Catalytic activity of iron in the water vapour gasification of sulphur-containing cokes

The influence of sulphur on the catalytic activity of iron in gasification with H₂-H₂O mixtures at different total pressures and temperatures was studied with model cokes of various sulphur contents, prepared by copyrolysis of PVC and elemental sulphur at 600 °C. Sulphur represents a strong poison which may completely inhibit the catalytic activity of iron, owing to the presence of extremely stable sulphur surface compounds. The inhibition may partly be compensated by increase of pressure or temperature. The beneficial effect of pressure results from hydrodesulphurization of the cokes in the early stages of gasification, especially at low water vapour partial pressures. High temperatures effect a reduction of the sulphur surface compounds. A general reaction scheme is proposed and it is concluded that gradual inhibition of the catalytic activity of iron is caused by partial blocking of active centres on the iron surfac.     

Ultrasonic study of the effects on metallurgical cokes of heat treatment and gasification

To monitor changes in the fissure density in the interior of coke, pieces of an industrial metallurgical coke,were examined before and after heat treatment and gasification in carbon dioxide at 1173 K, using an ultrasonic non-destructive method (PUNDIT). Seven coke pieces were heat treated to 1173 K in nitrogen and six showed increases in pulse velocity of 30–40%. Ten coke pieces were gasified at 1173 K in carbon dioxide and all showed decreases in pulse velocity of about 10%. The effects of extended heat treatment and gasification are reported.     

Aspects of gasification and structure in cokes from coals

Cokes were prepared from nine coals of different rank and characterized by surface area measurement, reactivity to carbon dioxide at 1473K and Raman-laser spectroscopy. Rates of gasification of cokes on a unit surlface area basis (K¹ = g m^?2 min^?1) decreased with increasing rank of parent coal based on maximum oil reflectances. However rates of gasification could not be related to coke structure as measured by Raman-laser spectroscopy.     

Catalysis of gasification of coal-derived cokes and chars

Calcium is the most important in-situ catalyst for gasification of US coal chars in O₂, CO₂ and H₂O. It is a poor catalyst for gasification of chars by H₂. Potassium and sodium added to low-rank coals by ion exchange and high-rank coals by impregnation are excellent catalysts for char gasification in O₂, CO₂ and H₂O. Carbon monoxide inhibits catalysis of the CH₂O reaction by calcium, potassium and sodium; H₂ inhibits catalysis by calcium. Thus injection of synthesis gas into the gasifier will inhibit the CH₂O reaction. Iron is not an important catalyst for the gasification of chars in O₂, CO₂ and H₂O, because it is invariably in the oxidized state. Carbon monoxide disproportionates to deposit carbon from a dry synthesis gas mixture (3 vol H₂ + 1 vol CO) over potassium-, sodium- and iron-loaded lignite char and a raw bituminous coal char, high in pyrite, at 1123 K and 0.1 MPa pressure. The carbon is highly reactive, with the injection of 2.7 kPa H₂O to the synthesis gas resulting in net carbon gasification. The effect of traces of sulphur in the gas stream on catalysis of gasification or carbon-forming reactions by calcium, potassium, or sodium is not well understood at present. Traces of sulphur do, however, inhibit catalysis by iron.     

Distribution of volatile sulphur containing products during fixed bed pyrolysis and gasification of coals

Three sub-bituminous and two bituminous coals from Western Canada were used to study the evolution of H₂S, COS and SO₂ during the pyrolysis and gasification processes in a fixed bed reactor. For all types of coals, most of H₂S and SO₂ were released during the devolatilization stage. COS was formed only during the gasification stage in the presence of CO₂. The mineral matter of coal may have played a role during the gasification stage. Some observations made during this latter stage in CO₂ and/or steam were interpreted in terms of the equilibrium effects.     

Quantification of oxygen capture in mineral matter during gasification

It has been observed that during the transformation of minerals at higher temperatures (>1000 °C), mineral species are formed containing a high number of oxygen molecules, i.e. gehlenite (Ca₂Al₂SiO₇), mullite (Al₆Si₃O₁₅), margarite (CaAl₄Si₂O₁₀(OH)₂) and almandine (Fe₃Al₂Si₃O₁₂).Results of the coal sources evaluated in this investigation indicated significant differences in mineral elemental composition, i.e. the CaO content varied between 5 mass % and 10 mass %, the Fe₂O₃ content varied between 1.6 mass % to more than 5 mass %, as well as differences in the TiO₂, P₂O₅ and MgO content. The coal sources producing the highest concentration of Ca-Al-Si species (CaAl₂Si₂O₈ anorthite and CaAl₄Si₂O₁₀(OH)₂ margarite), which crystallized from the slag-liquid phase during the combustion stage, also contained the highest amount of acidic components or highest percentage of kaolinite. The highest concentration of mullite and free SiO₂ after the gasification reaction (before the combustion zone), also resulted in the highest concentration of Ca-Al-Si compounds forming during the oxidation phase. The free-SiO₂ in the mineral structure of the coal sources resulted then in the formation of mineral structures with Mg, Na or Ca when present in the mineral structure, to form new mineral compounds such as KAl₃Si₃O₁₀(OH)₂ (muscovite), Mg₅Al₂Si₃O₁₀(OH)₈ (clinochlore), or other high oxygen molecule-containing mineral compounds. Thus, if free-SiO₂ was not present after the gasification phase, and mostly taken up in the form of anorthite (due to high or higher CaO contents or Fe-contents in high Fe-containing coal sources), the concentration of Si-oxygen capture compounds are relatively low.An acceptable linear correlation between oxygen capture tendencies (increase in mineral matter content during the combustion phase) versus CaO-content was obtained with the South African coal sources evaluated. This confirmed the observations obtained based on HT-XRD and FactSage modelling. It can be concluded that the linear model to predict oxygen capture behavior from CaO-content is acceptable and can be used as a predictive tool. The SiO₂ content, for example, has an inverse affect on oxygen trends up to a specific concentration of CaO in the coal. However, this model is only valid for the coal types tested (South African Highveld coal sources), and additional test work will have to be conducted for other coal types, i.e. northern hemisphere coal.     

Gasification kinetics of oil sands coke

Kinetics of steam gasification of delayed and fluid cokes derived from Athabasca bitumen have been studied in 6.35 cm diameter stirred and fixed bed reactors. Experiments were carried out at atmospheric pressure and at temperatures between 800°C and 930°C. The coke particle size ranged from 0.1 to 3.5 mm, and the steam partial pressure was varied from 15.2 to 60.6 kPa. Scanning electron microscopy, surface area analysis, and mercury porosimetry were employed to relate physical structure changes in the solids to experimental kinetic data. Several kinetic models for gasification were tested with the experimental gasification data. Rate expressions are presented for carbon conversion and for the release of sulphur.     

Influence of coal characteristics on CO2 gasification

The rate of CO₂ gasification of a coke is one of the most important qualities of metallurgical coke. Many workers are trying to estimate the rate of CO₂ gasification of coke by studying properties of coal, such as the reflectance of vitrinite and the amounts of inertinite and ash in coal. The specific-gravity separation method is used to prepare coals which possess almost the same reflectance, but contain different amounts of inertinite and ash. The relation between the rate of gasification and the properties of coal is quantitatively explained.     

Influence of microstructure on thermal expansion and graphitization of oil cokes

The influence of the feedstock coke properties on graphite behaviour is of significant importance in the production of graphite. The feedstock coke properties depend mainly on the coke microstructure. The objective of this preliminary work has been to study the relation between the microstructure and the coke properties. The results showed that there were close and definite relations between microstructure, spacing of extinction contours observed by polarized light microscopy and coke properties, such as coefficient of thermal expansion and graphitization.     

煤气化废水处理过程中湿焦脱水工艺对比分析

随着活性焦吸附工艺的应用推广,湿焦脱水成了一项新的技术难题。对不同湿焦脱水工艺实际运行情况和主要影响因素进行对比分析,研究结果表明:真空皮带脱水机脱水后焦饼含水率高达80%,故障率高,不能满足生产要求,不建议使用;离心脱水机脱水后焦饼含水率为60%~70%,自动化程度高,但耗药量大,且经常堵塞;板框压滤机脱水后焦饼含水率可达到50%,但人工操作强度高,对人员素质要求高。因此,在进行活性焦脱水工艺选择时,应从活性焦特性、运行状况、人员素质、对焦饼的要求、干焦最终去向以及资金、成本等几个方面综合考虑,做出相对合理的选择。     

Upgrading of delayed and fluid cokes from oil sand by desulfurization

Calcination of delayed and fluid oil sand cokes with alkaline reagents at high sodium/sulfur ratios followed by leaching gave almost complete desulfurization in terms of gaseous combustion products. Use of smaller proportions of alkaline reagents with hydrodesulfurization at 650 to 850°C also resulted in extensive removal of sulfur as hydrogen sulfide.     

Dry gas cleaning process by adsorption of H2S into activated cokes in gasification of carbon resources

Gasification of carbon resources including biomass and coal is one of promising energy production technologies. The R&D on effective and convenient gas cleaning processes for removal of contaminants as well as high efficient reliable gasifiers is essential for industrial application in broad fields. In this study, a dry process of synthesis gas cleaning by adsorption of H₂S into activated cokes was proposed as a candidate of desulfurization technologies in gasification. The H₂S adsorption performance of activated coke produced from coal, which are used industrially for de-SO_x and de-NO_x, was evaluated by the thermogravimetric analyses and the adsorption examination in a fixed bed under the atmospheric and high pressures. Activated coke was not only the most active at about 423 K for the H₂S adsorption rate but also regenerative over 573 K by H₂S desorption with a sufficient rate under an inert gas flow of nitrogen. The H₂S adsorption performance of the activated coke was not inhibited by the co-existence of CO₂ or COS but enhanced rather by the co-existence. The adsorbent was promisingly active for both H₂S and COS adsorption as well. These behaviors suggest that the activated coke are available for simultaneous desulfurization of H₂S and COS. The H₂S breakthrough examination in the fixed bed revealed that it was possible to remove H₂S to lower level than 1 ppm for a long time depending on the residence time of gas flow in the bed. When the adsorption operation was carried out under high pressures up to 0.6 MPa, the regeneration of activated coke by H₂S desorption took place under the pressure reduced to the atmosphere. As the results, it was implied that the present activated coke could be applicable to the desulfurization process in coal gasification.     

Experimental study on catalytic steam gasification of natural coke in a fluidized bed

The gasification characteristics of natural coke from Peicheng mine with steam were investigated in a fluidized bed reactor. The effects of catalyst type, composition and dosage of catalyst on the yield, components and heating value of product gas, and carbon conversion rate were examined. The results show that fluidized bed gasification technology is an effective way to gasify natural coke. Also the results indicate that individual addition of K-, Ca-, Fe-, Ni-based catalyst effectively increases the gasification reaction rate of the natural coke samples. With the increase in catalyst dosage, the yield and heating value of product gas per hour increase obviously, and carbon conversion rate is improved substantially. Each of aforementioned catalysts has similar catalytic effect and trend, among which the effect of Ca-based catalyst is a little weaker. The optimum metal atom ratio of mixed catalyst is Fe/Ni/others = 35/55/10, and the mixed catalyst displays maximum catalytic performance when the catalyst dosage in the natural coke is about 4%. The experimental findings provide an interesting reference for large-scale development and utilization of natural coke.     

生物质半焦的催化气化动力学特性

采用恒温热重分析法对稻草的催化气化反应动力学进行了研究,同时研究了生物质对石油焦气化的催化作用。采用修正随机孔模型对气化反应转化速率与转化率的关系进行了拟合计算,得到生物质焦气化的活化能和指前因子。结果表明,加入催化剂后半焦的气化反应活性增大,活性顺序为：加入K+半焦> 加入Ca2+半焦> 加入Mg2+半焦> 原半焦> 酸洗后半焦,表明了生物质焦能明显提高石油焦的气化活性。不同半焦气化的活化能大小顺序为：加入K+半焦<加入Ca2+半焦<加入Mg2+半焦<原半焦<酸洗后半焦,表明了生物质半焦的加入能降低石油焦气化的活化能。     

Kinetics of catalytic steam gasification of bitumen coke

The catalytic steam gasification of coke from Athabasca bitumen was investigated by thermogravimetric analysis using K₂CO₃ and Na₂CO₃ as catalysts, both of which reduced the activation energy of the reaction considerably to 1.2 × 10⁵ J mol⁻¹ and 1.3 × 10⁵ J mol⁻¹, respectively, down from 2.1 × 10⁵ J mol⁻¹ for the uncatalyzed reaction. The reaction rates varied with the partial pressure of steam between 60 kPa and 85 kPa consistent with a Langmuir-Hinshelwood model, but a first order equation was also sufficient given the low partial pressures. The initial rate of gasification of the coke particles correlated linearly with the estimated external surface area of the particles, as expected from a surface reaction involving a non-porous solid. The initial reaction rate increased with increasing the catalyst loading up to 2.4 (mol potassium)/kg. A portion of the catalyst penetrated into the coke, as confirmed by secondary ion mass spectroscopy analysis, where it could not promote the reaction with steam. This result was consistent with a small increase observed in the reaction rate at low catalyst loading. The shrinking core model was successful in predicting the rates at higher conversions from the initial rate data, despite increases in BET surface area with conversion.     

煤焦CO2气化反应动力学研究

在热天平实验装置上进行了霍林河、义马、兖州、平朔、神华、大同6种煤焦的CO2气化反应性实验，实验温度为900～1050℃。通过对实验数据处理，取得了6种煤焦的反应动力学参数等，利用不同的参数对煤焦CO2气化的反应活性进行了比较。     

Some aspects of the role of coal thermoplasticity and coke structure in coal gasification. 2. The effects of pressure and heating rate on dilatometric parameters and optical anisotropy development

An examination of the influence of pressure and heating rate on the thermoplastic properties of a weakly coking coal and of coal with various pitch-like additives was carried out using a high pressure dilatometer. Pressure up to 4 MPa markedly increased the swelling properties and increased the plastic range by decreasing the softening temperature, but the effects of pressure were strongly influenced by rate of heating with high heating rates enhancing the effects. Additions of tar or pitch also enhanced swelling at low pressure. The solid carbonization residues from the dilatometer were examined by polarized light microscopy to determine the content and composition of optically anisotropic species. The anisotropic content was increased by increases in pressure and heating rate and pitch additives enhanced the anisotropic content, especially at low pressure, without affecting the composition of the anisotropy. No direct correlations exist between the dilatometric parameters and the optical anisotropy but their dependence on the conditions emphasizes that when considering high pressure gasification of coal, it is necessary to obtain data under appropriate conditions.     

一种石油焦与CO2高温气化原位反应特性

采用高温热台显微镜原位研究了气化温度和颗粒粒度对石油焦气化反应的影响,并对比了神府烟煤和石油焦的反应特性。研究发现,石油焦在气化过程中颗粒收缩,表面结构发生变化,反应速率的改变由低温下逐渐减小,到高温下1300℃时先增大后减小。相同转化率下,反应时间随温度的升高而减少,随颗粒粒度的减小而减少。对比神府煤焦和石油焦的气化反应发现,石油焦反应活性低,为神府烟煤焦平均气化反应速率的1/6。     

水煤浆气化制氢的气化压力选择

为确定最适合水煤浆制氢装置的气化压力,以石油焦为原料,采用单喷嘴水煤浆气化技术,在20万m~3/h制氢规模下,对4.0和6.5 MPa两种不同气化压力下的装置配置、技术经济指标、消耗、投资进行综合对比。结果表明,4.0 MPa压力等级下的气化装置和净化装置均出现系列数增加或设备结构尺寸变大的情况,导致投资增加;系列数的增加还会导致备用率降低,在线率和装置可靠性下降,不利于连续稳定供氢;4.0 MPa压力等级低,装置消耗增加,尤其对于低温甲醇洗单元,冷量消耗将大幅增加。因此,针对20万m~3/h制氢规模,6.5 MPa气化压力下的装置在投资、消耗、占地、在线率、可靠性以及操作和维修的复杂性、生产成本等方面均优于4.0 MPa气化压力,在选择气化压力时应优先考虑6.5 MPa压力等级。