铜基甲醇催化剂失活因素及解决措施研究进展

铜基催化剂是甲醇合成反应中最为普遍使用的催化剂。介绍了铜基催化剂失活原因,包括烧结失活、中毒失活等,结果发现烧结是铜基催化剂失活的主要原因,这是由于催化剂的烧结容易诱导活性中心铜粒子团聚长大而导致有效活性位急剧减少,从而导致催化剂稳定性急剧下降。此外,还介绍了提高催化剂稳定性目前提出的主要解决办法,主要包括加入助剂、形成合金、优化金属与载体之间相互作用、最大化粒子间距离、限域作用等。     

Electronic effects in the coke deactivation of platinum-alumina catalysts

By means of XPS, ESR, DTA, and pyridine flash desorption techniques; micropulse reactor studies; and quantum-chemical calculations, it was shown that, during the coking of platinum-alumina catalysts in hydrocarbon media, the electron density of the platinum atom increases up to the formation of Pt⁰, which is a deactivating factor from the viewpoint of the electronic effects. The stabilization of the activity of platinum-alumina catalysts consists in an increase in the effective positive charge on the platinum atom; this function is fulfilled by modifier elements. It was found that the platinum protection mechanism differs, depending on the nature of the modifying additive: certain elements function via another, additional mechanism of catalyst stabilization, the blocking action. The theoretical conclusions made in this study are corroborated by the results of testing a new, Pt-Sb-Re catalyst supported on Al₂O₃-Cl with predicted properties.     

固定床渣油加氢催化剂失活的原因分析及对策

固定床渣油加氢技术是重油改质的重要手段,是优化重油催化裂化装置原料的主要措施,而固定床渣油加氢装置催化剂的价格昂贵、使用周期短且不具再生使用性,因此探讨固定床渣油加氢催化剂失活的原因并采取相应的对策,对延长催化剂的使用周期有积极的意义。通过对固定床渣油加氢装置催化剂末期运行的现象、废旧催化剂化学组成等方面的分析,发现导致固定床渣油加氢装置催化剂失活的主要原因是积炭和金属沉积。同时分析催化剂级配装填的比例、催化剂硫化、原料油的性质和反应温度的分布等因素对固定床渣油加氢催化剂失活的影响,提出了采用抗积炭和容垢能力高的催化剂,进行合理的催化剂级配装填,控制好原料的性质,调整各床层反应温度的匹配分布和控制好催化剂开工条件等措施,可有效延长催化剂的使用寿命。     

Specifics of the deactivation of acid and zinc-containing propane aromatization catalysts

The specifics of the deactivation of acid and Zn-containing MFI catalysts in the propane aromatization reaction at high-feed space velocities (600–2400 h^?1) and temperatures (550–610°C) was studied. The kinetics of the buildup of carbonaceous products (coke) was investigated in situ during the catalytic reaction in a thermal analyzer coupled to a mass spectrometer and a gas chromatograph (TA-MS-GC). The nature of the coke was studied by means of differential thermal analysis (DTA) and elemental analysis. It was found that the buildup of heavy coke on the H-MFI zeolite takes place on the outer crystal surface and pore openings, thus leading to a decrease in the propane conversion at the beginning of the reaction. In contrast, light coke appears first and is transformed to heavy coke at later stages on Zn/H-MFI. The light coke leads to a decrease in the yield of methane, ethane, and ethylene, and the heavy coke impedes the formation of aromatic hydrocarbons.     

Ni负载催化剂积炭失活的研究进展

Ni负载催化剂在天然气化工和煤化工等工业中应用广泛,积炭失活是影响催化剂寿命的主要原因之一。提高催化剂抗积炭性能是Ni负载催化剂研究的重点。综述了Ni催化剂积炭方式、积炭形成机理和积炭对催化剂活性的影响,探讨了添加助剂、改性催化剂载体表面和孔结构、调节反应气氛等抑制催化剂积炭的方法。     

甲醇氧化羰基化合成DMC催化剂及其失活研究进展

针对甲醇液相和气相氧化羰基化合成碳酸二甲酯(DMC)两种生产工艺,分别综述了两种工艺所采用的多相铜系催化剂,包括CuCl/CuCl2负载型催化剂、固体离子交换型低氯和完全无氯铜基负载型催化剂,并分析总结了催化剂分别在液相和气相反应中的失活原因,得出副产物水不能及时移出是液相合成DMC催化剂失活的主要原因,而氯离子的流失和催化剂的热烧结及积炭则会造成气相合成DMC催化剂的失活。     

TH系列贵金属CO_2脱氢催化剂的应用与失活原因分析

介绍了华烁科技股份有限公司气体净化事业部开发的TH系列脱氢催化剂分别在以渣油、天然气和煤为原料的尿素厂CO2原料气脱氢中的应用情况;重点分析了TH系列脱氢催化剂失活原因。分析结果认为,硫中毒仍然是导致脱氢催化剂失活的主要原因,并提出了具体的解决办法。     

合成气一步法合成甲酸甲酯催化剂的失活原因

对反应前后催化剂活性进行了考察 ,并研究了反应过程中催化剂组成的变化与活性的关系 ,以及在催化剂体系中加入助剂对反应活性的影响。运用XRD及BET技术对不同催化剂进行了表征。结果表明 ,铜锰催化剂在反应过程中被还原是其失活的主要原因 ,而甲醇钠劣化为甲酸钠是其失活的主要途径。同时 ,加入某些助剂可以延缓催化剂的失活。     

Experience in use of zeolitic catalysts in hydrotreating processes

Translated from Khimiya i Tekhnologiya Topliv i Masel, No. 6, pp. 14–15, June, 1988.     

Kinetic model for hydrocracking of Iranian heavy crude with dispersed catalysts in slurry-phase

A five-lump kinetic model has been presented to describe the process of heavy oil hydrocracking, and tested in moderate condition. In the condition of low temperature and pressure relatively, coke formation can be controlled and the model is well applied with product distribution. In this paper, we explored the process of hydrocracking in slurry-phase by using dispersed catalyst at higher temperature and pressure, it was found that at the high residue conversion, the coke formation could be controlled even if the residue conversion is up to 90%. Then, a five-lump model by analytical method based on Monte Carlo technique was used to calculate the kinetic parameters, and the product distribution in the condition of high conversion was predicted successfully.     

CH_4-CO_2重整制合成气Ni基催化剂的失活研究

ＣＨ４－ＣＯ２重整制合成气反应（ＭＣＲ）中导致Ｎｉ基催化剂失活的主要原因可能有二：一是助剂组份碳酸化生成稳定碳酸盐物种毒化了反应活性位；二是笼状（包括石墨态和无定型态）炭的沉积覆盖了催化剂表面。ＭＣＲ反应中炭的沉积主要有两种形式：一是以须状形式进行堆集，二是以笼状形式覆盖于催化剂表面，前者对于催化剂活性的保持似无明显影响，后者则是导致催化剂失活的主要原因之一。     

Ecological aspects of use of lubricating oils

Translated from Khimiya i Tekhnologiya Topliv i Masel, No. 1, pp. 37–40, January, 1992.     

可控震源技术使用误区分析

本文针对可控震源技术应用和参数选取的问题,重点讨论了垂直叠加、驱动幅度、扫描斜坡和激发能量等方面的问题,并提出了一些新的认识和建议。垂直叠加对时不变噪声不起作用,提高覆盖次数比提高震次更有利于压制噪声;驱动幅度增加到一定程度时,不一定能增加扫描信号的下传能量,而是增加了谐波成分;扫描斜坡对低频有压制作用,并能减少吉布斯现象;震动能量与扫描长度成正比,单位频率扫描能量与扫描频宽成反比。在可控震源的使用中,人们应克服凭经验选取参数的缺点,通过增强科学分析和定量计算选取参数。     

Ecological aspects of the use of spent lubricants

Translated from Khimiya i Tekhnologiya Topliv i Masel, No. 11, pp. 3–8, November, 1990.