生物质炭水蒸气气化制取富氢合成气

以生物质炭为原料在上吸式固定床气化炉中进行水蒸气气化制备富氢合成气,考察了不同原料、粒径和催化剂对生物质炭水蒸气气化影响。结果表明,不同类型炭气化结果存在较大差异,其中木片炭气化结果最优,其次是玉米芯炭和稻壳炭,秸秆炭气化结果最差,木片炭产氢率最大为222.8g/kg。粒径的改变主要影响炭转化率,炭转化率随着粒径的增加呈增加趋势。通过炭吸收方式负载催化剂为有效的方法,其中在相同钾盐质量分数下,KOH催化能力较优于K₂CO₃,且气化速率为未加催化剂条件下的两倍。炭转化率随着碱液浓度的增加而增加,但浓度过高会增加灰分含量从而不利于产氢率,玉米芯炭催化气化最高产氢率为197.8g/kg,在碱质量分数为6%下获得。     

木屑炭水蒸气气化制备合成气

以木屑炭为原料,在上吸式固定床气化炉中进行水蒸气气化制备合成气,考察了温度和水蒸气流量对木屑炭水蒸气气化的产物分布、炭转化率、产气率、组成含量和H₂/CO值的影响。结果表明：升高温度有助于木屑炭气化,炭转化率和产气率分别在950 ℃下达到最大值99.2%和4.16 L/g,但温度升高会导致H₂从65.8%降至61.2%,同时H₂/CO也呈下降趋势,从10.3降至3.35;水蒸气流量的增加可提升H₂,从59.8%升至62%,但流量升至0.6 g/min时气化结果趋于稳定。水蒸气气化的最佳操作条件为900 ℃,水蒸气流量0.6 g/min,此条件下炭转化率、产气率和热值分别达到93.3%、4.06 L/g和9.04 MJ/m³,H₂/CO值为4.11,适合于合成甲烷。     

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。     

高灰熔点煤的加压催化气化：K2CO3催化活性及钾回收特性

以高灰熔点煤和含钾催化剂的灰渣为研究对象,分别考察了加压固定床反应器中K₂CO₃催化半焦水蒸气气化的反应性和灰渣中钾催化剂的回收特性。实验结果表明煤中添加K₂CO₃能够促进碳的转化,随着K₂CO₃负载量和气化温度的增加,碳转化率增大,CH₄收率增加。在3.5 MPa和800℃下,K₂CO₃负载量为15%时,碳转化率达到96.1%,CH₄收率达到0.24 m³·（kg C）^-1。灰渣中钾催化剂的回收率随碳转化率的增加先升高后减小,这与催化剂在灰渣中的存在方式有关。通过优化水洗和消解条件,高碳转化率下灰渣中的钾催化剂的总回收率高达96.5%。     

改性生物质炭负载铁类Fenton体系降解亚甲基蓝研究

以棉花秸秆作为前驱体,用K₂CO₃活化后制备出改性生物质炭K₂CO₃@BC,置于FeSO₄溶液中形成悬浮液,干燥并煅烧,制得改性生物质炭负载铁催化剂Fe/K₂CO₃@BC。采用XRD、FT-IR、SEM等对Fe/K₂CO₃@BC进行表征,并研究其耐酸耐碱性。以亚甲基蓝作为目标污染物,将Fe/K₂CO₃@BC催化剂和H₂O₂组成非均相类Fenton体系降解水中的亚甲基蓝,探究了溶液pH、Fe/K₂CO₃@BC投加量、H₂O₂用量、温度等因素对亚甲基蓝降解效果的影响。结果表明,催化剂Fe/K₂CO₃@BC中的Fe物种主要以Fe₃O₄形式...     

K2CO3对兰炭催化气化特性的影响

在固定床中考察了不同K₂CO₃植入浓度和不同温度条件下兰炭催化气化特性。结果表明，5%的催化剂植入浓度主要起到填充孔隙的作用，当植入浓度增加到10%以后，催化剂发生堆积会使颗粒表面及内部形成较多孔隙。提高气化温度可提高兰炭转化率，超过750℃之后碳转化率增幅减缓，催化剂饱和装载浓度为10%。在颗粒表面和开放孔隙中的高浓度C(O)才具有较高的脱附速率，并提高CO生成速率。在非催化条件下，随着气化的进行CO/CO₂下降，而H₂/(2CO₂+CO)先增后减。在催化条件下，H₂/(2CO₂+CO)稳定在1.5～1.7。催化剂兰炭样品中出现了K₂Ca(CO₃)₂双金属碳酸盐、K₂O、KO₂等活性组分，并随催化剂植入浓度的增加而增加。催化剂植入浓度的增加会导致失活现象加重，但兰炭在750℃条件下气化1 h 催化剂没有完全失活。     

基于ReaxFF-MD和DFT的废旧PP塑料水蒸气气化机理研究

气化技术是处理日益增多的废旧塑料并生产富H₂合成气的重要方法。利用ReaxFF-MD与DFT方法相结合研究了聚丙烯(PP)塑料水蒸气气化的反应机理及各产物气的生成路径,进一步探究了温度、水含量对合成气产物分布的影响。研究结果表明：PP塑料的水蒸气气化前期以解离能较小处的单体连接键断裂形成丙烯(CH₃—CH\stackrel{}{̿}CH₂)单体为主要反应过程。随后,单体继续解离生成更小的C₁~C₂烃类分子及·H、CH₃·等自由基片段。在水蒸气重整反应阶段,H₂的生成有多种路径,但由前期含C结构上脱掉的游离·H自由基与H₂O的结合是H₂的最主要生成路径,占据了H₂生成量的70%。同时伴随产生的·OH自由基通过与小分子结合,脱H等过程,是CO的主要生成方式。提高温度和含水量可促进烃类的水蒸气重整反应,从而提高H₂和CO合成气产率,但改善效果逐渐减弱。以上结果对于掌握塑料水蒸气反应进程,以及实验参数调整有重要指导意义。     

木屑水蒸气气化制取富氢燃气研究

以木屑为原料,利用高温固定床反应器,通过高温水蒸气气化制取富氢燃气,考察了气化温度(750~1000℃)和水蒸气流量(0.290~1.409 g/min)对燃气中H₂的体积分数、热值、产气率等指标的影响。实验结果表明:不同的气化温度和水蒸气流量对燃气各组分体积分数有很大的影响,较高的气化温度和适当的水蒸气引入量有利于氢气的产生,但是过高的温度和过量水蒸气的引入会造成燃气热值降低。综合考虑各方面影响,水蒸气气化的最适条件为气化温度900℃,水蒸气流量1.033 g/min,在该条件下,所制得的气化燃气中H₂体积分数为45.74%,热值为11.69 MJ/m³,产气率为1.96 L/g。     

滴管炉内不同煤阶煤焦水蒸气气化反应特性

在滴管炉内对煤焦与水蒸气气化反应进行了实验研究,考察了煤阶、气化温度、水蒸气与进料煤焦质量比（气焦比）对气化气体产物释放特性以及煤焦转化率的影响。实验温度为1100、1200、1300和1400℃,气焦比分别为0.4：1、0.6：1和1：1。研究发现：滴管炉内不同煤焦的水蒸气气化气体产物以H₂含量最高,CH₄含量最低。不同煤阶热解焦、气化温度以及气焦比的变化影响滴管炉内水蒸气气化产物气体组成和转化率的高低。随气化温度的升高,神府煤焦和北宿煤焦气化气体产物中H₂和CO产率不断增大,H₂/CO的比值则逐渐减小,碳转化率有不断增加的趋势。在气化温度大于1200℃的条件下,当气焦比从0.4：1增至0.6：1,神府煤焦和北宿煤焦的碳转化率变化幅度不大（5%以内）;当气焦比从0.6：1增至1：1,北宿煤焦的碳转化率略微降低,而神府煤焦的碳转化率增幅则在15%以上。     

锡林郭勒褐煤在超临界水和不同气氛下的液化性能

研究了锡林郭勒褐煤在超临界水和N₂气氛下,以及K₂CO₃,FeS+S和KOH三种催化剂分别作用下的液化性能,并与其在供氢溶剂四氢萘和H₂气氛下的液化性能进行比较。结果表明:锡林郭勒褐煤在供氢溶剂四氢萘和H₂气氛下具有较高的液化活性,在420℃、无催化剂条件下褐煤的液化转化率和油水气收率分别为76.8%和51.0%;而在相同温度、添加5%甲酸的超临界水和N₂气氛下,褐煤的液化转化率和油水气收率分别降为32.0%和29.2%,且褐煤液化主要转化为附加值高的油气部分。K₂CO₃,FeS+S和KOH三种催化剂对锡林郭勒褐煤在超临界水中液化都具有较好的催化活性,按催化活性由高到低排序为K₂CO₃,FeS+S,KOH;420℃时K₂CO₃对锡林郭勒褐煤具有最好的催化效果,褐煤的液化转化率和油水气收率最高,分别为46.5%和42.2%。气氛对锡林郭勒褐煤在超临界水中的液化性能具有较大的影响,在CO气氛下锡林郭勒褐煤的液化活性最高,420℃时褐煤的液化转化率和油水气收率最高,分别为52.2%和44.4%。这是由于在CO气氛下能够发生水煤气变换反应,可以为液化过程提供原位活性H,从而促进了油气收率和液化转化率的提高。     

Hydrogen production by catalytic gasification of cellulose in supercritical water

Cellulose, one of the important components of biomass, was gasified in supercritical water to produce hydrogen-rich gas in an autoclave which was operated batch-wise under high-pressure. K₂CO₃ and Ca(OH)₂ were selected as the catalysts (or promoters). The temperature was kept between 450°C and 500°C while pressure was maintained at 24–26 MPa. The reaction time was 20 min. Experimental results showed that the two catalysts had good catalytic effect and optimum amounts were observed for each catalyst. When 0.2 g K₂CO₃ was added, the hydrogen yield could reach 9.456 molkg^-1 which was two times of the H₂ amount produced without catalyst. When 1.6 g Ca(OH)₂ was added, the H₂ yield was 8.265 molkg^-1 which is lower than that obtained using K₂CO₃ as catalyst but is still 1.7 times that achieved without catalyst. Comparing with the results obtained using K₂CO₃ or Ca(OH)₂ alone, the use of a combination of K₂CO₃ and Ca(OH)₂ could increase the H₂ yield by up to 2.5 times that without catalyst and 25% and 45% more than that obtained using K₂CO₃ and Ca(OH)₂ alone, respectively. It was found that methane was the dominant product at relatively low temperature. When the temperature was increased, the methane reacts with water and is converted to hydrogen and carbon dioxide.     

沉淀剂对Cu-Zn-Al-Mg甲醇合成催化剂性能的影响

采用二步共沉淀法,选取不同沉淀剂Na_2CO_3、K_2CO_3和Na HCO_3制备Cu-Zn-Al-Mg合成甲醇催化剂,考察不同沉淀剂对催化剂性能的影响。采用N_2低温吸附、XRD、H_2-TPR和TG-DTG等对样品进行分析,结果表明,K_2CO_3为沉淀剂时,催化剂前驱体中锌铝水滑石物相多且结晶好,Na_2CO_3为沉淀剂时,催化剂前驱体中有更多的Zn~(2+)发生取代生成(Cu,Zn)_2(OH)_2CO_3物相,有利于CuO分散,NaHCO_3为沉淀剂时,催化剂比表面积小,平均孔径及CuO晶粒尺寸大。     

CO2 absorption and regeneration of alkali metal-based solid sorbents

Potassium-based sorbents were prepared by impregnation with potassium carbonate on supports such as activated carbon (AC), TiO₂, Al₂O₃, MgO, SiO₂ and various zeolites. The CO₂ capture capacity and regeneration property were measured in the presence of H₂O in a fixed-bed reactor, during multiple cycles at various temperature conditions (CO₂ capture at 60 °C and regeneration at 130–400 °C). Sorbents such as K₂CO₃/AC, K₂CO₃/TiO₂, K₂CO₃/MgO, and K₂CO₃/Al₂O₃, which showed excellent CO₂ capture capacity, could be completely regenerated above 130, 130, 350, and 400 °C, respectively. The decrease in the CO₂ capture capacity of K₂CO₃/Al₂O₃ and K₂CO₃/MgO, after regeneration at temperatures of less than 200 °C, could be explained through the formation of KAl(CO₃)₂(OH)₂, K₂Mg(CO₃)₂, and K₂Mg(CO₃)₂·4(H₂O), which did not completely converted to the original K₂CO₃ phase. In the case of K₂CO₃/AC and K₂CO₃/TiO₂, a KHCO₃ crystal structure was formed during CO₂ absorption, unlike K₂CO₃/Al₂O₃ and K₂CO₃/MgO. This phase could be easily converted into the original phase during regeneration, even at a low temperature (130 °C). Therefore, the formation of the KHCO₃ crystal structure after CO₂ absorption is an important factor for regeneration, even at the low temperature. The nature of support plays an important role for CO₂ absorption and regeneration capacities. In particular, the K₂CO₃/TiO₂ sorbent showed excellent characteristics in CO₂ absorption and regeneration in that it satisfies the requirements of a large amount of CO₂ absorption (mg CO₂/g sorbent) and fast and complete regeneration at a low temperature condition (1 atm, 150 °C).     

钾对低温耐硫变换催化剂的影响

采用不同钾源制备低温耐硫变换催化剂Mo-Co-K/Al_2O_3,通过XRD、N_2吸附-脱附法和微反评价等研究钾源对催化剂的钾流失率、孔结构及反应过程中钾硫酸盐化的影响。结果表明,以K_2SO_4为钾源的催化剂钾流失率最大,活性最低。KNO_3和KOH对拟薄水铝石的胶溶能力较强,易形成小孔径结构的催化剂。K_2SiO_3可以有效避免催化剂中钾在反应过程中的硫酸盐化。     

纸浆黑液和钙混合催化剂进行高变质无烟煤水蒸气气化的研究

The catalytic effects of single and mixed catalysts, i.e. single 3%Ca and 5%Na-BL（black liquor） catalysts and mixed 3%Ca＋5%Na-BL catalyst, on carbon conversion, gasification reaction rate constant and activation energy, relative amount of harmful pollutant like sulphur containing gases have been investigated by thermogravimetry in steam gasification under temperature 750℃ to 950℃ at ambient pressure for three high-metarnorphous anthracites （Longyan, Fenghai and Youxia coals in Fujian Province）. The mixed catalyst of 3%Ca＋5%Na-BL increases greatly the carbon conversion and gasification rate constant by accelerating the gasification reaction C＋H2O→CO＋H2 due to presence of alkali surfacecompounds [COM], [CO2M] and exchanged calcium phenolate and calcium carboxylate （-COO）2. By adding CaCO3 into BL catalyst in gasification, in addition to improving the catalyst function and enhancing the carbon conversion, the effective desulphurization is also achieved, but the better operating temperature should be below 900℃. The homogenous and shrinking core models can be successfully employed to correlate the relations between the conversion and the gasification .time .and to estimate the reaction rate constant, The reaction acUvaUon energy and pre-exponential factor are estimated and the activation energy for mixed catalyst is in a range of 98.72-166.92 kJ·mol^-1, much less than 177.50-196.46 kJ·mol^-1 for non-catalytic steam gasification for three experimental coals.     

Promotion effect of residual K on the decomposition of N2O over cobalt–cerium mixed oxide catalyst

A series of cobalt–cerium mixed oxide catalysts (Co₃O₄–CeO₂) with a Ce/Co molar ratio of 0.05 were prepared by co-precipitation (with K₂CO₃ and KOH as the respective precipitant), impregnation, citrate, and direct evaporation methods and then tested for the catalytic decomposition of N₂O. XRD, BET, XPS, O₂-TPD and H₂-TPR methods were used to characterize the catalysts. Catalysts with a trace amount of residual K exhibited higher catalytic activities than those without. The presence of appropriate amount of K in Co₃O₄–CeO₂ may improve the redox property of Co₃O₄, which is important for the decomposition of N₂O. When the amount of K was constant, the surface area became the most important factor for the reaction. The co-precipitation-prepared catalyst with K₂CO₃ as precipitant exhibited the best catalytic performance because of the presence of ca. 2 mol% residual K and the high surface area. We also discussed the rate-determining step of the N₂O decomposition reaction over these Co₃O₄–CeO₂ catalysts.