一种轻质高效焦炉气甲烷化催化剂的性能研究

考察了温度、压力、空速等条件对所制备的焦炉气甲烷化催化剂活性的影响,结果显示所制备的催化剂活性高,并具有良好的抗结炭性能,能满足焦炉气甲烷化反应过程的要求。     

新型焦炉气甲烷化催化剂的性能研究

针对传统甲烷化催化剂在水煤气或焦炉煤气等高碳含量原料气甲烷化过程中耐热性和抗积炭性差等缺点,开发出适用于焦炉气、水煤气甲烷化制合成天然气（SNG）的新型W907甲烷化催化剂。考察了催化剂还原温度、反应压力、空速、反应温度及水气分压对反应活性的影响,同时对该催化剂进行了连续220 h稳定性考察。结果表明,催化剂在较宽的空...     

焦炉气甲烷化催化剂替代进口

正近日,西南化工研究院甲烷化催化剂替代丹麦托普索公司产品在内蒙古三聚家景新能源有限公司4亿Nm~3/a焦炉气甲烷化制天然气装置一次开车成功,各项指标均达到装置设计要求。这是国产甲烷化催化剂首次实现对国外甲烷化催化剂的替代,标志着该院焦炉气甲烷化催化剂成为目前唯一能比肩国外先进技术     

焦炉气制甲醇工艺中硫化物的脱除

介绍了以煤为原料,经纯氧连续气化得到焦炉气,焦炉气经净化、甲烷转化,合成甲醇的工艺流程。讨论了焦炉气中硫化物的存在对甲烷转化催化剂、甲醇合成催化剂活性的影响。采用湿法脱硫串干法脱硫的方法,以及两次催化加氢串两次氧化锌脱硫工艺,有效脱除了焦炉气中的H_2S、COS、CS_2、硫醚、硫醇和噻吩等硫化物,探讨了有机硫化物噻吩的脱除方法,并比较了各种方法的优缺点。     

焦炉气甲烷化制天然气技术开发

焦炉气甲烷化制合成天然气SNG、压缩天然气CNG和液化天然气LNG是焦炉气高效利用的新途径。讨论并对比分析了焦炉气甲烷化制天然气的不同工艺流程,进行了经济评价。结果表明,焦炉气甲烷化制合成天然气或压缩天然气、液化天然气,原料利用率更高,环保效果更佳,且经济效益更优。     

国内首套焦炉气甲烷化制CNG装置运行总结

介绍了国内首套焦炉气甲烷化制天然气工业化装置的工艺原理。对加氢脱硫催化剂的硫化和甲烷化催化剂的还原运行情况进行了总结。运行结果表明该装置具有工艺简单、操作平稳、设备投资少、能耗低等特点。     

焦炉气加氢脱硫催化剂的研究

以高浓度CO、CO_2焦炉气为原料,对催化剂CNDS-19分别进行了脱氧、脱烯烃、脱硫活性测试,并考察了催化剂抑制甲烷化副反应能力,确定了两段反应的实验条件,对催化剂CNDS-19进行了1000h寿命实验,结果表明:当一段反应温度260℃,空速2000h,二段反应温度360℃,空速1000h,压力2.5-2.8MPa时,催化剂加氢活性高,稳定性好,尾气噻吩含量始终维持在0.1ppm以下,总的碳基甲烷化率为1.94%。     

焦炉气甲烷化制9×10~7 Nm~3/aCNG装置运行总结

简述了国内焦炉煤气甲烷化制天然气的工业应用情况。介绍了用焦炉煤气制压缩天然气的工艺过程及所采用的催化剂,对粗焦炉气的预处理、加氢脱硫和焦炉气甲烷化运行情况进行阐述。结果表明,该装置具有操作温度低、运行平稳、能耗低的特点,首次采用两段一体式废锅回收热量,还具有设备投资少的优点。     

焦炉气制甲烷的新型催化剂及其应用工艺

介绍了一种用于焦炉气回收制甲烷的新型催化剂,模拟工业条件的测试实验数据显示,该新型催化剂具有高活性、良好的耐热性和抗结炭性,适用于焦炉气或煤制气制合成甲烷的工艺.根据该催化剂性能提出2种新型工艺流程:一是以焦炉气为原料,设置两段绝热催化反应加变压吸附系统的工艺,以制取天然气和纯氢产品;二是在焦炉气中添加煤气或富含碳氧化...     

甲烷化技术国产化研究进展

甲烷化是焦炉气制天然气、煤制天然气生产流程的关键步骤,为打破国外技术垄断,国内研究机构积极进行技术开发。系统梳理了甲烷化技术的国产化研究进展,分析了焦炉气甲烷化技术的应用现状,探讨煤制天然气甲烷化技术的应用前景,并就降低首次工程应用风险提出几点建议。国内甲烷化技术已经实现广泛开发,焦炉气甲烷化技术成功实现工业化应用,其国内市场占有率高于国外技术。煤制天然气甲烷化技术已成功开发,工业化应用前景广阔,首次工程应用时应注重经验借鉴、安全分析及设备选型等。     

柴油加氢反应器不同位置精制剂的失活分析

针对某炼油厂柴油加氢裂化装置停工换剂时发现加氢精制反应器床层顶部的精制剂表面覆盖垢物的现象,对不同位置的精制剂进行取样分析。对所取精制剂进行甲苯抽提、再生后采用比表面积及孔径分析仪、碳-硫分析仪（C-S）和扫描电子显微镜（SEM）等手段进行检测。结果表明：不同位置的失活精制剂上积炭量均较低,而比表面积等孔结构参数均显著降低,尤以装填位置靠上的精制剂更为明显,失活精制剂的再生效果均不理想;再生精制剂上出现磷酸铝特征衍射峰,精制剂表面沉积含磷、硅、铁和少量砷元素的无机物,或少量进入精制剂孔道,其是导致精制剂失活的主要原因,而且沿着物流自上而下的流向精制剂上杂质的沉积量逐渐减少,催化剂的失活程度减弱。     

Hydrogenation of cottonseed oil with reused catalyst

Cottonseed oil was hydrogenated using both new (Rufert catalyst flakes) and reused (up to five uses) catalysts at 130–169C, at a pressure of 45 psig, and with high degrees of agitation. The activity of the catalyst increased initially with use, especially at 130C, but with continued use the activity decreased. The selectivity of the hydrogenation decreased with reuse of the catalyst, especially at lower temp. Isomerization decreased slightly as the catalyst was used only at higher temps. The induction period found with fresh catalyst at 130C was eliminated in runs with second- and third-use catalyst. A small induction period was noted with fifth-use catalyst. Treatment of once-use catalyst with air severely reduced the catalyst activity. Steam- and vacuum-treatment of the catalyst resulted in a slightly less active catalyst than a hydrogen-treated catalyst. None of these treatments significantly affected selectivity or isomerization. Results of this investigation can be explained in large part by the concn of hydrogen absorbed on the catalyst surface.     

Study of Deactivation of Pd(OH)2/C Catalyst in Reductive Debenzylation of Hexabenzylhexaazaisowurtzitane

The conversion of hexabenzylhexaazaisowurtzitane (HBIW) to 2,6,8,12‐tetraacetyl‐4,10‐dibenzyl‐2,4,6,8,10,12‐hexaazaisowurtzitane (TADB) is the major challenge in the production of hexanitrohexaazaisowurtzitane (HNIW) which only proceeds over supported palladium catalyst in a reductive debenzylation reaction. The catalyst is quickly deactivated during the debenzylation reaction. In this study, the change in Pd content in the catalyst during the reaction was measured. It was demonstrated that a portion of the palladium particles in the catalyst was leached during the reaction. The H₂ chemisorption isotherm on the catalyst at 303 K showed that the volume of chemisorbed H₂ on spent catalyst was significantly less than that on fresh catalyst. The N₂ physisorption isotherm on the catalyst at 77 K revealed that the surface area of spent catalyst was less than that of fresh catalyst. Moreover, the FESEM‐EDS and TEM images and also wide‐angle XRD patterns demonstrated that the mean sizes of palladium crystallites and particles in spent catalyst were larger than those in the fresh catalyst. These results demonstrated that the leaching of palladium particles and the aggregation of palladium particles in catalyst play active roles in the deactivation of catalyst in the debenzylation of HBIW.     

聚烯烃催化剂载体材料研究进展

综述了近年来聚烯烃茂金属催化剂载体的研究进展,包括新型载体的研制、结构特点及以此载体负载茂金属对聚合产物性能的影响。人工合成的具有空心结构SiO2团粒载体,可望作为一种新型催化剂载体,不仅可以应用于传统催化剂的Ziegler-Natta催化剂、茂金属催化剂,还可以应用于后茂金属催化剂以及非茂金属催化剂等聚烯烃催化剂,替代国外进口载体,实现硅胶作为聚烯烃催化剂载体的国产化。     

Optimization of the reactor–regenerator system with catalytic parallel–consecutive reactions

The system with moving deactivating catalyst, composed of a cocurrent tubular reactor and a catalyst regenerator with an additional flux of a fresh catalyst, has been investigated. For the temperature dependent catalyst deactivation, the optimization problem has been formulated in which a maximum of a process profit flux is achieved by a best choice of temperature profile along tubular reactor, best catalyst recycle ratio and best catalyst activity after regeneration. The set of parallel–consecutive reactions, A+B→R and R+B→S, with desired product R has been taken into account. A relatively unknown, powerful discrete algorithm in which a suitably defined Hamiltonian is constant along the optimal path, has been applied for optimization. The optimal solutions have been discussed. In particular, it has been shown that an increase of the unit cost of catalyst regeneration or an increase of the catalyst recycle ratio causes such optimal temperatures in reactor which save the catalyst, as the optimal temperature profiles are then shifted towards lower temperatures. Finally these profiles reach isothermal shape at the level of minimum allowable temperature and then there is no further possibility to control the reactor process by the temperature profile. Thus the catalyst activity after regeneration, as well as an average catalyst activity in the reactor do decrease when the unit catalyst regeneration cost increases. This is a new form of catalyst saving, as the catalyst deactivation rate becomes reduced when an average catalyst activity is allowed to decrease. It is important that this form of catalyst saving appears in the region where any saving of the catalyst by an optimal choice of temperature profile is impossible. It has been also shown that for small values of the catalyst recycle ratio, the catalyst regenerator should be removed from the system. In such a case, the renewal of catalyst takes place due to a fresh catalyst input, exclusively.     

CIM-6单元镍油脂氢化催化剂的研制

在用H2 冷等离子体处理常规Cu -Ni二元油脂加氢催化剂 ,发现一种新的、有用的催化剂表面结构和研制开发成功CIMCu -Ni二元油脂加氢催化剂及其相关技术的基础上 ,研制成了CIM - 6单元镍油脂加氢催化剂。实验结果表明 :1 CIM - 6催化剂用于豆油加氢制食用氢化油 ,其活性 (以催化剂的时空转化率计 )是SP - 7催化剂 (美国EngelhardCo.)的 4 5倍 ;用于菜油加氢制食用氢化油 ,其活性是SP - 7的 7 3倍。 2 CIM - 6的抗硫能力 (n(S) =3× 10 - 6 )是SP - 7的1 6倍。 3 CIM - 6的选择性比SP - 7略好     

A novel microfabricated Pd/SiO2 model catalyst for the hydrogenation of 1,3-butadiene

The hydrogenation of 1,3-butadiene was successfully demonstrated using a microfabricated catalyst. The reaction was carried out at atmospheric pressure and 100°C with a hydrogen to hydrocarbon ratio of 125. Data from a thin film Pd/silica catalyst is also presented for comparison. The conversion for the microfabricated catalyst is more stable and slightly lower than that for the thin film catalyst; however, the geometric surface area of the thin film catalyst is 7.5 times greater than that of the microfabricated catalyst. The selectivity of the reaction products is greatly different between the two catalysts. The microfabricated catalyst has a much lower selectivity for 1-butene and favors the 2-butenes more so than does the thin film catalyst.     

丁辛醇合成催化剂制备及工业侧线研究

丁辛醇是合成精细化工产品的重要原料,低压羰基合成为目前主要的工业生产工艺,其核心催化剂为三苯基膦乙酰丙酮羰基铑（ROPAC）。介绍了ROPAC催化剂制备过程及工业侧线实验结果,并通过工业放大生产实验,解决了ROPAC催化剂制备过程中的问题,二步合成单程总收率可达98%以上,ROPAC催化剂中氯离子质量分数小于0.005%。依托于天津渤化永利化工有限公司的450 kt/a丁辛醇装置,成功进行了ROPAC催化剂国产化替代工业侧线试验,自制催化剂与进口参比催化剂在100%负荷下各运行520 h,自制ROPAC催化剂与进口催化剂醛耗丙烯、产物正异比和母液中聚合物含量等指标一致,产品醛各项指标合格,催化剂整体性能与进口催化剂基本一致。     

Monte Carlo simulation of the PEMFC catalyst layer

The performance of the polymer electrolyte membrane fuel cell (PEMFC) is greatly controlled by the structure of the catalyst layer. Low catalyst utilization is still a significant obstacle to the commercialization of the PEMFC. In order to get a fundamental understanding of the electrode structure and to find the limiting factor in the low catalyst utilization, it is necessary to develop the mechanical model on the effect of catalyst layer structure on the catalyst utilization and the performance of the PEMFC. In this work, the structure of the catalyst layer is studied based on the lattice model with the Monte Carlo simulation. The model can predict the effects of some catalyst layer components, such as Pt/C catalyst, electrolyte and gas pores, on the utilization of the catalyst and the cell performance. The simulation result shows that the aggregation of conduction grains can greatly affect the degree of catalyst utilization. The better the dispersion of the conduction grains, the larger the total effective area of the catalyst is. To achieve higher utilization, catalyst layer components must be distributed by means of engineered design, which can prevent aggregation.     

制备方法对Co-Pd/TiO2催化剂催化CH4-CO2梯阶转化的影响

以钴、钯为活性金属, 分别采用浸渍法和溶胶-凝胶法制备了Co-Pd/TiO₂催化剂, 考察了不同制备方法制备的Co-Pd/TiO₂催化剂对CH₄-CO₂梯阶转化直接合成C₂含氧化合物的影响。利用XRD、XPS和N₂-吸附-脱附对催化剂进行了表征。结果表明:两种方法制备的催化剂反应前与反应后表面织构都存在较大变化, 且催化剂中均存在CoTiO₃物种, 这是活性金属Co与载体TiO₂之间发生强相互作用, CO²⁺替代TiO₂晶格中的Ti⁴⁺的结果;CoO和金属Pd可能是该反应的活性中心;反应前与反应后溶胶-凝胶法制备的催化剂的表面Co含量均低于浸渍法制备的催化剂, 而表面Pd含量则均高于浸渍法制备的催化剂, 且溶胶-凝胶法制备的催化剂各种产物的生成速率均高于浸渍法制备的催化剂, 因此, 与浸渍法制备的催化剂相比, 溶胶-凝胶法制备的催化剂具有更好的催化活性。