生物质气化过程催化剂应用研究进展

生物质气化技术已在国内外得到广泛的开发和运用，但由于燃气品位较差，焦油较多，限制了生物质气化气的进一步利用。在生物质气化过程中应用催化剂是一种有效的提升燃气质量和催化裂解焦油的方法，近年来已引起了国内外的广泛注意。本文对国内外生物质催化气化及相关研究进展进行了综合评述，分析了催化剂对减少生物质气化焦油的生成和改进燃料气品质的作用结果，提出了进一步的研究方向。     

生活垃圾衍生燃料分段催化气化

利用下吸式分段催化固定床反应器对生活垃圾衍生燃料进行了气化实验。研究了气化温度、当量空气系数、气化介质和催化剂对气化产物的影响。结果表明,生活垃圾衍生燃料以塑料、纸类和厨余组分为主,热值在10 MJ·kg~(-1)以上,适合直接气化。随着气化温度升高,气化气中H_2和CO的含量、产气率、气化气热值、碳转化率和冷煤气效率升高,而焦油和CO_2含量明显降低;随着当量空气系数升高,CO_2含量、产气率和碳转化率升高,而焦油含量和气化气热值降低,在当量空气系数为0.33时冷煤气效率最高;当采用富氧空气作为气化介质时,N_2对于气化气的稀释作用减弱;添加催化剂能有效减少气化气中焦油的含量,提高H_2和CO的含量。采用下吸式分段催化气化,能有效提高气化气品质和冷煤气效率。     

下吸式气化炉处理城市生活垃圾

下吸式气化炉具有原料适应性好,燃气中焦油含量少的特点。使用下吸式气化炉对广州城市生活垃圾进行了空气气化实验,并对燃气成分、焦油含量和灰渣重金属含量进行了分析。分析结果表明:燃气气体热值可达4600kJ/m3,燃气焦油含量为2.0g/m3。另外,对灰渣中的金属成分也进行了分析。试验结果表明:下吸式气化炉是处理复杂城市生活垃圾的一种有效手段。     

预煅烧铜渣与生物质混合催化气化

在热重分析仪上,以1 000℃预煅烧5h铜渣为催化剂,在氧气气氛下,进行生物质的催化气化实验.在预煅烧铜渣/生物质(质量比)为0.5～2.5范围内,考察铜渣的催化性能.实验结果表明,在所研究的比例范围内,生物质热解阶段和气化阶段的最大失重速率呈现先增大后减小的趋势,且在比例为2时都达到最大值.研究表明,铜渣中的铁氧化物在气化过程中被还原为金属Fe和FeO,而生成的FeO与SiO2反应生成Fe2SiO4.在铜渣与生物质混合催化气化反应中,金属Fe从铜渣中的铁氧化物中被还原出来而提供了活性位,表明铜渣因含有易还原的铁元素而具有催化作用.     

下吸式气化炉处理城市生活垃圾

下吸式气化炉具有原料适应性好，燃气中焦油含量少的特点。使用下吸式气化炉对广州城市生活垃圾进行了空气气化实验，并对燃气成分、焦油含量和灰渣重金属含量进行了分析。分析结果表明：燃气气体热值可达4600kJ／m^3，燃气焦油含量为2．0g／m^3。另外，对灰渣中的金属成分也进行了分析。试验结果表明：下吸式气化炉是处理复杂城市生活垃圾的一种有效手段。     

生物质废弃物催化裂解制备富氢燃气实验研究

由生物质废弃物催化裂解制取氢气是一种可再生的制氢方法,本研究采用2段加热管式反应器,前段装生物质,后段装催化剂,用以研究生物质催化裂解制取氢气的特性,并提出潜在氢产率的概念对生物质制氢的经济技术可行性进行深入的分析.测试的3种生物质废弃物为:松木粉、木质素和纤维素,测试温度为600～700℃.实验结果表明,加入催化剂后3种物料的产氢率从5.48～15.06g/kg增加到12.94～37.73g/kg;催化剂对潜在产氢率的影响较小,加入催化剂前后的变化范围为:36.25～98.86g/kg到37.40～116.98g/kg.生物质废弃物催化裂解产氢率与相同温度下空气-水蒸气气化的氢产率相当,实验结果证明,生物质废弃物催化裂解是一种有效的制氢方法.     

流化床生物质气化过程的中试研究

在流化床生物质气化炉内 ,用空气进行气化生物质 (花生壳 )的试验研究 ,分析的参数是ER(0 .2— 0 .45 ) ,气化床的温度 (75 0— 85 0℃ )。当当量比ER在 0 .2 5— 0 .33范围内 ,气化燃气热值为 6 .2— 6 .8MJ/Nm3,气体产量在 2 6 0—30 0Nm3/h。并对七种农、林废弃物进行了初步气化实验研究。生成的燃气成分 :CO在 14%— 17%之间 ,H2 含量一般低于10 % ,甲烷含量为 5 %— 10 %。燃气热值多数在 5 30 0— 6 5 0 0kJ/Nm3,气化效率 72 .6 %。实验结果表明 ,流化床生物质气化炉可用于生物质气化     

流化床生物质气化过程的中试研究

在流化床生物质气化炉内，用空气进行气化生物质（花生壳）的试验研究，分析了参数是ER（0.2-0.45)，气化床的温度750－850℃），当当量比ER在0.25-0.33范围内，气化燃气热值为6．2％－6.8MJ/Nm^3，气体产量在260－300Nm^3/h，并对七膛，林废弃物进行了初步实验研究，生成的燃气成分：CO在14％－17％之间，H2含量一般低于10％，甲烷含量为5％－10％，燃气热值多数在5300－6500kJ/Nm^3，气化效率72．6％，实验结果表明，流化床生物质气化炉可用于生物质气化。     

生物质废弃物催化裂解制备富氢燃气实验研究

由生物质废弃物催化裂解制取氢气是一种可再生的制氢方法，本研究采用2段加热管式反应器，前段装生物质，后段装催化剂，用以研究生物质催化裂解制取氢气的特性，并提出潜在氢产率的概念对生物质制氢的经济技术可行性进行深入的分析。测试的3种生物质废弃物为：松木粉、木质素和纤维素，测试温度为600～700℃。实验结果表明，加入催化剂后3种物料的产氢率从5．48～15．06g／kg增加到12．94～37．73g／kg；催化剂对潜在产氢率的影响较小，加入催化剂前后的变化范围为：36、25～98、86g／kg到37．40～116．98g／kg。生物质废弃物催化裂解产氢率与相同温度下空气-水蒸气气化的氢产率相当，实验结果证明，生物质废弃物催化裂解是一种有效的制氢方法。     

生活垃圾衍生燃料催化气化制备合成气

以生活垃圾衍生燃料RDF(refuse derived fuel)为原料,在750℃下进行了催化气化-改质实验,研究了氧气供应量、Ni基催化剂组分等操作要素对合成气生成特性的影响。结果表明:氧气供应量ER(equivalent ratio)的增加可以提高碳素转化率和冷气体效率;在Ni基催化剂中添加Mg、Ce、K、Ca和Zn等金属助剂可以有效改善改质催化性能,促进焦油分解,提高有效气体收率。在750℃温度条件下,控制供氧量ER=0.04时,通过催化气化-改质处理,可以从RDF获得H_2体积分数约29.00%的清洁合成气,冷气体效率和碳素转化率分别为44.41%和82.41%,合成气收率可达0.244 m~3·kg~(-1)(RDF)。     

Woody biomass and RPF gasification using reforming catalyst and calcium oxide

This study focused on steam gasification and reforming of waste biomass using a reforming catalyst. The purpose of the study was to evaluate the durability of a commercial Ni reforming catalyst and the effect of CaO on the reforming behavior, and to clarify detailed factors of catalytic performance, as well as the effect of operating parameters on the characteristics of produced gas composition. Moreover, catalyst regeneration was carried out and the behavior of catalytic activity based on gas composition was investigated. Using a fluidized bed gasifier and a fixed bed reformer, gasification and reforming of waste biomass were carried out. Commercial Ni-based catalyst and calcined limestone (CaO) were applied to the reforming reaction. Temperature of the gasifier and reformer was almost 1023 K. Ratio of steam to carbon in the feedstock [mol mol⁻¹] and equivalence ratio (i.e., ratio of actual to theoretical amount of oxygen) [-] were set at about 2 and 0.3, respectively. The feed rate of the feedstock into the bench-scale gasifier was almost 15 kg h⁻¹. The results of waste biomass gasification confirmed the improvement in H₂ composition by the CO₂ absorption reaction using the reforming catalyst and CaO. In addition, CaO proved to be especially effective in decreasing the tar concentration in the case of woody biomass gasification. Catalytic activity was maintained by means of catalyst regeneration processing by hydrogen reduction after air oxidation when woody biomass was used as feedstock.     

Bench-scale gasification of cedar wood – Part II: Effect of Operational conditions on contaminant release

Here, we present the evolution profile of tar in the product gas during cedar biomass gasification. We also discuss the evolution of other contaminants (H₂S, COS, NH₃, HCN, and HCl). The cedar wood was gasified under various operating conditions in a bench-scale externally heated updraft gasifier; this was followed by thermal reforming.Tar levels in the product gas were significantly affected by the operating conditions used. At a gasification temperature of 923 K, there was no clear relation between the evolution of phenolic tar in the product gas as a function of residence time. The evolution of PAH tar at a low gasification temperature was lower than the evolution of phenolic tar. With increasing temperature, the proportion of PAH tar content became significant. At a gasification temperature of 1223 K, increasing the residence time reduced the content of PAH tar owing to a catalytic effect associated with ash generation at high temperatures. Increasing the steam-to-carbon (S/C) ratio under thermal conditions had a slight effect on PAH conversion. However, increasing the equivalence ratio (ER) effectively reduced the tar levels.The conversion of fuel-sulfur and fuel-nitrogen to volatile-sulfur and volatile-nitrogen, respectively, increased with increasing S/C ratio and ER. The evolutions of COS and HCN gases were much smaller than the evolution of H₂S and NH₃. The evolution of HCl in the product gas decreased slightly with increasing ER. Increasing the S/C ratio decreased the HCl levels in the product gas. The effect of temperature on contaminant levels could not be fully understood due to limited availability of experimental data at various temperatures. We also compare our findings with data in the literature.     

Investigation of Nitrogen-Bearing Species in Catalytic Steam Gasification of Poultry Litter

Abstract

The production of broiler chickens has become one of the largest sectors in U.S. agriculture, and the growing demand for poultry has led to an annual production growth rate of 5%. With increased demand for poultry, litter management has become a major challenge in the agriculture industry. Although the catalytic steam gasification has been accepted as a possible and feasible method for litter management, concern has been expressed about the presence of nitrogen and phosphorus containing species in the fuel gas and/or in the final solid residue. The possible release of phosphorus as phosphine gas in the fuel gas can have an adverse impact on the environment. Similarly, possible release of ammonia from the nitrogen containing species is also not acceptable. Hence, under partial U.S. Department of Agriculture support, a study was conducted to examine the fate and the environmental impact of the nitrogen- and phosphorus-containing species released during catalytic steam gasification of poultry litter. From various preliminary tests, it was concluded that most (～100%) of the phosphorus would remain in the residue, and some (20–70%) of the nitrogen would end up as ammonia in the fuel gas. The effects of temperature, catalyst loading, and type of catalyst on ammonia liberation were studied in a muffled furnace setup at atmospheric pressure. The fraction of nitrogen released as ammonia was found to decrease with an increase in temperature during pyrolysis and steam gasification. It also decreased with an increase in catalyst loading.     

Investigation of nitrogen-bearing species in catalytic steam gasification of poultry litter

The production of broiler chickens has become one of the largest sectors in U.S. agriculture, and the growing demand for poultry has led to an annual production growth rate of 5%. With increased demand for poultry, litter management has become a major challenge in the agriculture industry. Although the catalytic steam gasification has been accepted as a possible and feasible method for litter management, concern has been expressed about the presence of nitrogen and phosphorus containing species in the fuel gas and/or in the final solid residue. The possible release of phosphorus as phosphine gas in the fuel gas can have an adverse impact on the environment. Similarly, possible release of ammonia from the nitrogen containing species is also not acceptable. Hence, under partial U.S. Department of Agriculture support, a study was conducted to examine the fate and the environmental impact of the nitrogen- and phosphorus-containing species released during catalytic steam gasification of poultry litter. From various preliminary tests, it was concluded that most (approximately 100%) of the phosphorus would remain in the residue, and some (20-70%) of the nitrogen would end up as ammonia in the fuel gas. The effects of temperature, catalyst loading, and type of catalyst on ammonia liberation were studied in a muffled furnace setup at atmospheric pressure. The fraction of nitrogen released as ammonia was found to decrease with an increase in temperature during pyrolysis and steam gasification. It also decreased with an increase in catalyst loading.     

Gas reforming and tar decomposition performance of nickel oxide (NiO)/SBA-15 catalyst in gasification of woody biomass

In the gasification of biomass, it is necessary to limit the amount of by-product tar and increase the yields of hydrogen (H₂) and carbon monoxide (CO) (syngas). Therefore, we conducted gasification and reforming experiments on woody biomass using an electric tubular furnace, to evaluate the gas reforming and tar decomposition performance of a NiO/SBA-15 catalyst. As a result, we found that this catalyst is effective for H₂ production. It is believed that the increase in H₂ volume due to the catalyst occurs through a steam reforming reaction involving hydrocarbons, including methane (CH₄), and the water-gas shift reaction. With respect to the influence of the gasifying agent on the reforming effect of the catalyst, the amount of generated carbon dioxide (CO₂) and hydrogen (H₂) increases because the shift reaction is promoted by supplying steam. On the other hand, it was inferred that the shift reaction rarely occurred because it approaches equilibrium by supplying O₂. Furthermore, it is suggested that light aromatic hydrocarbons are decomposed by the catalyst.

Implications: The mesoporous silica catalyst NiO/SBA-15 was highly effective for H₂ production and decomposition of light aromatic compounds in the gasification of woody biomass. In the catalyst reaction, supplying steam promoted H₂ production. From thermodynamic analysis and discussion, it was also inferred that supplying O₂ might prevent the water gas shift reaction. The results are useful for designing a process needed for rich H₂ production and gas refining process for further use of syngas.     

Catalytic gasification of biomass (<Emphasis Type="Italic">Miscanthus</Emphasis>) enhanced by CO<Subscript>2</Subscript> sorption

The main objective of this work concerns the coupling of biomass gasification reaction and CO₂ sorption. The study shows the feasibility to promote biomass steam gasification in a dense fluidized bed reactor with CO₂ sorption to enhance tar removal and hydrogen production. It also proves the efficiency of CaO-Ca₁₂Al₁₄O₃₃/olivine bi-functional materials to reduce heavy tar production. Experiments have been carried out in a fluidized bed gasifier using steam as the fluidizing medium to improve hydrogen production. Bed materials consisting of CaO-based oxide for CO₂ sorption (CaO-Ca₁₂Al₁₄O₃₃) deposited on olivine for tar reduction were synthesized, their structural and textural properties were characterized by Brunauer–Emmett–Teller (BET), X-ray diffraction (XRD), and temperature-programmed reduction (TPR) methods, and the determination of their sorption capacity and stability analyzed by thermogravimetric analysis (TGA). It appears that this CaO-Ca₁₂Al₁₄O₃₃/olivine sorbent/catalyst presents a good CO₂ sorption stability (for seven cycles of carbonation/decarbonation). Compared to olivine and Fe/olivine in a fixed bed reactor for steam reforming of toluene chosen as tar model compound, it shows a better hydrogen production rate and a lower CO₂ selectivity due to its sorption on the CaO phase. In the biomass steam gasification, the use of CaO-Ca₁₂Al₁₄O₃₃/olivine as bed material at 700 °C leads to a higher H₂ production than olivine at 800 °C thanks to CO₂ sorption. Similar tar concentration and lighter tar production (analyzed by HPLC/UV) are observed. At 700 °C, sorbent addition allows to halve tar content and to eliminate the heaviest tars.     

A review of the catalysts used in the reduction of NO by CO for gas purification

The reduction of NO by the CO produced by incomplete combustion in the flue gas can remove CO and NO simultaneously and economically. However, there are some problems and challenges in the industrial application which limit the application of this process. In this work, noble metal catalysts and transition metal catalysts used in the reduction of NO by CO in recent years are systematically reviewed, emphasizing the research progress on Ir-based catalysts and Cu-based catalysts with prospective applications. The effects of catalyst support, additives, pretreatment methods, and physicochemical properties of catalysts on catalytic activity are summarized. In addition, the effects of atmosphere conditions on the catalytic activity are discussed. Several kinds of reaction mechanisms are proposed for noble metal catalysts and transition metal catalysts. Ir-based catalysts have an excellent activity for NO reduction by CO in the presence of O₂. Cu-based bimetallic catalysts show better catalytic performance in the absence of O₂, in that the adsorption and dissociation of NO can occur on both oxygen vacancies and metal sites. Finally, the potential problems existing in the application of the reduction of NO by CO in industrial flue gas are analyzed and some promising solutions are put forward through this review.

     

The Use of Combined-Cycle Power Systems in Nonpolluting Central Stations

The body of information presented in this paper is directed to power engineers oncerned with reducing pollution from future electric utility power stations. An Air Pollution Control Office sponsored study of advanced-cycle power systems and methods of desulfurizing fuels investigated a large number of conventional and nonconventional power systems for use by electric utilities. These systems included current and advanced steam systems, steam systems with topping and bottoming cycles, closed-cycle gas turbines, and open-cycle gas turbines alone and combined with steam systems. Also considered were various methods for desulfurizing coal and residual oil, such as mechanical and chemical separation, hydrodesulfurization and gasification followed by gas clean up. The major conclusion of this study is that the most effective and economical means of reducing objectionable effluents from future fossil-fueled power stations appears to be gasification of high-sulfur fuel to produce a low-heating-value fuel gas for use in a combined gas turbine and steam (COGAS) power system. Recent and prospective advances in military and commercial aircraft gas turbine technology, particularly in the area of high-temperature operation, can be applied to industrial gas turbines to yield the high-performance, low-cost, and long-lifetime characteristics desired for base-load power generation.

A COGAS pilot plant burning gasified coal should be built at the earliest possible time. Experience gained in the pilot plant could allow introduction of commercial sized stations within this decade.     

生物质燃气高温过滤材料的研究

日趋严格的环保要求和某些工艺过程的特殊需要，对生物质燃气中灰尘的数量和粒度提出了更高的要求，即对生物质气化系统中的过滤工艺有了新的要求。针对生物质气化工艺的特点及其灰尘的特性，重点研究了针刺过滤毡和金属多孔材料两类高温过滤材料。通过研究比较，两种材料各有优缺点，针刺过滤毡过滤精度高，运行工况比较稳定，但是过滤气速小，适用温度低，设备比较庞大；金属多孔材料过滤精度相对较低，但是过滤气速和使用温度高，设备相对紧凑。     

粉煤灰和电石渣对聚丙烯塑料裂解的影响研究

研究了粉煤灰和电石渣对聚丙烯塑料裂解的影响,讨论了加入量对裂解速度和裂解产物的影响.结果表明:粉煤灰和电石渣都使裂解产物中的轻质部分(汽油和裂解气)增加、重油降低;粉煤灰比电石渣更能加快反应的进行,而且加入量越多,反应越快,需时越短;粉煤灰比电石渣对聚丙烯塑料的裂解具有明显的催化促进效果.