Comparison of pulp-mill-integrated hydrogen production from gasified black liquor with stand-alone production from gasified biomass

When gasified black liquor is used for hydrogen production, significant amounts of biomass must be imported. This paper compares two alternative options for producing hydrogen from biomass: (A) pulp-mill-integrated hydrogen production from gasified back liquor; and (B) stand-alone production of hydrogen from gasified biomass. The comparison assumes that the same amount of biomass that is imported in Alternative A is supplied to a stand-alone hydrogen production plant and that the gasified black liquor in Alternative B is used in a black liquor gasification combined cycle (BLGCC) CHP unit. The comparison is based upon equal amounts of black liquor fed to the gasifier, and identical steam and power requirements for the pulp mill. The two systems are compared on the basis of total CO₂ emission consequences, based upon different assumptions for the reference energy system that reflect different societal CO₂ emissions reduction target levels. Ambitions targets are expected to lead to a more CO₂–lean reference energy system, in which case hydrogen production from gasified black liquor (Alternative A) is best from a CO₂ emissions’ perspective, whereas with high CO₂ emissions associated with electricity production, hydrogen from gasified biomass and electricity from gasified black liquor (Alternative B) is preferable.     

Catalytic supercritical water gasification of black liquor along with lignocellulosic biomass

Supercritical water gasification (SCWG) is a novel technology for environmental pollution management and hydrogen production from biomass and wastes. In this study, the SCWG of black liquor (BL) which is high-potential biomass and rich in alkalis was investigated. The experiments were conducted in a batch reactor at 350–400 °C, reaction time of 1–60 min, and constant concentration of 9 wt% of BL in the absence and presence of heterogeneous catalysts (3–5 wt%), lignocellulosic biomass, and formic acid (5 and 7 wt %) in three parts. First, the SCWG of BL was performed without any additive. The experimental results showed that the maximum production of H₂, CO₂, and CH₄ was obtained at the highest temperature and reaction time; 400 °C and 60 min. The hydrogen yield was also enhanced by increasing the temperature, and reached 3.51 mol H₂/kg dry ash free-black liquor (DAF-BL) at 400 °C. Reaction time increment improved the gas product and gasification efficiency up to 28.03 mmol and 21.73%, respectively. Subsequently, three heterogeneous catalysts (MnO₂, CuO, and TiO₂) were used, however 5 wt% of MnO₂ was the best catalyst, significantly improving the hydrogen yield compared to the same condition of BL gasification without a catalyst. Hydrogen yield reached 5.09 mol H₂/kg (DAF-BL) at 400 °C and the reaction time of 10 min. Finally, BL with poplar wood residue as a lignocellulosic biomass and formic acid was gasified separately and the highest hydrogen yield was obtained in the case of 5 wt% of formic acid (10.79 mol H₂/kg (DAF-BL)). Overally, SCWG dramatically reduced the chemical oxygen demand of BL to 76% using 5 wt% of formic acid.     

Sustainable hydrogen production options from food wastes

In this study, two thermochemical processes, namely steam gasification and supercritical water gasification (SCWG), were comparatively studied to produce hydrogen from food wastes containing about 90% water. The SCWG experiments were performed at 400 and 450 °C in presence of catalyst (Trona, K₂CO₃ and seaweed ash). The maximum hydrogen yield was obtained at 450 °C in presence of K₂CO₃ catalyst. In second process, hydrothermal carbonization was used to convert food wastes into a high-quality solid fuel (hydrochar) that was further gasified in a dual-bed reactor in presence of steam. The steam gasification of hydrochar was carried out with and without catalysts (iron?ceria catalyst and dolomite). The maximum hydrogen yield obtained from steam gasification process was 28.08 mmol/g dry waste, about 7.7 times of that from SCWG. This study proposed a new concept for hydrogen production from wet biomass, combination of hydrothermal carbonization following steam gasification.     

Solar receiver/reactor for hydrogen production with biomass gasification in supercritical water

A novel receiver/reactor driven by concentrating solar energy for hydrogen production by supercritical water gasification (SCWG) of biomass was designed, constructed and tested. Model compound (glucose) and real biomass (corncob) were successfully gasified under SCW conditions to generate hydrogen-rich fuel gas in the apparatus. It is found that the receiver/reactor temperature increased with the increment of the direct normal solar irradiation (DNI). Effects of the DNI, the flow rates and concentration of the feedstocks as well as alkali catalysts addition were investigated. The results showed that DNI and flow rates of reactants have prominent effects on the temperature of reactor wall and gasification results. Higher DNI and lower feed concentrations favor the biomass gasification for hydrogen production. The encouraging results indicate a promising approach for hydrogen production with biomass gasification in supercritical water using concentrated solar energy.     

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.     

Hydrogen production by supercritical water gasification of biomass: Explore the way to maximum hydrogen yield and high carbon gasification efficiency

Supercritical water gasification (SCWG) is a promising technology for wet biomass utilization. In this paper, orthogonal experimental design method, which can minimize the number of experiments compared with the full factorial experiments, was used to optimize the operation parameters of SCWG with a tubular reactor system. Using this method, the influences of the main parameters including pressure, temperature, residence time and solution concentration on biomass gasification were also investigated. Simultaneously, in order to further improve the gasification efficiency of biomass, acid hydrolysis pretreatment of feedstock, oxidizers addition and increasing reaction temperature were employed. Results from the experiments show that in the range of experimental parameters, the order of the effects of the factors on H₂ yield of corn cob gasification in SCW is temperature > pressure > feedstock concentration > residence time. Temperature and pressure have a significant and complicated effect on biomass gasification. Hydrogen yield increases by the acid hydrolysis pretreatment of feedstock, and oxidizer addition reduces the hydrogen yield but it promotes the increase in carbon gasification efficiency. Biomass feedstock with high concentration was gasified successfully at high reaction temperature.     

Supercritical water gasification of food waste: Effect of parameters on hydrogen production

Food waste is a type of municipal solid waste with abundant organic matter. Hydrogen contains high energy and can be produced by supercritical water gasification (SCWG) of organic waste. In this study, food waste was gasified at various reaction times (20–60 min) and temperatures (400 °C-450 °C) and with different food additives (NaOH, NaHCO₃, and NaCl) to investigate the effects of these factors on syngas yield and composition. The results showed that the increase in gasification temperature and time improved gasification efficiency. Also, the addition of food additives with Na⁺ promoted the SCWG of food waste. The highest H₂ yield obtained through non-catalytic experiments was 2.0 mol/kg, and the total gas yield was 7.89 mol/kg. NaOH demonstrated the best catalytic performance in SCWG of food waste, and the highest hydrogen production was 12.73 mol/kg. The results propose that supercritical water gasification could be a proficient technology for food waste to generate hydrogen-rich gas products.     

Supercritical water gasification of black liquor with wheat straw as the supplementary energy resource

Supercritical water gasification (SCWG) is a new treatment of black liquor (BL) for both energy recovery and pollution management. To provide more energy for the pulp mill, it is proposed to use the pulping raw material as supplementary energy source because it is readily available, inexpensive and renewable. In this study, co-gasification of BL and wheat straw (WS) in supercritical water was investigated. The synergistic effect was observed in the co-gasification because the addition of wheat straw can make better use of the alkali in BL. The maximum improvement of the gasification by the synergistic effect was obtained with the mixing ratio of 1:1. The influences of the temperature (500–750 °C), reaction time (5–40 min), mixture concentration (5.0–19.1 wt%), mixing ratio (0–100%) and the wheat straw particle diameter (74–150 μm) were studied. It was found that the increase of temperature and reaction time, and the decrease of concentration and wheat straw particle size favored the gasification by improving the hydrogen production and gasification efficiency. The highest carbon gasification efficiency of 97.87% was obtained at 750 °C. Meanwhile, the H₂ yield increased from 12.29  mol/kg at 500 °C to 46.02  mol/kg. This study can help to develop a distributed energy system based on SCWG of BL and raw biomass to supply energy for the pulp mill and surrounding communities.     

Low temperature supercritical water gasification of biomass constituents: Glucose/phenol mixtures

Supercritical water gasification (SCWG) is an interesting technology for the production of energy from wet and residual biomass. To date, the complete understanding of the fundamental phenomena involved in SCWG is still an open issue. An interesting aspect to be investigated is represented by the interactions among the single constituents of biomass, such as cellulose and lignin. This can be accomplished by using glucose and phenol as model compounds. In the present study, four glucose/phenol mixtures were utilized. All mixtures presented a constant organics mass fraction of 5%, where the relative fraction of phenol ranged from 0% (pure glucose) to 30%. The mixtures were gasified at 400 °C and 25.0 MPa in a continuous tubular reactor, with a residence time between 10 and 240 s. Results showed that, at the considered reaction conditions, phenol mostly behaves as a sort of inert in terms of total gas production, although it plays an inhibitory action towards H₂. The analysis of the liquid phase revealed that phenol likely inhibits Cannizzaro and de-carbonylation reactions and it advantages the pathways involving de-hydration reactions.     

Supercritical water gasification and partial oxidation of municipal sewage sludge: An experimental and thermodynamic study

Supercritical gasification (SCWG) and supercritical partial oxidation (SCWPO) technologies have emerged as preferred means of converting wet biomass to hydrogen-rich gases. We experimentally investigated the effects of moisture content, pressure and oxidation coefficient (n) on mole fraction, yield, gasification efficiency and energy recovery of gaseous products from SCWG or SCWPO of municipal sewage sludge, as well as on the carbon and nitrogen contents in liquid products. Potential of sludge for producing gaseous products was thermodynamically analyzed by an Aspen Plus model. The results show that 87 wt%, 25 MPa and n = 0 were optimum conditions for sludge gasification. Sludge with 87 wt% moisture content was pumpable at 75 °C, and further increasing the moisture content decreased the heating value and energy recovery of gaseous products. Pressure played little role in both the experimental and equilibrium gas yields. Highest mole fractions and yields of H₂ and CH₄ were achieved at n = 0.     

Gasification characteristics of organic waste by molten salt

Recently, along with the growth in economic development, there has been a dramatic accompanying increase in the amount of sludge and organic waste. The disposal of such is a significant problem. Moreover, there is also an increased in the consumption of electricity along with economic growth. Although new energy development, such as fuel cells, has been promoted to solve the problem of power consumption, there has been little corresponding promotion relating to the disposal of sludge and organic waste. Generally, methane fermentation comprises the primary organic waste fuel used in gasification systems. However, the methane fermentation method takes a long time to obtain the fuel gas, and the quality of the obtained gas is unstable. On the other hand, gasification by molten salt is undesirable because the molten salt in the gasification gas corrodes the piping and turbine blades. Therefore, a gasification system is proposed by which the sludge and organic waste are gasified by molten salt. Moreover, molten carbonate fuel cells (MCFC) are needed to refill the MCFC electrolyte volatilized in the operation. Since the gasification gas is used as an MCFC fuel, MCFC electrolyte can be provided with the fuel gas. This paper elucidates the fundamental characteristics of sludge and organic waste gasification. A crucible filled with the molten salt comprising 62 Li₂CO₃/38 K₂CO₃, is installed in the reaction vessel, and can be set to an arbitrary temperature in a gas atmosphere. In this instance, the gasifying agent gas is CO₂. Sludge or the rice is supplied as organic waste into the molten salt, and is gasified. The chemical composition of the gasification gas is analyzed by a CO/CO₂ meter, a HC meter, and a SO_x meter gas chromatography. As a result, although sludge can generate CO and H₂ near the chemical equilibrium value, all of the sulfur in the sludge is not fixed in the molten salt, because the sludge floats on the surface of the carbonate by the specific gravity of sludge lighter than the carbonate, and is not completely converted into CO and H₂. Moreover, the rice also shows good characteristics as a gasifying agent. Consequently, there is high expectation to using the organic waste as a molten salt gasifying agent. However, this requires lengthening the contact time between the organic waste and the molten salt.     

Investigation of the conversion mechanism for hydrogen production by coal gasification in supercritical water

The technology of supercritical water gasification (SCWG) of coal has a great prospect because it converts coal into hydrogen-rich gas products efficiently and cleanly. However, there are bottlenecks affecting the complete gasification of coal in supercritical water (SCW) without catalyst under moderate conditions. This work is to explore the restricted factor for complete gasification of coal in SCW by investigating the conversion mechanism. The conversion mechanism of SCWG of coal with and without K₂CO₃ is proposed. Polycyclic aromatic hydrocarbons (PAHs) with graphite phase structures are formed by the condensation of aromatic structures at 550–750 °C. It is the restricted factor due to its characteristic of difficulty to be gasified. There is no condensation of aromatic structures in the process of SCWG of coal with K₂CO₃, which effectively inhibited the formation of PAHs with graphite phase structures. K₂CO₃ dramatically promoted the SCWG of coal, leading to carbon gasification efficiency (CE) reaching 98.43%.     

Gasification of diosgenin solid waste for hydrogen production in supercritical water

The potential of diosgenin solid waste (DSW) to be a proper feedstock for hydrogen production from supercritical water gasification was assessed through thermodynamic analysis and experimental study. The thermodynamic analysis of DSW gasification in SCW was performed by Aspen Plus software based on the principle of minimum Gibbs free energy. The effects of temperature (500–650 °C), flow ratio of feedstock slurry to preheated water on the gasification were studied. K₂CO₃ and black liquor were used to catalyze the gasification of DSW. The morphological structures of DSW and residue char were characterized by SEM. The results showed that DSW was almost completely gasified at 650 °C without catalyst and the carbon gasification efficiency reached up to 98.55%. K₂CO₃ could significantly promote the gasification reactivity of DSW at a lower temperature. H₂ yield was remarkably improved by adding black liquor. The SEM analysis indicated that parts of the organic matters reacted to form gases and liquid products, and K₂CO₃ was found to migrate into the residue char during the reactions.     

Gasification of horse dung in supercritical water

Horse dung naturally contains phosphorus and nitrogen which affect the environment negatively, if the nutrients are not recovered and utilized. In this paper, the influence of alkali on the gasification of horse dung at 560 °C, 25 MPa was investigated. The results show that LiOH addition increased H₂ fraction and the gas yield. The precipitated alkali in the reactor still showed high catalytic effect on the subsequent gasification of horse dung without further adding the alkali. A novel 4-lump kinetic model for horse dung in SCWG including feedstock, CH₄, CO, and CO₂ lumps is proposed.     

Catalytic effect of black liquor on the gasification reactivity of petroleum coke

CO₂ gasification of petroleum coke using black liquor as a catalyst was performed in a thermogravimetric analyzer (TGA) under temperatures 1223–1673 K at ambient pressure to evaluate the effect of black liquor loading on petroleum coke gasification. It was found that the gasification reactivity of petroleum coke was improved greatly by black liquor. The gasification reactivity was affected by different loading methods in the order: wet grinding > dry grinding > physical impregnation > dry mix. The catalytic activity of black liquor was higher than that of pure alkali metal. The effect of temperature on the gasification reactivity of petroleum coke was changed by black liquor. The reactivity reaches its maximum at 1573 K. The reactivity of petroleum coke was found higher than that of Shenfu coal when black liquor loading is 5 wt.% (of petroleum coke), clearly demonstrating that black liquor could be an effective catalyst for petroleum coke gasification.     

Comprehensive experimental study on supercritical water gasification of oilfield sludge: Effect of operation parameters,and catalysts on the products

Supercritical water gasification (SCWG) was adopted to treat oilfield sludge and produce syngas. The effect of temperature (400–450 °C), reaction time (30–90 min) and catalyst addition on syngas production and residual products during SCWG of oilfield sludge was studied. When increasing SCWG temperature from 400 to 450 °C with reaction time of 60 min, the H₂ yield and the selectivity of H₂ increased significantly from 0.53 mol/kg and 75.53% to 0.98 mol/kg and 78.09%, respectively. It is noteworthy that when the reaction time was too long, CO₂ and CO were converted to CH₄ with the consumption of H₂ via methanation reaction. The addition of Ni/Al₂O₃ catalyst can substantially promote the production of high-quality syngas from SCWG of oilfield sludge. The H₂ yield and its selectivity at 450 °C and 60 min were as high as 1.37 mol/kg and 84.05% with 10Ni/Al catalyst. Moreover, the catalysts with bimetal loading (Fe–Ni, Rb–Ni or Ce–Ni) were found to be beneficial for improving gasification efficiency, H₂ yield, and the degradation of organic compounds. Among them, 5 wt% Rb on 10Ni/Al catalyst performed the best catalytic activity for SCWG at 450 °C and 60 min, which had the highest H₂ yield of 1.67 mol/kg and selectivity of 86.09%. More than 90% of total organic carbon in sludge was decomposed after the SCWG with all the catalysts. These findings indicated that catalytic SCWG is a promising alternative for efficiently dealing with oilfield sludge.     

Hydrogen and syngas production from sewage sludge via steam gasification

High temperature steam gasification is an attractive alternative technology which can allow one to obtain high percentage of hydrogen in the syngas from low-grade fuels. Gasification is considered a clean technology for energy conversion without environmental impact using biomass and solid wastes as feedstock. Sewage sludge is considered a renewable fuel because it is sustainable and has good potential for energy recovery. In this investigation, sewage sludge samples were gasified at various temperatures to determine the evolutionary behavior of syngas characteristics and other properties of the syngas produced. The syngas characteristics were evaluated in terms of syngas yield, hydrogen production, syngas chemical analysis, and efficiency of energy conversion. In addition to gasification experiments, pyrolysis experiments were conducted for evaluating the performance of gasification over pyrolysis. The increase in reactor temperature resulted in increased generation of hydrogen. Hydrogen yield at 1000 °C was found to be 0.076 g_gas g_sample⁻¹. Steam as the gasifying agent increased the hydrogen yield three times as compared to air gasification. Sewage sludge gasification results were compared with other samples, such as, paper, food wastes and plastics. The time duration for sewage sludge gasification was longer as compared to other samples. On the other hand sewage sludge yielded more hydrogen than that from paper and food wastes.     

Biomass gasification in supercritical water: II. Effect of catalyst

In this study, the effect of the type of catalyst on hydrothermal gasification of three specifically chosen samples of natural biomass was investigated. Biomass feedstocks, including lignocellulosic materials (cotton stalk and corncob) and the tannery waste, were gasified in supercritical water by the addition of catalyst. The catalysts used were K₂CO₃, Trona (NaHCO₃·Na₂CO₃·2H₂O), red mud (Fe-oxide containing residue from Al-production) and Raney-Ni. The gasification experiments were performed in a batch autoclave at 500 °C. The amounts and compositions of the gases and the amounts of water soluble compounds from gasification were determined. The effect of catalysts on gasification varied with the type of biomass. The catalysts significantly increased the hydrogen yield by supporting the water–gas shift reaction and the methane reformation.     

Effects of Lewis acid on catalyzing gasification of sewage sludge and model compounds in supercritical water

In this work, we investigated how different types and concentrations of Lewis acids effect gas yield and composition from supercritical water gasification (SCWG) of dewatered sewage sludge (DSS). Furthermore, the catalytic mechanism was investigated using AlCl₃ as a representative Lewis acid catalyst. Results showed that non-catalytic gasification of DSS produced a hydrogen yield of 0.13 mol/kg organic matter (OM) and total gas yield of 4.82 mol/kg OM; while the addition of 10 wt% Lewis acid resulted in a significantly improved H₂ and total gas yield of 0.77–7.76 mol/kg OM and 7.57–22.88 mol/kg OM, respectively. In addition, the Lewis acids tested herein depicted the following activity trend: AlCl₃＞FeCl₃＞NiCl₂＞ZnCl₂. The required temperature for generating hydrogen from SCWG of DSS was greatly reduced when AlCl₃ was present during the heating process. Furthermore, AlCl₃ significantly increased the hydrogen yield from SCWG of the model compounds. Finally, AlCl₃ catalyzed SCWG of guaiacol and glycerol showed the best hydrogen selectivity.     

Characteristics and prediction model of hydrogen production of oily sludge by supercritical water gasification

Harmless treatment and resource utilization of oily sludge are urgent and related to the sustainable green, and low-carbon development of the petroleum industry. Aiming to the supercritical water gasification (SCWG) of oily sludge for hydrogen production, this paper investigated the effects of critical factors, including reaction temperature, initial pressure, retention time, and feed concentration, on the mole fraction, the gas yield, the gasification efficiency, and the hydrogen yield potential. The interaction mechanisms among these four factors were discussed and revealed with a reasonable prediction model of hydrogen production. Results showed that the longer retention time, higher temperature, and lower feed concentration could accelerate hydrogen production from oily sludge by SCWG. The synthetic promotion of the hydrogen yield exists between the temperature and the retention time, while the temperature predominates. A 2.63-fold increase in the H₂ yield was obtained when the condition changed from 135 min to 380 °C to 10 min and 555 °C. The hydrogen production of oily sludge by SCWG, at lower temperature and higher pressure was worse than that at higher temperature and lower pressure.