Potassium-catalyzed steam gasification of petroleum coke for H2 production: Reactivity, selectivity and gas release

Potassium-catalyzed steam gasification of petroleum coke for H₂ production was performed using a laboratory fixed-bed reaction system with an on-line quadruple mass spectrometer. The gasification reactivity, gasification selectivity and gas release for the catalytic gasification were investigated, compared with the non-catalytic gasification. The catalytic gasification could not only effectively promote these reactions (the water-carbon reaction, the water-gas shift reaction and the methane-steam reforming reaction), but also elevate greatly the gasification selectivity towards CO₂ (a high gasification selectivity towards CO₂ meant a high H₂ production). A quantitative calculation method for the gasification selectivity towards CO and CO₂ was proposed to further understand the catalytic behaviors of catalysts. In the case of catalytic gasification, the gasification temperature had opposite effects on the gasification reactivity and the gasification selectivity towards CO₂, suggesting that there existed an optimum gasification temperature (about 750 °C) for H₂ production from the potassium-catalyzed steam gasification of petroleum coke. In addition, petroleum coke could be feasibly utilized as the feedstocks for the catalytic steam gasification to produce gases with high H₂ (55.5-60.4%) and virtually no CH₄ (below 0.1%).     

Biomass-derived hydrogen from an air-blown gasifier

The goal of this research is to produce high concentrations of hydrogen from gasification of biomass. Air-blown gasification of biomass in fluidized bed reactors produces relatively low concentrations of hydrogen (about 8 vol.%). Steam reforming of tars and light hydrocarbons and reacting steam with carbon monoxide via the water–gas shift reaction can increase hydrogen content in the producer gas to almost 30 vol.%. In these experiments, the temperature, space velocity, and steam/gas ratio were varied to determine the effect of these variables on hydrogen production. Characterization of the catalysts by X-ray photoelectron spectroscopy (XPS) and BET analysis was also performed. These analyses showed that coke and small quantities of sulfur and chlorine deposited on the catalysts, although catalytic deactivation was not evident during the tests.     

生物质水蒸气气化制取富氢合成气及其应用的研究进展

生物质水蒸气气化是有效的热化学转化手段,可将原材料转化为富氢合成气,气体应用更加广泛,有替代化石能源制氢的潜在价值。不同的生物质资源气化和产氢能力存在差异,物料的选择对气化制取富氢合成气至关重要,而调整气化操作参数包括反应温度、水蒸气加入量、催化剂和吸收剂等可进一步优化合成气质量,提升氢气含量。本文首先综述了不同操作条件对生物质水蒸气气化制取富氢合成气的影响。其次,介绍了生物质炭气化制取富氢合成气的研究现状,炭气化可制得高品质的富氢合成气,但过程受动力学限制,需要加入催化剂以提升炭气化速率。文中还简述了以钾盐为催化剂时的催化机理,并展望了富氢合成气的应用,包括制备高纯氢应用于燃料电池和制备合成天然气。     

Application of K2CO3 catalysts in the coal gasification process using nuclear heat

Conventional gasification processes use coal not only as feedstock to be gasified but also for supply of energy for reaction heat, steam production, and other purposes. With a nuclear high temperature reactor (HTR) as a source for process heat, it is possible to transform the whole of the coal feed into gas. This concept offers advantages over existing gasification processes: saving of coal, as more gas can be produced from coal; less emission of pollutants, as the HTR is used for the production of steam and electricity instead of a coal-fired boiler; and a lower production cost for the gas. However, the process has the disadvantage that the temperature is limited to the outlet temperature (950 °C max) of the helium cooling gas of the HTR. Therefore the possibility of catalytic steam gasification was examined. Model calculations based on experimental results show that use of 3–4 wt% relative to coal of K²CO³ catalyst increases the throughput of a large scale nuclear gasification plant by ≈65%, while gas production costs decrease by ≈15%. Corrosion by catalysts is not significant at low concentration (< 5 wt%) and low temperature (< 900 °C).     

A study on the direct catalytic steam gasification of coal for the bench-scale system

Various techniques have been developed to increase the efficiency of coal gasification. The use of a catalyst in the catalytic-steam gasification process lowers the activation energy required for the coal gasification reaction. Catalytic-steam gasification uses steam rather than oxygen as the oxidant and can lead to an increased H₂/CO ratio. The purpose of this study was to evaluate the composition of syngas produced under various reaction conditions and the effects of these conditions on the catalyst performance in the gasification reaction. Simultaneous evaluation of the kinetic parameters was undertaken through a lab-scale experiment using Indonesian low rank coals and a bench-scale catalytic-steam gasifier design. The composition of the syngas and the reaction characteristics obtained in the lab- and bench-scale experiments employing the catalytic gasification reactor were compared. The optimal conditions for syngas production were empirically derived using lab-scale catalytic-steam gasification. Scale-up of a bench-scale catalytic-steam gasifier was based on the lab-scale results based on the similarities between the two systems. The results indicated that when the catalytic-steam gasification reaction was optimized by applying the K₂CO₃ catalyst to low rank coal, a higher hydrogen yield could be produced compared to the conventional gasification process, even at low temperature.     

Pyrolysis-gasification of plastics, mixed plastics and real-world plastic waste with and without Ni-Mg-Al catalyst

Polypropylene, polystyrene, high density polyethylene and their mixtures and real-world plastic waste were investigated for the production of hydrogen in a two-stage pyrolysis-gasification reactor. The experiments were carried out at gasification temperatures of 800 or 850 °C with or without a Ni-Mg-Al catalyst. The influence of plastic type on the product distribution and hydrogen production in relation to process conditions were investigated. The reacted Ni-Mg-Al catalysts were analyzed by temperature-programmed oxidation and scanning electron microscopy. The results showed that lower gas yield (11.2 wt.% related to the mass of plastic) was obtained for the non-catalytic non-steam pyrolysis-gasification of polystyrene at the gasification temperature of 800 °C, compared with the polypropylene (59.6 wt.%) and high density polyethylene (53.5 wt.%) and waste plastic (45.5 wt.%). In addition, the largest oil product was observed for the non-catalytic pyrolysis-gasification of polystyrene. The presence of the Ni-Mg-Al catalyst greatly improved the steam pyrolysis-gasification of plastics for hydrogen production. The steam catalytic pyrolysis-gasification of polystyrene presented the lowest hydrogen production of 0.155 and 0.196 (g H₂/g polystyrene) at the gasification temperatures of 800 and 850 °C, respectively. More coke was deposited on the catalyst for the pyrolysis-gasification of polypropylene and waste plastic compared with steam catalytic pyrolysis-gasification of polystyrene and high density polyethylene. Filamentous carbons were observed for the used Ni-Mg-Al catalysts from the pyrolysis-gasification of polypropylene, high density polyethylene, waste plastic and mixed plastics. However, the formation of filamentous carbons on the coked catalyst from the pyrolysis-gasification of polystyrene was low.     

The effect of steam on pyrolysis and char reactions behavior during rice straw gasification

Steam gasification of biomass can generate hydrogen-rich, medium heating value gas. We investigated pyrolysis and char reaction behavior during biomass gasification in detail to clarify the effect of steam presence. Rice straw was gasified in a laboratory scale, batch-type gasification reactor. Time-series data for the yields and compositions of gas, tar and char were examined under inert and steam atmosphere at the temperature range of 873-1173 K. Obtained experimental results were categorized into those of pyrolysis stage and char reaction stage. At the pyrolysis stage, low H₂, CO and aromatic tar yields were observed under steam atmosphere while total tar yield increased by steam. This result can be interpreted as the dominant, but incomplete steam reforming reactions of primary tar under steam atmosphere. During the char reaction stage, only H₂ and CO₂ were detected, which were originated from carbonization of char and char gasification with steam (C + H₂O→CO + H₂). It implies the catalytic effect of char on the water-gas shift reaction. Acceleration of char carbonization by steam was implied by faster hydrogen loss from solid residue.     

胜利褐煤水蒸气气化制富氢合成气及其固有矿物质的催化作用

利用微型固定床反应装置,研究了内蒙古胜利褐煤水蒸气气化过程中H₂、CO₂、CO和CH₄生成规律及其固有矿物质的催化效应。原煤(SL-raw)、盐酸洗脱(SL-HCl)、氢氟酸洗脱(SL-HF)及盐酸洗脱液回添煤样(SL-HCl-Re)在水蒸气气化反应过程中,H₂、CO₂和CO生成速率存在明显差异,充分说明胜利褐煤中某些固有的矿物质对其水蒸气气化反应具有显著的催化作用,可大幅度提高其气化反应速率,并使其起始气化温度降低96℃,气化反应主体温度降低150℃以上,同时促进了合成气中H₂生成,抑制了CO的生成,使胜利褐煤水蒸气气化反应过程中一直维持着较高的H₂/CO摩尔比,SL-raw、SL-HCl-Re水蒸气气化所得合成气中H₂/CO摩尔比分别为17.3和4.3,而SL-HCl和SL-HF水蒸气气化所得合成气中H₂/CO摩尔比均只有1.22。SL-HCl和SL-HF水蒸气气化生成H₂、CO₂和CO的规律基本相同,说明起催化作用的物质是可溶解在盐酸洗脱液中的矿物质。经过分析,发现矿物质对胜利褐煤水蒸气气化反应的催化作用主要是通过提高水煤气变换反应(WGSR)速度实现的。最后结合文献报道提出了胜利褐煤水蒸气气化反应过程中矿物质的原位催化机理。     

Steam gasification of coal char catalyzed by K2CO3 for enhanced production of hydrogen without formation of methane

Steam gasification of coal char catalyzed by potassium carbonate was investigated on a laboratory fixed-bed reactor to examine the catalytic effects not only on the reaction rate but also on the reaction selectivity, and non-catalytic gasification of coal char was performed by way of contrast. It was observed that the catalytic gasification of coal char with steam occurred significantly in a temperature range of 700-750 °C, producing a hydrogen-rich gas with slight formation of carbon monoxide and virtually no formation of methane. An oxygen transfer and intermediate hybrid mechanism of the catalytic char gasification with steam is proposed for understanding of the experimental data regarding both the kinetic behaviors and reaction selectivity. The study has highlighted the advantages of the catalytic gasification of coal char over the conventional coal gasification with respect to the reaction selectivity. The catalytic steam gasification of coal char makes it possible to eliminate or simplify the methane reforming and water-gas shift processes in the traditional gas-to-hydrogen purification system.     

An Experimental Investigation of Hydrogen Production from Biomass

In gaseous products of biomass steam gasification, there exist a lot of CO, CH4 and other hydrocarbons that can be converted to hydrogen through steam reforming reactions. There exists potential hydrogen production from the raw gas of biomass steam gasification. In the present work, the characteristics of hydrogen production from biomass steam gasification were investigated in a small-scale fluidized bed. In these experiments, the gasifying agent (air) was supplied into the reactor from the bottom of the reactor and the steam was added into the reactor above biomass feeding location. The effects of reaction temperature, steam to biomass ratio, equivalence ratio (ER) and biomass particle size on hydrogen yield and hydrogen yield potential were investigated. The experimental results showed that higher reactor temperature, proper ER, proper steam to biomass ratio and smaller biomass particle size will contribute to more hydrogen and potential hydrogen yield.     

Process modeling for parametric study on oil palm empty fruit bunch steam gasification for hydrogen production

Biomass steam gasification with in-situ carbon dioxide capture using CaO exhibits good prospects for the production of hydrogen rich gas. The present work focuses on the process modeling for hydrogen production from oil palm empty fruit bunch (EFB) using MATLAB for parametric study. The model incorporates the reaction kinetics calculations of the steam gasification of EFB (C_3.4H_4.1O_3.3) with in-situ CO₂ capture, as well as mass and energy balances calculations. The developed model is used to investigate the effect of temperature and steam/biomass ratio on the hydrogen purity, yield and efficiency. Based on the results, hydrogen purity of more than 76.1 vol.% can be achieved. The maximum hydrogen yield predicted at the outlet of the gasifier is 102.6 g/kg of EFB. It is found that increment in temperature and steam/biomass ratio promotes hydrogen production. However, it is also predicted that the efficiency decreases when using more steam. Due to the still on-going empirical work, the results are compared with published literatures on different systems. The comparison shows that the results are in agreement to some extent due to the different basis.     

Low temperature gasification of brown coals catalysed by nickel

Nickel catalyst exhibited an extremely high activity in the gasification of some low rank coals at a temperature as low as 750 K. Approximately 85% of Yallourn coal was converted within 30 min in steam at 773 K. A high nickel loading, > 4 wt% was necessary. It seems essential for coal high in oxygen and low in sulphur to be gasified in this manner. Oxygen-containing functional groups on the coal surface seemed to play an important role in keeping the nickel catalyst in a finely dispersed state. Hydrogen sulphide was strongly adsorbed on the nickel catalyst and retarded this reaction. Hydrogen and carbon dioxide were the main products of low-temperature steam gasification. Similar low-temperature gasification reactions were also observed in hydrogen and in carbon dioxide.     

木炭水蒸气催化气化制取合成气

以木炭为原料,选用KOH、K₂CO₃、KHCO₃、KNO₃为催化剂,在上吸式固定床气化炉中,进行水蒸气催化气化制取合成气实验。考察了不同催化剂、催化剂用量、水蒸气流量、气化温度对木炭水蒸气气化的炭转化率、产氢率、气体组成体积分数和H₂/CO值的影响。实验通过炭吸收催化剂溶液来负载催化剂,实验结果表明：4种催化剂都可提高木炭气化效率,在浸渍相同质量分数的催化剂溶液下,催化活性顺序为KOH>K₂CO₃>KHCO₃>KNO₃。碳转化率及产氢率都随着催化剂溶液浓度的增加而增大,但浓度过高增加趋势逐渐变缓,催化剂溶液质量分数在4%~6%较为合适。增加水蒸气流量,气体产物中H₂体积分数增大,H₂/CO值增大。升高温度可促进炭气化反应,950℃时碳转化率和产氢率分别达到98.7%和145.23g/kg。实验可得到H₂/CO比1.53~4.09范围间的合成气,可用于合成甲醇、甲烷、二甲醚等燃料。     

The catalytic steam gasification of one Australian and three Japanese coals using potassium and sodium carbonates

The catalytic steam gasification of four different coals using potassium and sodium carbonates as catalysts was carried out in a semi-flow type fixed-bed reactor. The coal was gasified with or without the catalyst under a steam—argon atmosphere at a heating rate of 50°C/s at 700–800°C. The catalytic activity of carbonates for gasification was remarkable for Japanese high-volatile coals (Miike and Takashima coals), and moderate for Australian medium-volatile coal (New Lithgow coal); however, the carbonates had little effect on gasification of Japanese lignite (Taiheiyo coal). It is assumed that Miike and Takashima coals soften and melt during the heating process to make the contact between char and catalyst better. New Lithgow and Taiheiyo coals do not have this property. Gasification was promoted significantly at lower temperatures when the catalyst was used. In both catalyzed and uncatalyzed runs the main products were hydrogen and carbon dioxide; the reaction temperature did not affect the composition of the gases much. A water—gas shift reaction occurred during gasification resulting in a large amount of carbon dioxide under a large excess of steam flow.     

甲醇水蒸气重整制氢研究进展

氢气需求的持续增长,带动制氢技术的不断进步。煤制氢技术投资较高,天然气制氢原料来源受到限制,电解水制氢成本较高。甲醇制氢投资适中,适合各种规模的制氢装置,铜基催化剂反应温度低,低温活性和氢气选择性好,价格低廉,因而甲醇制氢技术得到广泛应用。催化剂载体和助剂的改进研究,对工业催化剂的改进具有重要的指导意义。综述甲醇水蒸气重整制氢工艺、反应机理和催化剂,介绍了催化剂载体和助剂等方面的研究进展情况。     

Experimental simulation of hard coal underground gasification for hydrogen production

The main objective of this study was the assessment of the feasibility of applying the underground hard coal gasification in the production of a hydrogen-rich gas. In the course of the experiment the so-called two-stage gasification process in which oxygen and steam were supplied to the reaction zone separately in alternate stages was investigated. For this purpose a special surface reactor has been constructed, in which the underground conditions were to be imitated both in respect to the coal seam and the surrounding rock layers. The surface simulation of the underground gasification was carried out on extra large coal samples, which allowed the recreation of near real underground conditions. In the reactor an experiment lasting almost 7 days has been performed, with the average hourly gas yields of 7.8 m³/h and 9.2 m³/h for the oxygen and the steam gasification stages, respectively. The average hydrogen concentration during the oxygen stage (heating up) was 15.28% with the maximum of 54.4%. The average hydrogen concentration during the steam stage was 53.77% with the maximum of 62.90%. Thus the feasibility of hydrogen-rich gas production in the process of underground gasification of hard coal has been demonstrated. During the course of the surface experiment an original and unprecedented database of temperature profiles has been acquired which now constitutes an invaluable source of thermodynamic information for the prospective underground gasification activities.     

Factors affecting steam gasification rate of low rank coal char in a pressurized fluidized bed

A high-pressure bubbling fluidized bed reactor was used to study the steam gasification of coal char under pressure. Indonesian sub-bituminous coal char (Adaro) and Australian lignite char (Loy Yang) were gasified with steam in the reactor at temperatures below 1173 K and at total pressures ranging from 0.1 to 0.5 MPa. The steam gasification rates of the coal chars were determined by analysis of the gaseous products. Activation energies for the steam gasification of the chars were as high as about 250 kJ/mol, which suggests that the temperature dependence of the gasification was substantial. The apparent gasification rates under the study conditions were described by a Langmuir–Hinshelwood (L–H)-type equation. Analysis of the reaction kinetics on the basis of the L–H equation indicated that increasing steam pressure effectively increased the gasification rate.     

Reaction kinetics of pulverized coal-chars derived from inertinite-rich coal discards: Gasification with carbon dioxide and steam

An investigation was undertaken to determine the kinetics of gasification of coal-chars (pulverized) derived from typical South African inertinite-rich (high-ash) coals involving char reactions with carbon dioxide and steam and the effects of carbon monoxide and hydrogen. The chars used were characterized with respect to structural, chemical, mineralogical and petrographic (maceral content) properties and gasification experiments were conducted in a TGA at atmospheric pressure with different gas mixtures within a temperature range of 1073–1223 K. The shrinking core model with a controlling surface reaction was shown to be applicable for the gasification of pulverized coal-chars consisting of essentially of carbon-rich particles. The validity of this model can be attributed to the core having an exceptional low porosity (high inertinite parent coal) and consequently negligible penetration of the gases. It was found that the gasification intrinsic reaction rates could be adequately described by Langmuir–Hinshelwood type rate equations and that established equations have been validated with corresponding constants according to new data processing procedures. It was found that the reaction rate constants for coal-chars derived from inertinite-rich (76–80%) coal discards were different to results published in the literature and that the intrinsic reaction rates differed only slightly (order of magnitude) for coal-chars with similar maceral (inertinite) compositions and different total ash contents. The marked inhibiting effect of the carbon monoxide and hydrogen on the carbon dioxide/carbon monoxide and steam/hydrogen gasification reactions is shown and relevant constants are reported. Experiments were done and models evaluated for a multi-component gasification mixture consisting of a feed mixture of carbon dioxide, carbon monoxide, steam and hydrogen. Reaction constants determined with results from binary mixtures were used to predict results and it was found that the overall rate is best described with the assumption that the important reactions proceed on separate sites.     

Dynamic experimental simulation of hydrogen oriented underground gasification of lignite

The main goal of the study presented in the paper was to experimentally demonstrate the feasibility of lignite gasification to hydrogen-rich gas under the underground conditions simulated in the ex situ reactor. The in situ gasification conditions were simulated both in respect to the coal seam and the surrounding stratum. In the 54-h experiment the process of lignite gasification with oxygen and steam as gasifying medium was tested. The experiment was initially divided into three stages: the ignition stage, the oxygen stage and the steam stage.The gas produced in the steam gasification stage was characterized by the calorific value of 7.8 MJ/m³ and average hydrogen content of 46.3 vol.%. Unfortunately a rapid decrease in the temperature levels and in the amount of produced gas proved that the tested lignite of 53 vol.% moisture content was not suitable for steam gasification. A great amount of thermal energy was consumed for water evaporation which led to a considerable heat loss. An addition of stoichiometric amount of water in the system by adding steam caused the seam to extinguish. Thus only oxygen could be used as the gasifying medium in the gasification of the tested lignite. The average calorific value of gas produced in the stable operation during oxygen gasification stage equaled 5.2 MJ/m³ with the average gas production rate of 16.0 m³/h and the average hydrogen content in the produced gas of 26.4 vol.%.     

Gasification rate analysis of coal char with a pressurized drop tube furnace

Two coal chars were gasified with carbon dioxide or steam using a Pressurized Drop Tube Furnace (PDTF) at high temperature and pressurized conditions to simulate the inside of an air-blown two-stage entrained flow coal gasifier. Chars were produced by rapid pyrolysis of pulverized coals using a DTF in a nitrogen gas flow at 1400°C. Gasification temperatures were from 1100 to 1500°C and pressures were from 0.2 to 2 MPa. As a result, the surface area of the gasified char increased rapidly with the progress of gasification up to about six times the size of initial surface area and peaked at about 40% of char gasification. These changes of surface area and reaction rate could be described with a random pore model and a gasification reaction rate equation was derived. Reaction order was 0.73 for gasification of the coal char with carbon dioxide and 0.86 for that with steam. Activation energy was 163 kJ/mol for gasification with carbon dioxide and 214 kJ/mol for that with steam. At high temperature as the reaction rate with carbon dioxide is about 0.03 s⁻¹, the reaction rate of the coal char was controlled by pore diffusion, while that of another coal char was controlled by surface reaction where reaction order was 0.49 and activation energy was 261 kJ/mol.