. In this work, the masks are pyrolyzed at temperatures of 400–580 °C and the volatiles generated are cracked without or with catalysts at 440–580 °C. The catalysts used include metal oxides (Al2O3, kaolin, Fe2O3, CeO2, TiO2) and molecular sieves (HZSM5, HY, β(25H), β(60H)). The yields and composition of gas and liquid products are studied in detail where the tetrahydrofuran (THF) soluble compounds are defined as the liquid product and the n-hexane soluble compounds are defined as the oil. The liquid product and the oil were identified by GC-MS and quantified by GC. Results indicate that 440 °C is sufficient for the masks’ pyrolysis and the yields of gas, liquid product and oil are 23.4, 74.7 and 42.1 wt%, respectively. About 30% of the liquid product are C6-C35 hydrocarbons while about 70% are C36-C70 hydrocarbons trapped in the GC column (termed as column residue). The gas products are mainly C5, propylene and butene, accounting for 54.8%, 22.8% and 14.5% of the total gas product, respectively. Cracking of volatiles over various catalysts converts the liquid product mainly to propylene, butene and smaller organic gases. TiO2, HY and β(60H) are good catalysts, especially β(60H), which increases the yield of gas product to 86.5 wt% with 73.0% being ethylene, propylene and butene at 580 °C.

Effects of torrefaction on product distribution and quality of bio-oil from food waste pyrolysis in N2 and CO2

Waste food utilization to produce bio-oil through pyrolysis has received increasing attention. The feedstock can be utilized more efficiently as its properties are upgraded. In this work, the mixed food waste (MFW) was pretreated via torrefaction at moderate temperatures (250–275 °C) under an inert atmosphere before fast pyrolysis. The pyrolysis of torrified MFW (T-MFW) was performed in a bubbling fluidized-bed reactor (FBR) to study the influence of torrefaction on the pyrolysis product distribution and bio-oil compositions. The highest liquid yield of 39.54 wt% was observed at a pyrolysis temperature of 450℃. The torrefaction has a significant effect on the pyrolysis process of MFW. After torrefaction, the higher heating values (HHVs) of the pyrolysis bio-oils (POs) ranged from 31.51 to 34.34 MJ/kg, which were higher than those of bio-oils from raw MFW (27.69–31.58 MJ/kg). The POs mainly contained aliphatic hydrocarbons (alkenes and ketones), phenolic, and N-containing derivatives. The pyrolysis of T-MFW was also carried out under the CO2 atmosphere. The application of CO2 as a carrier gas resulted in a decrease in the liquid yield and an increase in the gas product yield. In addition, the carbon and nitrogen content of POs increased, whereas the oxygen was reduced via the release of moisture and CO. Using CO2 in pyrolysis inhibited the generation of nitriles derivatives in POs, which are harmful to the environment. These results indicated that the application of CO2 to the thermal treatment of T-MFW could be feasible in energy production as well as environmental pollution control.

Catalytic pyrolysis of biomass with char modified by cathode materials of spent lithium-ion batteries for tar reduction and syngas production

The char modified by the battery cathode material was studied for catalytic pyrolysis of rice husk (RH). Compared to the direct mixing, the addition of cathode material to char by the impregnation was more favorable to synthesize the lignin char catalyst (i.e. char 1) with hierarchical pore structure and larger specific surface area. The char 1 decreased the Ea of the RH pyrolysis from 79 kJ/mol to 66 kJ/mol. The char 1 decreased the yield of liquid product from 23.2% to 12.3% and increased the yield of gas product from 35.2% to 52.2%. The char 1 decreased the contents of acids from 20.6% to 3.6% and phenols (tar surrogates) from 29.4% to 8.0%. The increase of hydrocarbons and CO2 indicated that the char catalysts had high catalytic reactivity in converting the oxygenated components (e.g., sugars, furans, acids, phenols) into light hydrocarbons (e.g., alkanes, aromatics) and micro-molecular gases (e.g., CO2, H2).

Production of hydrogen- and methane-rich gas by stepped pyrolysis of biomass and its utilization in IC engines

Automobile industries primarily use petroleum-based fuels like petrol and diesel, creating environmental hazards, a high carbon footprint, and severe health issues. The world focuses on compressed natural gas (CNG)-based energy solutions and developing CNG infrastructures to minimize environmental concerns from fossil fuel. The current focus to introduce a fraction of hydrogen with CNG in the existing fuel system is initiated here. Therefore, biomass utilization is taken into account to produce high hydrogen-containing fuel to cut down the carbon footprint and environmental issues. Biomass residues such as sun hemp, pigeon pea, mustard stem, wheat straw, dhaincha, and vantulasi were slowly pyrolyzed in a stepped manner to produce a hydrogen-rich clean fuel. The yield of product gas (hydrogen-rich CNG; HCNG) obtained by the pyrolysis process (21–29%) contains a volumetric composition of 40–55% hydrogen and 10–25% methane balanced with oxides of carbon depending on different biomass feedstocks. This study also focused on utilizing obtained HCNG in IC engine (2KVA Honda Genset) in terms of its running duration and efficiency. The maximum running time observed in sun hemp is 30 min, followed by the mustard stem is 28 min, the lowest in vantulasi is 16 min. However, the highest process efficiency is 87% for dhaincha which is 3.6 times more effective, and the lowest is 74% for Sun hemp, which is 3 times more effective than petrol in Genset for power production. A correlation is developed between ultimate analysis and product gas composition for running time estimation.Graphical abstract

Pyrolysis of fast growing wood Macaranga gigantea: Product characterisation and kinetic study

Fast-growing wood Macaranga gigantea has been pyrolyzed and its pyrolysis products have been characterized and their formation kinetics studied. Pyrolysis of M. gigantea wood was carried out by varying the temperature and time of pyrolysis to determine the effect of these two parameters on product yields and product characteristics. In general, an increase in pyrolysis temperature and time increased the yield of liquid and gas products, the concentration of cellulose, hemicellulose and lignin-derived compounds, but decreased the biochar yield. The organic phase liquid pyrolysis products mainly contained phenolic compounds and their derivatives, eugenols, furans, aldehydes and ketones. Fourier-transform infrared spectroscopy and pyrolysis–gas chromatography–mass spectrometry analyses of biochar showed that thermal decomposition of M. gigantea required temperatures higher than 300 °C to optimize thermal decomposition and carbonization of lignin, cellulose and hemicellulose. The concentration of phenols and benzenediols in biochar decreased with an increase in pyrolysis temperature. M. gigantea pyrolysis kinetics studies showed that wood pyrolysis occurred through four main stages with activation energy (Eα) values, based on calculations by the Friedman and Kissinger-Akahira-Sunose methods, of 28.1–99.0 kJ/mol and 35.6–104.9 kJ/mol, respectively. The spectra produced by thermogravimetric analyzer coupled with a Fourier-transform infrared spectroscopy showed that H2O and CO2 were produced during pyrolysis and the volatile compounds produced were predominantly phenolic compounds, in accord with characterization results of the liquid products by gas chromatography–mass spectrometry and nuclear magnetic resonance spectroscopy.

Agricultural waste-derived biochars from co-hydrothermal gasification of rice husk and chicken manure and their adsorption performance for dimethoate

This study aimed to combine energy utilisation of agricultural wastes with the dimethoate (DT) adsorption from agricultural wastewater via hydrogen and biochar production using co-hydrothermal gasification (CHTG). The gasification behaviour after CHTG of five ratios of rice husk (RH) and chicken manure (CM) and the corresponding adsorption performance of biochars on DT were evaluated. The results demonstrated that the feedstock of 3RH+ 1CM achieved the maximum gas yield and hydrogen gasification efficiency (HGE), and the highest adsorption capacity of the derived biochars was 3.57 mg g−1. Surface characterisation and elemental analysis showed that the biochar derived under different C/N ratios varied considerably. The results of the isotherm and kinetic simulation showed that the Langmuir model and pseudo-first-order model best fitted the experimental data. The superior performance of agricultural waste-derived biochars (AWB) over five cycles of regeneration and adsorption indicated that AWB is a green and stable adsorption material for farmland tailwater. In addition, the degradation pathway of DT during hydrothermal gasification (HTG) regeneration of the spent adsorbent was comprehensively discussed. The CHTG treatment enhanced the yield of gaseous products from RH and CM and produced AWBs with high adsorption capacities for DT. This provides a green and efficient technology for resource utilisation of agricultural waste and treatment of agricultural wastewater using pesticide residues.

Catalytic production of low-carbon footprint sustainable natural gas

Natural gas is one of the foremost basic energy sources on earth. Although biological process appears as promising valorization routes to transfer biomass to sustainable methane, the recalcitrance of lignocellulosic biomass is the major limitation for the production of mixing gas to meet the natural gas composition of pipeline transportation. Here we develop a catalytic-drive approach to directly transfer solid biomass to bio-natural gas which can be suitable for the current infrastructure. A catalyst with Ni2Al3 alloy phase enables nearly complete conversion of various agricultural and forestry residues, the total carbon yield of gas products reaches up to 93% after several hours at relative low-temperature (300 degrees Celsius). And the catalyst shows powerful processing capability for the production of natural gas during thirty cycles. A low-carbon footprint is estimated by a preliminary life cycle assessment, especially for the low hydrogen pressure and non-fossil hydrogen, and technical economic analysis predicts that this process is an economically competitive production process.

Production of Producer Gas from Densified Agricultural Biomass in Downdraft Gasifier and Its Application to Small Diesel Engines

Biomass is becoming one of the most popular renewable energy sources, especially from agricultural wastes. These wastes can be gasified and utilized in various industries. This experimental study investigated producer gas generation from densified agricultural fuels such as corncobs, rice husks, wood chips, and oil palm fronds in a 50 kWth throatless downdraft gasifier. This system produced combustible gases such as H2, CO, and CH4, which were utilized as a substitute for diesel fuel in a small diesel engine for power generation. The results showed that the gasifier performs successfully and seems to prefer pellets to briquettes. Producer gas contains 18%–20% carbon monoxide, 1%–6% hydrogen, and 0.9%–1.9% methane. Maximum gasification efficiencies of 53%–71% were achieved with biomass pellets from wood chips, corncobs, oil palm fronds, and rice husks, with producer gas calorific value of 2.94–3.85 MJ/Nm3. The average fuel consumption rate was between 6.72–14.43 kg/h, while the producer gas yield was between 2–3 Nm3/kg. The average gravimetric concentration of biomass tar in the raw product gas was found to be in the range of 23–50 g/Nm3, in which pelletized fuel appeared to show slightly lower tar than briquette fuel. The tar was primarily composed of five compounds: Benzo (a) pyrene, chrysene, pyrene, phenanthrene, 1-methylnaphthalene, and several other polycyclic aromatic compounds. The producer gas from oil palm frond briquettes and biodiesel were tested in a gas engine system in a dual fuel mode. A thermal efficiency of 22.21% was achieved with 2500 W electric load and a 72% biodiesel displacement rate, respectively.

Catalyzed pyrolysis of scrap tires rubber

Every day, a huge volume of scrap tires are produced worldwide, and landfill is an ineffective method of disposing of such hazardous waste. Pyrolysis can be used to convert tire rubber into energy, allowing for the management of such waste in the context of a circular economy. The composition and pyrolysis kinetics of granulated (0.6–0.8 mm) scrap tire rubber (TR) were assessed using thermogravimetry (TG). Data on rubber composition revealed that TG is a quick and accurate technique for determining TR composition. The TG tests with catalysts revealed that using alkali (K, Ca, and Mg) carbonates as catalysts improved the thermal degradation rate. The MgCO3 was able to duplicate the rate of TR thermal degradation. Data from a fixed bed pyrolysis reactor revealed oil yields of around 50% in the 673–773 K temperature range. The effect of alkali carbonate catalysts inferred from TG tests was confirmed by catalyzed pyrolysis tests. The calcium and magnesium carbonate catalysts significantly increased the gas product yield, with the CaCO3 catalyst having the greatest drop in oil yield due to likely secondary pyrolysis processes. Because of the low pyrolysis temperature, the acidic catalysts (SiO2, TiO2, Al2O3, and montmorillonite) had almost no effect on the pyrolysis product distribution. For all of the catalysts used, the ATR-FTIR spectra of the produced oils exhibited characteristics similar to those of diesel fuel. Data showed that alkali carbonate catalysts (mainly Mg and Ca), cheap and environmentally benign materials, can be used to tailor the TR pyrolysis products distribution allowing a more profitable process.

Low energy consumption and high quality bio-fuels production via in-situ fast pyrolysis of reed straw by adding metallic particles in an induction heating reactor

An in-situ fast pyrolysis of biomass by adding metallic particles in an induction heating reactor was proposed to produce high quality bio-fuels. After adding metallic particles into biomass, the times required to reach complete pyrolysis during reed straw pyrolysis process were significantly reduced up to 28.9%. The yields of combustible gas and bio-oil products were significantly increased. Furthermore, higher-quality combustible gas and bio-oil products were obtained with the LHV of gas products and HHV of bio-oil (dry basis) increased by 14.2%–19.1% and 4.16%–16.35%, respectively, under 400–600 °C. The lower oxygen content and higher yields of aromatics, alkenes and alkanes contents in bio-oil were obtained after metallic particles addition. More importantly, up to 26.5% of the total energy consumption during pyrolysis process was reduced after adding metallic particles into biomass in an induction heating reactor. The results indicate that adding metallic particles into biomass in an induction heating reactor can significantly enhance the heat transfer, decomposition reaction intensity and energy utilization efficiency of biomass pyrolysis process with lower energy consumption and higher-quality bio-fuel production.

Effect of additives on the distribution of three-phase products of oily sludge subjected to microwave pyrolysis

This study aimed to explore the influence of activated carbon, oily sludge pyrolysis residue, and biochar and their contents on the distribution of three-phase products of oily sludge subjected to microwave pyrolysis. A microwave reaction system, refinery gas analyzer, and chromatography-mass spectrometry were used to carry out the experiment and analyze the results. The results showed that all three additives reduced the yield of solid products and increased the yield of gas products. With an increase in the additive content, the volatile matter and moisture content in the pyrolysis residue greatly reduced. The content of CH4 and H2 in the pyrolysis gas increased with an increase in the additive content. When the amount of activated carbon was 20%, the H2 content reached a maximum (39.7%), and when the amount of biochar was 20%, the CH4 content reached a maximum (44.5%). All three additives increased the content of small molecules in the pyrolysis oil; when 10% activated carbon was added, the oil recovery rate reached up to 78.5%. The results of this study can guide the industrial application of microwave pyrolysis oily sludge.

Gasification of Densified Biomass (DB) and Municipal Solid Wastes (MSW) Using HTA/SG Technology

The necessity of economical and rational use of natural energy sources caused a rapid development of research on the possibilities of using non-conventional energy resources. Taking the above into account, a new technological process of thermochemical conversion of biomass and communal waste, commonly known as High Temperature Air/Steam Gasification (HTA/SG) and Multi-Staged Enthalpy Extraction Technology (HTAG-MEET), was developed. In relation to traditional techniques of gasification or combustion of hydrocarbon fuels, the presented concept is characterized by higher thermal efficiency of the process, low emission of harmful compounds of carbon, sulfur, nitrogen, dioxins, furans and heavy metals. The use of a high-temperature gasification factor causes an increased thermochemical decomposition of solid fuels, biomass and municipal waste into gaseous fuel (syngas), also with increased hydrogen content and Lower Calorific Value (LCV). In this study, the possibility of using a batch type reactor (countercurrent gasifier) was analyzed for gasification of biomass and municipal waste in terms of energy recovery and environmental protection. The proposed research topic was aimed at examining the possibility of using the thermal utilization of biomass and municipal waste through their high-temperature decomposition in the presence of air, a mixture of air and steam. The main goals of the research were achieved during the implementation of several parallel stages of the schedule, which included, primarily: (a) study of the possibility of using thermal utilization of biomass and municipal waste through their high-temperature gasification in the presence of air or a mixture of air and steam and, secondary (b) analytical and numerical modeling of high-temperature gasification of biomass and municipal waste with the use of ANSYS CFD Fluent 6.3 software. Selected results of the experimental and numerical studies are properly presented. The higher temperature gasification concept shows the capability of this technology for maximizing the gaseous product yield in an up-draft fixed bed gasifier. It was also observed that at a high temperature, steam addition contributed to the thermal conversion of biofuels to gas with higher production of hydrogen.

Investigation on effect of coal fly ash on properties of corn straw pyrolysis products

The impact of coal fly ash (FA) is often ignored in the co-utilization of biomass and coal. Therefore, the influence of FA on the properties of pyrolysis products made from corn straw (CS) was investigated in this study. First, the distribution of co-pyrolysis bio-oil was investigated using pyrolysis-gas chromatography and mass spectrometry at 500°C-800 °C. Then, in a free-falling fixed-bed reactor, FA and CS were co-pyrolyzed, gaseous product yields were computed, and solid product composition and morphology were determined using X-ray diffraction, scanning electron microscopy, and the N2 adsorption–desorption isotherm, respectively. According to the findings, FA greatly promoted the degradation of oxygen-containing components in bio-oil and the formation of aromatic compounds at higher temperatures. The CS5-FA1 was the most favorable ratio for bio-oil production at 800 °C. Furthermore, the addition of FA had the highest stimulating effect on CO2 at 500 °C and 800 °C, and the yield of the other pyrolysis gases (CH4, CO, and H2) was also increased at 800 °C.

Repsol to invest EUR 2.5 bn to ramp up renewable hydrogen capacity

Glycerol steam reforming (GSR) is one of the promising technologies that can realize renewable hydrogen production and efficient utilization of crude glycerol. To illuminate the functions of Ca content (3%, 6%, 9%, and 12 %, by mass) and preparation method for Ni/ATP catalyst structure and its catalytic behaviors, the Ni-xCa/ATP (x=3%, 6%, 9%, and 12%, by mass) catalysts are prepared by co-impregnation (ci) and hydrothermal synthesis (hs) method and then tested in GSR. Characterization results of XRD, N2 adsorption-desorption, H2-TPR, HRTEM, XPS, and NH3/CO2-TPD demonstrate that the combined effect between appropriate Ca additive (6%, by mass) and hs enhance catalyst reducibility, uniform distribution of Ca additive and nickel species over ATP, and adsorption for CO2. This attributes to hs method protects the ATP framework through suppressing the interaction of Ca with ATP and promotes the formation of Ni-CaOx interface sites. Therefore, Ni-6Ca/ATP-hs exhibits the highest conversion (86.77%) of glycerol to gas product and H2 yield (76.17%) and selectivity (58.56%) during GSR. Furthermore, XRD, HRTEM, TG-DTG and Raman analyses confirm that Ni-6Ca/ATP-hs also reveals outstanding anti-sintering and coke resistance. In addition, the structural evolution process of Ni/ATP catalyst with Ca introduction and hs method is presented. Considering the high performance, simple preparation process and low cost, the as-prepared catalyst providing new opportunities for utilization of glycerol derived from biodiesel industry.

BASF builds battery recycling prototype and pilot catalyst units

Glycerol steam reforming (GSR) is one of the promising technologies that can realize renewable hydrogen production and efficient utilization of crude glycerol. To illuminate the functions of Ca content (3%, 6%, 9%, and 12 %, by mass) and preparation method for Ni/ATP catalyst structure and its catalytic behaviors, the Ni-xCa/ATP (x=3%, 6%, 9%, and 12%, by mass) catalysts are prepared by co-impregnation (ci) and hydrothermal synthesis (hs) method and then tested in GSR. Characterization results of XRD, N2 adsorption-desorption, H2-TPR, HRTEM, XPS, and NH3/CO2-TPD demonstrate that the combined effect between appropriate Ca additive (6%, by mass) and hs enhance catalyst reducibility, uniform distribution of Ca additive and nickel species over ATP, and adsorption for CO2. This attributes to hs method protects the ATP framework through suppressing the interaction of Ca with ATP and promotes the formation of Ni-CaOx interface sites. Therefore, Ni-6Ca/ATP-hs exhibits the highest conversion (86.77%) of glycerol to gas product and H2 yield (76.17%) and selectivity (58.56%) during GSR. Furthermore, XRD, HRTEM, TG-DTG and Raman analyses confirm that Ni-6Ca/ATP-hs also reveals outstanding anti-sintering and coke resistance. In addition, the structural evolution process of Ni/ATP catalyst with Ca introduction and hs method is presented. Considering the high performance, simple preparation process and low cost, the as-prepared catalyst providing new opportunities for utilization of glycerol derived from biodiesel industry.

Evonik is building a new alkoxides plant in Southeast Asia

Glycerol steam reforming (GSR) is one of the promising technologies that can realize renewable hydrogen production and efficient utilization of crude glycerol. To illuminate the functions of Ca content (3%, 6%, 9%, and 12 %, by mass) and preparation method for Ni/ATP catalyst structure and its catalytic behaviors, the Ni-xCa/ATP (x=3%, 6%, 9%, and 12%, by mass) catalysts are prepared by co-impregnation (ci) and hydrothermal synthesis (hs) method and then tested in GSR. Characterization results of XRD, N2 adsorption-desorption, H2-TPR, HRTEM, XPS, and NH3/CO2-TPD demonstrate that the combined effect between appropriate Ca additive (6%, by mass) and hs enhance catalyst reducibility, uniform distribution of Ca additive and nickel species over ATP, and adsorption for CO2. This attributes to hs method protects the ATP framework through suppressing the interaction of Ca with ATP and promotes the formation of Ni-CaOx interface sites. Therefore, Ni-6Ca/ATP-hs exhibits the highest conversion (86.77%) of glycerol to gas product and H2 yield (76.17%) and selectivity (58.56%) during GSR. Furthermore, XRD, HRTEM, TG-DTG and Raman analyses confirm that Ni-6Ca/ATP-hs also reveals outstanding anti-sintering and coke resistance. In addition, the structural evolution process of Ni/ATP catalyst with Ca introduction and hs method is presented. Considering the high performance, simple preparation process and low cost, the as-prepared catalyst providing new opportunities for utilization of glycerol derived from biodiesel industry.