Review of heterogeneous catalysts for sub- and supercritical water gasification of biomass and wastes

Nowadays, substantial efforts are devoted to decrease our dependence on fossil fuels. This change will heavily rely on development of new and improved catalytic processes. Over the past two decades, catalytic hydrogen production from wet biomass and organic compounds in sub- and supercritical water (SCW) has gained significant attention. In this process, catalysts are employed to enhance the gas formation rate at moderate temperatures. Catalysts can be also utilized to shift the product distribution toward a more desirable compound (e.g. hydrogen). The effectiveness of various types of heterogeneous catalysts, mainly containing nickel and ruthenium, have been demonstrated for hydrothermal gasification of organic compounds. Catalyst formulation along with operating conditions such as temperature and feed concentration can significantly affect the conversion and selectivity of the process. This paper reviews the major findings of hydrothermal gasification over the past two decades with the aid of heterogeneous catalysts in terms of activity, hydrogen selectivity and stability. Commercially available and laboratory-prepared catalysts including supported and skeletal metal catalysts, activated carbon, oxides, metal wires and other innovative catalysts are considered. Results of supercritical water gasification (SCWG) of various feedstocks reported in the literature are compared and possible mechanisms and rates of deactivation of heterogeneous catalysts are discussed.     

Investigation of the interaction between intermediates from gasification of biomass in supercritical water: Formaldehyde/formic acid mixtures

Supercritical water gasification (SCWG) is a promising technology for converting wet biomass and waste into renewable energy. While the fundamental mechanism involved in SCWG of biomass is not completely understood, especially hydrogen (H₂) production produced from the interaction among key intermediates. In the present study, formaldehyde mixed with formic acid as model intermediates were tested in a batch reactor at 400 °C and 25 MPa for 30 min. The gas and liquid phases were collected and analyzed to determine a possible mechanism for H₂ production. Results clearly showed that both gasification efficiency (GE) and hydrogen efficiency (HE) increased with addition of formic acid, and the maximum H₂ yield reached 17.92 mol/kg with a relative formic acid content of 66.67% in the mixtures. The total organic carbon removal rate and formaldehyde conversion rate also increased to 67.33% and 89.81% respectively. The reaction pathways for H₂ formation form mixtures was proposed and evaluated, formic acid promoted self-decomposition of formaldehyde to generate H₂, and induced a radical reaction of generated methanol to produce more H₂.     

Comparative study on corrosion characteristics of Al2O3/316L and TiO2/316L stainless steel in supercritical water

Al₂O₃ and TiO₂ coatings were fabricated on 316L stainless steel by atmospheric plasma spraying to improve the corrosion resistance of 316L stainless steel in supercritical water. The corrosion characteristics of the samples were evaluated in a batch reactor at 500 °C and 25 MPa with an oxygen concentration of 1000 mg/L for 80 h. The adhesive strengths of the coated samples were tested, and the weight changes, morphologies and elements distributions of the fresh and corroded samples were analyzed. Results showed that the bond strength of TiO₂/316L was 1.5 times than that of Al₂O₃/316L (26.639 N/mm²). The surface morphology of Al₂O₃/316L showed gully erosion with much pores and cracks after exposed in SCW, which provided channels for oxygen and SCW to get into the substrate and also the elements in substrate to diffuse to the surface of the coating. The corroded Al₂O₃/316L suffered significant weight loss, and most of the coatings were peeled off. However, the surface morphology of TiO₂/316L was relatively dense and the thickness of the coating was not found to decrease obviously.     

Gasification of biomass model compounds in supercritical water: Detailed reaction pathways and mechanisms

Supercritical water gasification (SCWG) technology is an efficient and clean method to utilize biomass wastes. But the real biomass is complicated, bringing difficulties for the research of reaction pathway. In this paper, xylose was selected as a model compound for hemicellulose and the experiment was conducted in quartz reactors. The degradation pathway of xylose in supercritical water (SCW) was discussed. The main intermediates included phenols, furans, arenes, organic acids, ketones and alcohols. Phenols and arenes were difficult to be gasified while furans, organic acids, ketones and alcohols could be easily gasified. The degradation pathways of glucose and guaiacol as model compounds for cellulose and lignin in SCW have also been discussed in previous studies. By comparing the experimental data, it is found that guaiacol was more difficult to be gasified than glucose and xylose. The main organics in residual liquid of xylose and glucose were furans, cyclic ketones, open-chain compounds, phenols and arenes while that of guaiacol were phenols, arenes and open-chain compounds. The degradation of phenols and arenes was the key step of SCWG of biomass model compounds.     

Effects of temperature on corrosion performances of TiO2/SS316L in supercritical water for hydrogen production

Temperature is the most important factor for hydrogen generation during supercritical water gasification process. However, the increasing temperature could accelerate the corrosion of the reactor material, at the presence of oxygen, as less amount of oxygen can promote the hydrogen production. In this study, we prepared a 0.1 mm thick of TiO₂ coating on the surface of 316L stainless steel (SS316L) to enhance the corrosion resistance of SS316L during hydrogen production process in supercritical water. The influences of temperature (400–500 °C) on surface morphologies and corrosion depth and rate of TiO₂/SS316L were evaluated at 25 MPa with 1000 mg/L oxygen for 80h. Results showed that cracks and pores were present on the surface of TiO₂/SS316L after corroded in SCW for 80h. The crack width and corrosion rate was aggravated at higher temperature. The remained thickness of the coating at 400 °C, 450 °C, 500 °C were 0.08 mm, 0.05 mm and 0.03 mm, respectively. NiO and NiFe₂O₄ were generated around the crack on the surface of TiO₂/316L at 500 °C, the coating had a tendency to peel off the substrate.     

Hydrogen production by partial oxidative gasification of biomass and its model compounds in supercritical water

Partial oxidative gasification in supercritical water is a new technology for hydrogen production from biomass. Firstly in this paper, supercritical water partial oxidative gasification process was analyzed from the perspective of theory and chemical equilibrium gaseous product was calculated using the thermodynamic model. Secondly, the influence of oxidant equivalent ratio on partial oxidative gasification of model compounds (glucose, lignin) and real biomass (corn cob) in supercritical water was investigated in a fluidized bed system. Experimental results show that oxidant can improve the gasification efficiency, and an appropriate addition of oxidant can improve the yield of hydrogen in certain reaction condition. When ER equaled 0.4, the gasification efficiency of lignin was 3.1 times of that without oxidant. When ER equaled 0.1, the yield of hydrogen from lignin increased by 25.8% compared with that without oxidant. Thirdly, the effects of operation parameters including temperature, pressure, concentration, and flow rate of feedstock on the gasification were investigated. The optimal operation parameters for supercritical water partial oxidative gasification were obtained.     

Technical and economic evaluation of solar hydrogen production by supercritical water gasification of biomass in China

A novel thermochemical method for solar hydrogen production was proposed by state key laboratory of multiphase flow in power engineering (SKLMFPE) of Xi’an Jiaotong University. In this paper, a technical and economic evaluation of the new solar hydrogen production technology was conducted. Firstly, the advantages of this new solar hydrogen production process, compared with other processes, were assessed and thermodynamic analysis of the new process was carried out. The results show that biomass gasification in supercritical water driven by concentrating solar energy may be used to achieve high efficiency solar thermal decomposition of water and biomass for hydrogen production. Secondly, the hydrogen production cost was analyzed using the method of the total annual revenue requirement. The estimated hydrogen production cost was 38.46RMB/kg for the experimental demonstration system with a treatment capacity of 1 ton wet biomass per hour, and it would be decreased to 25.1 RMB/kg if the treatment capacity of wet biomass increased from 1 t/h to 10 t/h. A sensitivity analysis was also performed and influence of parameters on the hydrogen production cost was studied. The results from technical and economic evaluation show that supercritical water gasification of biomass driven by concentrated solar energy is a promising technology for hydrogen production and it is competitive compared to other solar hydrogen production technologies.     

Gasification of two and three-components mixture in supercritical water: Influence of NaOH and initial reactants of acetic acid and phenol

Acetic acid (HAc) and phenol are the most common and refractory compounds during supercritical water gasification (SCWG) of organic waste water for hydrogen production. Here we report SCWG of HAc and the two and three-components mixture containing HAc and phenol with and without sodium hydroxide catalyst, which was conducted in a tubular flow reactor. Sodium hydroxide had a catalytic effect on the steam reforming reaction of methane during SCWG of HAc. For SCWG of HAc (0.5wt%) and phenol (1.0wt%) mixture, yield of hydrogen and carbon dioxide reached a maximum at 0.2wt% of sodium hydroxide. The hydrogenation of phenol to form benzene and further to cyclohexane can be reinforced by the acceleration of NaOH on hydrogen production. The amount of undesired long-chain alkyl esters were also found in the liquid products. Large amount of sodium acetate and sodium phenolate formed at high NaOH concentrations, which can lead to lower reaction efficiency and more serious deposition and coking problem. For SCWG of the three-components (methanol, HAc and phenol) mixture, TOC (Total Organic Carbon) removal efficiency, H and C gasification efficiency can be strongly retarded by both HAc and phenol. Decarboxylation of HAc leaded to relatively higher C gasification efficiency. Besides, their empirical quadric polynomial regression models were provided via response surface method.     

Hydrogen production by biomass gasification in supercritical water with bimetallic Ni-M/γAl2O3 catalysts (M = Cu, Co and Sn)

Supercritical water gasification (SCWG) of wet biomass is a very promising technology for hydrogen energy and the utilization of biomass resources. Ni-based catalysts are effective in catalyzing SCWG of original biomass and organic compounds for hydrogen production. In this paper, hydrogen production by SCWG of glucose over alumina-supported nickel catalysts modified with Cu, Co and Sn was studied. The bimetallic Ni-M (M = Cu, Co and Sn) catalysts were prepared by a co-impregnation method and tested in an autoclave reactor at 673 K with a feedstock concentration of 9.09 wt.%. XRD, XRF, N₂ adsorption/desorption, SEM and TGA were adopted to investigate the changes of chemical properties between Ni and Ni-M catalysts and the deactivation mechanism of catalysts. According to the experimental results, the hydrogen yield followed this order: Ni-Cu/γAl₂O₃ > Ni/γAl₂O₃ > Ni-Co/γAl₂O₃ > Ni-Sn/γAl₂O₃. The results show that Cu could improve the catalytic activity of Ni catalyst in reforming reaction of methane to produce hydrogen in SCWG. In addition, Cu can mitigate the sintering of alumina detected by SEM. Co was found to be an excellent promoter of Ni-based catalyst in relation to hydrogen selectivity.     

Influences of oxygen on corrosion characteristics of TiO2/316L stainless steel in supercritical water

Supercritical water gasification (SCWG) is a promising technology for converting organic wastes to hydrogen. Less amount of oxygen is beneficial for increasing hydrogen generation rate. However, the corrosion rate of reactor material would be accelerated. TiO₂ coating with a thickness of 0.1 mm was prepared on the surface of 316L stainless steel (SS316L) to improve its corrosion resistance in supercritical water (SCW). The corrosion performances of TiO₂/SS316L were tested in a bath SCW reactor at 400 °C, 25 MPa. The influences of oxygen concentration (0–1000 mg/L) on surface morphologies and corrosion depths were studied thoroughly. Results indicated that the surface of TiO₂/SS316L exhibited cracks and pores after exposed in SCW. And the average corrosion rates accelerated at higher oxygen concentrations. The interface between the coating and medium was relatively smooth and there was no obvious change in the thickness of the coating with oxygen concentration of 0 and 500 mg/L. While for that with 1000 mg/L oxygen, the surface of TiO₂/SS316L exhibited reticulate crack. The cross section showed a serrate structure, and only 0.08 mm thick of the coating was remained. In addition, the corrosion mechanism of coating was discussed.     

Hydrogen production by biomass gasification in supercritical water using concentrated solar energy: System development and proof of concept

A novel system of hydrogen production by biomass gasification in supercritical water using concentrated solar energy has been constructed, installed and tested at the State Key Laboratory of Multiphase Flow in Power Engineering (SKLMF). The “proof of concept” tests for solar-thermal gasification of biomass in supercritical water (SCW) were successfully carried out. Biomass model compounds (glucose) and real biomass (corn meal, wheat stalk) were gasified continuously with the novel system to produce hydrogen-rich gas. The effect of direct normal solar irradiation (DNI) and catalyst on gasification of biomass was also investigated. The results showed that the maximal gasification efficiency (the mass of product gas/the mass of feedstock) in excess of 110% were reached, hydrogen fraction in the gas product also approached to 50%. The experimental results confirmed the feasibility of the system and the advantage of the process, which supports future work to address the technical issues and develop the technology of solar-thermal hydrogen production by gasification of biomass in supercritical water.     

Conversion of brown coal in supercritical water without and with addition of oxygen at continuous supply of coal-water slurry

A study of conversion of organic matter of brown coal in supercritical water (SCW) at 30 MPa, 400−760 °C and continuous supply of coal-water slurry (CWS) into a tubular reactor is presented. It was found that 48−63% (depending on the SCW temperature) of coal organic matter (COM) is ejected from CWS coal particles as liquid and gaseous products when they move through the reactor. We termed this stage of SCW conversion as dynamic conversion (DC) of coal. It turns out that the particles which underwent the DC stage did not aggregate in the reactor during static conversion (SC) within a coal layer due to continuous pumping through this layer. The experimental data on the composition of DC and SC products, degree of coal conversion, and the data on the degree of combustion of carbon in the presence of oxygen are given.     

Hydrogen production by supercritical water gasification of biomass: Particle and residence time distribution in fluidized bed reactor

Particle distribution and residence time distribution (RTD) in supercritical water fluidized bed reactor (SCWFBR) greatly affect the hydrogen yield through determining the two phase mixing and reaction time. A Eulerian model incorporating the kinetic theory for solid particles was applied to simulate the solid distribution and RTD of feeding materials. The effect of four types of feeding methods and feeding rates on solid distribution and RTD were evaluated based on the simulation results. Results showed that double symmetrical feeding pipe with an feeding mouth angle of 45° provides more uniform solid distribution and longer residence time compared with those of other three types. A nonlinear relationship between feeding rate and RTD was observed, and an optimum feeding rate was found to be related to the best solid-fluid mixing in the study.     

Effect of nickel loading on hydrogen production and chemical oxygen demand (COD) destruction from glucose oxidation and gasification in supercritical water

Gasification and partial oxidation of 0.25 molar glucose solution was conducted over different metallic nickel (Ni) loadings (7.5, 11, and 18 wt%) on different catalyst supports (θ-Al₂O₃ and γ-Al₂O₃) in supercritical water. Experiments were carried out at three different temperatures (T) of 400, 450, and 500 °C at constant pressure of 28 MPa and a 30 min reaction time (t). For comparison, some experiments were conducted using high loading commercial catalyst (65 wt% Ni on Silica–alumina). Hydrogen peroxide (H₂O₂) was used as a source of oxygen in the partial oxidation experiments. Oxygen to carbon molar ratios (MR) of 0.5–0.9 were examined to increase the hydrogen production via carbon monoxide (CO) production. Results showed that in the absence of the catalyst, the optimum molar ratio was 0.8 i.e. 80% of the amount of oxygen required for complete oxidation of glucose. At a molar ratio of 0.8, the hydrogen yield was 0.3 mol/mol, as compared to 0.2 mol/mol glucose at molar ratio of 0.5 and 0.9. This optimized oxygen dose was adopted as a base line for catalysts evaluation. The main gaseous products were carbon dioxide (CO₂), carbon monoxide (CO), hydrogen (H₂), and methane (CH₄). Results also showed that the presence of Ni increased the total gas yield increased in the 7.5–18 wt Ni/Al₂O₃ catalyst. An increase in MR from 0.55 to 0.8 increased the of carbon dioxide and hydrogen yields from 1.8 to 3.8 mol/mol glucose and from 0.9 to 1.1 mol/mol. The carbon monoxide and methane yields remain constant at 2 and 0.5 mol/mol glucose, respectively. The introduction of hydrogen peroxide (H₂O₂) prior to the feed injection inhibited the catalyst activity and did not increase the hydrogen yield whereas the introduction of H₂O₂ after 15 min of reaction time increased the hydrogen yield from 0.62 mol/mol to 1.5 mol/mol. This study showed that approximately the same hydrogen yield can be obtained from the synthesized low nickel alumina loading (18 wt%) catalyst as with the 65 wt% nickel on silica–alumina loading commercial catalyst. The highest H₂ yield of 1.5 mol/mol glucose was obtained with commercial Ni/silica–alumina with a BET surface area of 190 m²/g compared to 1.2 mol/mol with the synthesized Ni/θ alumina with a BET surface area of 46 m²/g.     

Stability and activity of a co-precipitated Mg promoted Ni/Al2O3 catalyst for supercritical water gasification of biomass

We have investigated the stability and activity of a co-precipitated Mg promoted Ni/Al₂O₃ catalyst (Ni-Mg-Al) for supercritical water gasification (SCWG) of various biomass model compounds and real biomass. Phase stability and activity recovery of the Ni-Mg-Al catalyst were first compared with a catalyst prepared by impregnation method. It was found that the co-participated catalyst showed higher activity recoveries than the impregnated catalyst due to the stable Ni crystal size. Then, effects of SCWG variables including heating up rate, gasification temperature, catalyst loading amount and feedstock concentration, on the non-catalytic and catalytic gas yields and gasification efficiencies of glucose and phenol were evaluated. Results demonstrated that the presence of sufficient amount of Ni catalyst could realize complete carbon gasification of different organics, including phenol and real biomass. Catalyzed by Ni, CH₄ was the more favored produced gas at 400–500 °C while H₂ yields were more abundant at 500–600 °C. Without catalyst, carbon gasification efficiencies of SCWG of different feedstock were in the order: glycerol > glucose > cellulose ≈ corncob ≈ poplar leaf ≈ sawdust > phenol, while those catalyzed by Ni were in the order: glycerol ≈ glucose ≈ cellulose ≈ phenol > corncob ≈ poplar leaf ≈ sawdust, illustrating that the co-precipitated NiMgAl catalyst is more active on catalyzing the gasification of water-soluble organics than real biomass.     

Hydrogen production from 2-propanol over Pt/Al2O3 and Ru/Al2O3 catalysts in supercritical water

One of the alternative energy sources to fossil fuels is the use of hydrogen as an energy carrier, which provides zero emission of pollutants and high-energy efficiency when used in fuel cells, hydrogen internal combustion engines (HICE) or hydrogen-blend gaseous fueled internal combustion engines (HBICE). The gasification of organics in supercritical water is a promising method for the direct production of hydrogen at high pressures, with very short reaction times. In this study, hydrogen production from 2-propanol over Pt/Al₂O₃ and Ru/Al₂O₃ catalysts was investigated in supercritical water. To investigate the influences on hydrogen production, the experiments were carried out in the temperature range of 400–550 °C and in the reaction time range of 10–30 s, under a pressure of 25 MPa. In addition, different 2-propanol concentrations and reaction pressures were tested in order to comprehend the effects on the gasification yield and hydrogen production. It was found that Pt/Al₂O₃ catalyst was much more selective and effective for hydrogen production when compared to Ru/Al₂O₃. During the catalytic gasification of a 0.5 M solution of 2-propanol, a hydrogen content up to 96 mol% for a gasification yield of 5 L/L feed was obtained.     

Hydrogen and power generation from supercritical water reforming of glycerol and pressurized SOFC integrated system: Use of different CO2 adsorption process

The performance analysis of an integrated system of glycerol supercritical water reforming and pressurized SOFC was presented. The use of different CO₂ adsorption processes that include in situ and ex situ processes was compared to determine the suitable process for hydrogen and power generations. The influence of operating condition, e.g., temperature and pressure of reformer, supercritical water to glycerol (S/G) molar ratio, and calcium oxide to glycerol (CaO/G) molar ratio was examined. Then, the electrical performance of each integrated process was considered with respect to the SOFC conditions comprising temperature, pressure, and current density. The simulation results revealed that both processes have same favourable conditions for temperature and pressure operated at 800 °C and 240 atm, respectively. The suitable S/G and CaO/G molar ratios for in situ process are 10 and 2 whereas those for ex situ process are 20 and 1. Under these conditions, maximum hydrogen can be achieved as 87% and 75% for in situ and ex situ processes, respectively. When both integrated processes are operated at the optimal SOFC conditions as 900 °C, 4 atm, and current density of 10,000 A/m², the SOFC efficiency of 71.56% and 62.12% can provide for in situ and ex situ processes, respectively.     

Effect of sulfide on corrosion behavior of stainless steel 316SS and Hastelloy C276 in sub/supercritical water

Stainless steel 316SS and Hastelloy C276, as the representatives of iron-based and nickel-based alloy, respectively, were employed to explore the corrosion properties under reducing subcritical and supercritical water containing sulfide. Experiments were executed at a pressure of 25 MPa, temperatures of 350 °C–520 °C, and sulfur concentrations of 1000 and 5000 ppm for 80 h. An isothermal equilibrium phase diagram involving the oxidation/sulfidation products of Fe, Cr, and Ni, was established by theoretical calculation in supercritical water system at 520 °C, in order to predict the corresponding products under various conditions and assist the discussion on corrosion mechanism. The results show that whether in subcritical water or in supercritical water, 316SS always exhibited better corrosion resistance relative to C276. In subcritical water at 350 °C, a portion of corrosion film peeled off from 316SS specimen, while numerous pores or cracks appeared on the surface of scale for C276. Under supercritical water at 520 °C, a compact scale grown on 316SS sample surface was composed of Fe₃O₄, FeCr₂O₄, and FeS. For C276, a duplex-layer scale formed on alloy surface. However, due to the higher content of Ni in C276, Ni-sulfide channels through the inner layer were developed, accelerating the sulfidation corrosion of alloys. Overall, the high-temperature alloys with high Cr content and low Ni/Cr ratio can be considered as the candidate material of equipment in supercritical water gasification of sulfur-containing coal.     

Hydrogen production from co-gasification of coal and biomass in supercritical water by continuous flow thermal-catalytic reaction system

Hydrogen is a clean energy carrier. Converting abundant coal sources and green biomass energy into hydrogen effectively and without any pollution promotes environmental protection. The co-gasification performance of coal and a model compound of biomass, carboxymethylcellulose (CMC) in supercritical water (SCW), were investigated experimentally. The influences of temperature, pressure and concentration on hydrogen production from co-gasification of coal and CMC in SCW under the given conditions (20–25 MPa, 650°C, 15–30 s) are discussed in detail. The experimental results show that H₂, CO₂ and CH₄ are the main gas products, and the molar fraction of hydrogen reaches in excess of 60%. The higher pressure and higher CMC content facilitate hydrogen production; production is decreased remarkably given a longer residence time. Translated from Journal of Xi’an Jiao Tong University, 2005, 39(5): 454–457 [译自: 西安交通大学学报]     

Comparative study of bio-ethanol production from mahula (Madhuca latifolia L.) flowers by Saccharomyces cerevisiae and Zymomonas mobilis

Mahula (Madhuca latifolia L.) flower is a suitable alternative cheaper carbohydrate source for production of bio-ethanol. Recent production of bio-ethanol by microbial fermentation as an alternative energy source has renewed research interest because of the increase in the fuel price. Saccharomyces cerevisiae (yeast) and Zymomonas mobilis (bacteria) are two most widely used microorganisms for ethanol production. In this study, experiments were carried out to compare the potential of the yeast S. cerevisiae (CTCRI strain) with the bacterium Z. mobilis (MTCC 92) for ethanol fermentation from mahula flowers. The ethanol production after 96 h fermentation was 149 and 122.9 g kg⁻¹ flowers using free cells of S. cerevisiae and Z. mobilis, respectively. The S. cerevisiae strain showed 21.2% more final ethanol production in comparison to Z. mobilis. Ethanol yield (Yx/s), volumetric product productivity (Qp), sugar to ethanol conversion rate (%) and microbial biomass concentration (X) obtained by S. cerevisiae were found to be 5.2%, 21.1%, 5.27% and 134% higher than Z. mobilis, respectively after 96 h of fermentation.