B116型变换催化剂在净化黄磷尾气部分变换中试中的应用研究

采用B116型变换催化剂,对黄磷尾气部分变换制甲醇合成气进行中试实验,结果表明,三段催化剂装填方式优于两段装填,三段装填24 h内催化剂床层温度稳定,20 h时变换炉出口气体达到制甲醇合成气的要求;140 h内催化剂床层上部温度不能维持催化剂活性温度,且变换率逐渐降低,100 h时H2/CO体积比不能满足制甲醇合成气的要求.因此,将B116型催化剂用于黄磷尾气部分变换制甲醇合成气,存在不能长时间保持稳定的变换率,不能维持床层温度稳定的问题.因此为黄磷尾气综合利用实现工业化,需开发新型耐高浓度CO的变换催化剂.     

QDB-04型CO耐硫变换催化剂在Shell粉煤气化工艺中的应用

介绍了QDB-04型CO耐硫变换催化剂在Shell粉煤气化低水气比耐硫变换工艺中的应用情况。运行结果表明,选用QDB-04型催化剂,并采用控制反应水气比和床层入口温度等手段来控制反应深度和床层热点温度的办法是可行的。每段水气比的最高值不超过0.40,各段床层温升平稳,一段反应器温度一般为360~370℃,各段出口CO指标分配合理,最终出口CO体积分数小于0.4%,无甲烷化副反应的发生。     

甲醇水蒸气重整制氢固定床反应器的数学模拟

建立二维拟均相固定床反应器数学模型用于描述Cu₅₀Zn₃₀Ce₁₀Al₁₀催化剂颗粒的甲醇水蒸气重整制氢反应过程，该模型由流体相的质量、热量和动量传递方程组成，耦合催化剂颗粒内部的扩散-反应模型。通过将模型预测值与实验数据进行比较，验证反应器数学模型的准确性。在此基础上，分析关键组分CO₂和CO的效率因子随床层轴向的变化规律以及催化剂床层的轴径向温度分布。结果表明：催化剂床层的轴径向温差较大，导致CO₂效率因子变化较大，而CO由于浓度低，反应速率慢，其效率因子变化不明显。     

介孔CuCe/M/CuCe(M=Co,Mn,Zr)催化剂富H_2中优先氧化CO的催化性能

优先氧化是去除富H2中CO最有效的方法,铜铈催化剂是该领域的研究热点。以SBA-15为模板剂,采用纳米刻蚀法合成系列介孔Cu Ce/M/Cu Ce(M=Co,Mn,Zr)催化剂,采用XRD、N2吸附-脱附、TEM、H2-TPR和O2-TPD对催化剂结构及形貌进行表征,并对其在富H2中CO优先氧化性能进行研究。结果表明,Mn有利于催化剂表面吸附氧的增加,有助于大量氧空位的产生,进而促进CO优先氧化性能的提高;Zr的加入抑制了Cu O的还原,且其表面氧脱附温度范围过宽,不利于催化剂催化氧化性能的释放。掺杂Co与Mn可以形成Ce-Cu-M-O固溶体,促进了催化剂表面氧和晶格氧之间的相互转化,最终有利于铜铈催化剂CO优先氧化性能的提高。     

Fe-5A催化亚甲基蓝溶液湿式H2O2氧化

以九水硝酸铁[Fe(NO3)3?9H2O]和柱状5A分子筛为原料采用湿法浸渍法制备Fe?5A催化剂,催化湿式H2O2氧化亚甲基蓝溶液,考察了间歇反应器中pH值和温度对亚甲基蓝转化率的影响及在连续固定床反应器中床层催化剂装填量、进料液流量、温度和亚甲基蓝入口浓度对亚甲基蓝降解性能的影响. 结果表明,在间歇反应中,在亚甲基蓝浓度50 mg/L、温度70℃、pH为2、反应20 min的条件下,亚甲基蓝的转化率为95.9%. 固定床反应中,随温度降低及进料液流量增加,亚甲基蓝转化率降低;随亚甲基蓝入口浓度增加,亚甲基蓝和化学需氧量(COD)的转化率变化幅度很小. 在温度70℃及pH=2、进料液流量4 mL/min、Fe?5A催化剂装填量1.25 g、亚甲基蓝浓度50?300 mg/L、固定床连续运转5 h的条件下,亚甲基蓝的转化率超过98%,COD转化率大于82%,铁浸出浓度低于3.5 mg/L,相同条件下,装填2.5 g 5A分子筛的固定床中50 mg/L亚甲基蓝的转化率仅为73.3%.     

绕管移热反应器在泉稷“3052”项目变换装置的应用

介绍了绕管移热反应器在山西阳煤丰喜泉稷能源有限公司变换装置中的应用情况,简述了反应器的设备结构及管间催化剂的装填及硫化过程,验算了移热变换的平衡温距,结果表明,移热变换的平衡温距为9℃,说明该反应器可以很好地控制催化剂床层温度。实践证明,绕管移热反应器应用于大型煤化工装置的CO变换工段,可延长催化剂的使用寿命,提高装置热效率,减少设备投资。     

乙炔前加氢催化剂活性分析方法研究

乙炔加氢催化剂活性对反应器入口CO浓度变化非常敏感,量化CO浓度对催化剂活性的影响程度并预测催化剂活性与反应器入口温度的对应关系十分必要。通过反余切三角函数建立催化剂活性随CO浓度变化的模型,定量描述CO浓度对催化剂活性的影响,并结合反应器入口温度、入口原料气总质量、入口与出口各物质的含量等实际生产数据,优化动力学参数和失活模型参数,定性和定量描述催化剂活性变化后反应器入口温度的调整方法,利用此模型结合相关数据考察反应器入口温度对催化剂活性的影响。     

泡沫金属镍微型反应器内一氧化碳优先氧化

在微型反应器中,采用泡沫金属镍为载体负载Cu-Ce-Zr-O催化剂,用于优先氧化去除富氢气体中的CO。考察Zr掺杂量、焙烧温度和催化剂预处理工艺对催化剂性能的影响。结果表明,CuCe_9Zr_(1.5)O_δ催化剂表现出较好的催化性能,反应温度(160～260)℃,CO转化率达99%以上,出口气浓度降至100×10~(-6)以下,CO选择性维持在40%左右;反应温度(180～240)℃,富氢气体中CO浓度降至60×10~(-6)以下。经H_2预处理后的催化剂低温活性和反应性能略有提高。     

10 kW_(th)级串行流化床中木屑化学链燃烧试验

设计并建立了10 kWth级串行流化床化学链燃烧反应器系统,以NiO/Al2O3为载氧体,在该系统上进行生物质(松木木屑)化学链燃烧分离CO2的试验研究,探讨了燃料反应器温度T、水蒸气/生物质比率S/B对两个反应器(空气反应器和燃料反应器)气体产物组成以及燃烧效率的影响。试验结果表明,燃料反应器温度是影响生物质化学链燃烧过程的重要因素,随着温度的升高,燃料反应器气体产物中CO2浓度不断上升,CH4浓度显著降低,CO浓度先升高而后迅速下降;较高的反应器温度有助于燃烧效率的提高。随着S/B的增加,燃料反应器气体产物中CO和CH4浓度均会增大,CO2浓度以及燃烧效率有所降低。在100h的连续试验过程中,采用共沉淀法制备的NiO/Al2O3载氧体展现出良好的氧化-还原性能和较强的持续循环能力,是生物质化学链燃烧理想的载氧体。     

柴油车尾气四效组合催化剂的研究

提出设计双层组合催化剂净化新技术,即碳黑氧化燃烧催化剂床层和NOx还原催化剂床层的组合,该组合催化剂对柴油机尾气四种污染物的消除具有较高的催化活性。采用浸渍法制备了Al₂O₃负载不同量的La_0.8K_0.2MnO₃和相同负载量、不同K含量的La_1-xK_xMnO₃/Al₂O₃催化剂作为氧化催化剂处理碳烟、CO和HC;采用等体积浸渍法制备Cr/HZSM-5、Mo/HZSM-5、W/HZSM-5三系列催化剂作为还原催化剂处理NOx,并将其进行组合,得到优良的氧化还原组合催化剂,同时处理柴油车尾气中的四种污染物。在模拟柴油车尾气组成条件下,用乙炔代表烃类物质并采用固定床微型反应装置,考察了所制备的双层四效组合催化剂净化柴油车尾气的催化性能。研究发现,负载质量分数为50%的La_0.5K_0.5MnO₃/Al₂O₃和负载量为1.42×10^-4mol·g^-1的W/HZSM-5组合催化剂对于同时消除柴油车尾气NO、碳颗粒、CO和HC有较好的效果。NO还原为N₂的转化率在反应温度范围最高可达79%,同时碳颗粒的燃烧峰值温度为448 ℃,碳颗粒燃烧生成CO₂ 的最大选择性可达98%,乙炔完全转化的温度为364 ℃,从而实现了四种有害物质的同时催化净化。     

Development of residential PEFC cogeneration systems: Ru catalyst for CO preferential oxidation in reformed gas

The performance of the novel Ru catalyst in a single-stage CO preferential oxidation removal reactor was investigated for residential polymer electrolyte fuel cell (PEFC) cogeneration systems. The outlet CO concentration of the CO removal reactor was reduced to less than 1 ppm even at [O₂]/[CO]=1.5. The natural gas fuel processor equipped with the CO removal reactor achieved the target thermal efficiency of 77% (LHV). Moreover, the durability of the Ru catalyst has been confirmed for more than 16,000 h at a micro-reactor and for more than 8000 h at an actual CO removal reactor. Because of the low O₂/CO molar ratio, the high CO removal conversion and the long-term durability, the Ru catalyst contributes to the development of residential PEFC cogeneration systems.     

PtCoK/Al2O3催化剂涂层选择性氧化脱除富氢气氛中的CO

富氢气体中选择性氧化脱除CO是去除重整气中少量CO的有效方法。该文考察了K/Pt摩尔比对PtCoK/Al2O3催化剂涂层的影响。研究发现,适量K的添加能显著提高催化剂涂层的CO去除能力,最优K/Pt摩尔比是1～1.5,超过这个配比,CO脱除能力降低。将进口气氛中O2的体积分数从1%提高到1.5%,可提高CO转化率,但是对应的CO2选择性有所下降。富氢气中同时含有H2O和CO2对催化剂涂层活性影响微弱。连续反应100 h后,PtCoK/Al2O3催化剂涂层上CO转化率几乎未降低,催化剂涂层非常稳定,表明该催化剂涂层具有较强的工业化应用前景。     

Ru-La2O3/γ-Al2O3催化CO选择性氧化反应

采用浸渍法制备了Ru-La2O3/γ-Al2O3复合氧化物催化剂,在固定床微反装置中考察了催化剂中稀土La的掺杂量、氧气量、原料气中水和CO2含量以及空速等工艺条件对Ru-La2O3/γ-Al2O3催化剂在CO选择性氧化反应中催化性能的影响.结果表明,Ru/γ-Al2O3催化剂添加质量分数10%的La2O3后的催化性能较好,且具有较好到抗湿性和抗CO2能力.在原料气组成为65%H2,25%CO2,1%CO,9%He,氧气的分压与CO分压相等,气体流速为100 mL/min和气体空速为10 000 h-1的条件下,在110～170℃进行CO选择性氧化,CO转化率大于99%,CO的出口浓度小于100 μL/L,满足了质子交换膜燃料电池对富氢气体中CO浓度的要求.     

Performance of CO preferential oxidation reactor with noble-metal catalyst coated on ceramic monolith for on-board fuel processing applications

On-board fuel processors are being developed to provide hydrogen-rich gas to the polymer electrolyte fuel cell automotive propulsion systems. Whereas the anode catalyst in the fuel cell has low tolerance for carbon monoxide, 10–100 ppm, reforming of gasoline and other hydrocarbon fuels generally produces 1–2% of CO. Of the many methods of removing CO from the reformer gas, preferential oxidation (PrOx) of CO over noble-metal catalysts is practiced most frequently. In this paper, we present experimental data for CO conversion on a Pt-based catalyst that is active at room temperature and was coated on a ceramic monolith. The data is used to develop an empirical correlation for selectivity for CO oxidation as a function of CO concentration and oxygen stoichiometry at 30,000–80,000/h space velocity. The selectivity correlation is used in a model to analyze the performance of multi-stage, adiabatic PrOx reactors with heat exchange between the stages to cool the reformate to 100 °C. An optimization algorithm is used to determine the operating conditions that can reduce CO concentration to 10 ppm while minimizing parasitic loss of H₂ in the reformate stream. It is found that the 10 ppm constraint limits the maximum inlet CO concentration to 1.05% in a single-stage reactor and to 3.1% in a two-stage reactor. The results clearly show the incremental reduction in parasitic H₂ loss by addition of second and third stages.     

Performance of Pt-Fe/mordenite monolithic catalysts for preferential oxidation of carbon monoxide in a reformate gas for PEFCs

Pt-Fe/mordenite catalysts coated on ceramic straight-channel monoliths were evaluated for the preferential oxidation of carbon monoxide (PROX) in hydrogen-rich gas streams. In a feed gas containing 1% CO, 1% O₂, with the balance H₂, CO conversion reached almost 100% at temperatures ranging from 100 to 130 °C, i.e., an outlet CO concentration of less than 10 ppm. Even in a synthetic reformate gas (1% CO, 1% O₂, 15% H₂O, 20% CO₂, balance H₂), the monolithic catalyst exhibited excellent activity, reducing the CO concentration to less than 100 ppm. In particular, under optimized conditions, an outlet CO concentration of less than 10 ppm was realized. This is the first report that has demonstrated that monolithic catalysts could achieve the 10-ppm target level at a low O₂/CO ratio and a high space velocity in a single-stage reactor. Excellent durability of the monolithic catalyst is expected, based on a lack of deterioration in performance during 500 h of operation.     

SELF-SUSTAINED OSCILLATIONS DURING CO OXIDATION ON A Pt/γ-Al2O3 CATALYST

A systematic study of the effect of reaction environment and catalyst surface on self-sustained oscillations during CO oxidation on a Pt/γ-Al2O, catalyst is presented in this paper. The catalyst, consisting of a fixed bed of small particles, was subjected to three different pretreatments: fresh, O2 - H2 treated and poisoned by SO2. Self-sustained oscillations, lasting for as long as desired, were manifest in a narrow range of temperatures and O2/CO ratios. The structure of the oscillatory pattern varied with catalyst pretreatment, however, in all cases the predominant feature consisted in transitions between low and high conversion levels (ignition-quenching). The amplitude and frequency of the oscillations varied with surface pretreatment, however, they decreased as temperature and O2:/CO ratio increases. Small temperature fluctuations of less than 6°C, which mirrowed concentration oscillations were also observed. A unique feature observed under certain conditions, was an overshoot of CO2 outlet concentration in excess to the 100% conversion, which indicated the participation of surface stored CO. The results are discussed in terms of competitive CO and O2 adsorption-reaction coupled with reactor and surface balances.     

SELF-SUSTAINED OSCILLATIONS DURING CO OXIDATION ON A Pt/γ-Al2O3 CATALYST

A systematic study of the effect of reaction environment and catalyst surface on self-sustained oscillations during CO oxidation on a Pt/γ-Al2O, catalyst is presented in this paper. The catalyst, consisting of a fixed bed of small particles, was subjected to three different pretreatments: fresh, O2 - H2 treated and poisoned by SO2. Self-sustained oscillations, lasting for as long as desired, were manifest in a narrow range of temperatures and O2/CO ratios. The structure of the oscillatory pattern varied with catalyst pretreatment, however, in all cases the predominant feature consisted in transitions between low and high conversion levels (ignition-quenching). The amplitude and frequency of the oscillations varied with surface pretreatment, however, they decreased as temperature and O2:/CO ratio increases. Small temperature fluctuations of less than 6°C, which mirrowed concentration oscillations were also observed. A unique feature observed under certain conditions, was an overshoot of CO2 outlet concentration in excess to the 100% conversion, which indicated the participation of surface stored CO. The results are discussed in terms of competitive CO and O2 adsorption-reaction coupled with reactor and surface balances.     

Catalytic performance of K-promoted Rh/USY catalysts in preferential oxidation of CO in rich hydrogen

K-promoted Rh/USY (molar ratio: K/Rh=3) catalyst was found to exhibit high performance in preferential oxidation of CO in rich hydrogen. Such high performance was maintained in the presence of steam and CO₂. The CO oxidation activity of the K-Rh/USY catalyst was independent of the partial pressure of H₂, while the activity of the unpromoted Rh/USY catalyst was decreased significantly in hydrogen-rich stream. The effect of potassium addition on the catalyst structure was investigated and is discussed in terms of the differences in the catalytic performance.     

不同P与V比的Mo/VPO催化剂物相组成及其催化性能

采用有机相法制备了不同P与V物质的量比的Mo掺杂VOHPO₄·0.5H₂O前驱体,并通过体积分数为50%空气-40%氮气-10%水蒸汽混合气氛活化得到Mo/VPO催化剂,采用固定床反应器评价其催化正丁烷氧化制顺酐的性能。结果表明,Mo/VPO催化剂催化活性随P与V物质的量比的增大而降低,但顺酐选择性与P与V物质的量比并不呈线性关系,P与V物质的量比为0.9的Mo/VPO催化剂具有最佳的催化性能。XRD分析表明,Mo/VPO催化剂催化正丁烷氧化制顺酐的主要活性物相为(VO)₂P₂O₇和钒磷云母相,形成的主要因素不是P与V物质的量比,而是由焙烧条件决定。低P与V物质的量比的Mo/VPO中存在的少量V₂O₅物相能够提升催化剂的活性和顺酐选择性,但含量过高会因深度氧化降低催化性能。催化剂中存在的钒磷云母相有利于缩短催化剂稳定时间并提升催化性能。