丙烯环管聚合催化剂的应用比较

1997年,我国相继自行设计建设了几套丙烯环管聚合生产装置,生产中也成功地应用了国产N-2和 CS-2型催化剂。国产催化剂的应用显示,效果良好,两种国产催化剂反应活性均高于进口催化剂,某些指标略好于进口催化剂。证明国产催化剂完全可代替进口催化剂用于环管反应器。     

合成1,4-丁炔二醇的孔雀石催化剂放大研究

在催化剂小试装填10 g催化剂的基础上,采用放大评价装置评价合成1,4-丁炔二醇的孔雀石催化剂,反应器体积为20 L,装填催化剂1 000 kg,在模拟工业活化条件下对催化剂进行活化,分别对进口催化剂和国产催化剂的活性、选择性和稳定性进行了考察,结果表明国产合成1,4-丁炔二醇催化剂的性能与进口催化剂基本一致,国产催化剂的过滤性能要优于进口催化剂的过滤性能。国产催化剂的性能能够满足工业合成1,4-丁炔二醇装置的需要。     

DQ-1国产催化剂环管聚丙烯装置的应用

本文介绍了DQ-1国产催化剂在环管聚丙烯装置的试用情况，分析国产催化剂与进口催化剂的差别和国产CS-Ⅱ催化剂存在的问题。     

丙烯腈催化剂的工业应用与发展

总结了国产丙烯腈催化剂工业应用情况，提出了国产丙烯腈催化剂的不足，并结合生产实际提出了提高国产丙烯腈催化剂稳定性、选择性和清洁环保性能，提高国产丙烯腈催化剂对高负荷的适应性的建议。     

异戊橡胶生产用助催化剂国产化替代研究

在不改变原有催化剂配制方法的前提下,选用国产助催化剂替代进口助催化剂。利用异戊橡胶中试装置,开展进口助催化剂及国产助催化剂的对比实验,考察国产助催化剂对异戊橡胶生产工艺及产品性能的影响。结果表明:助催化剂国产化替代对异戊橡胶产品性能无明显影响,并可大幅降低异戊橡胶生产成本。     

二甲苯异构PX催化剂国产化简介——异构PX催化剂铂生命周期滋长

通过对C_8A异构化催化剂类型和国产异构化催化剂技术指标和特点的介绍,类比了国内在用催化剂的指标,提出了国产催化剂的性能完全可替代进口催化剂。     

合成1,4-丁炔二醇的孔雀石催化剂工业应用

国产开发的1,4-丁炔二醇合成催化剂,经过10 g催化剂小试评价和2 000 kg放大评价均达到了工业应用的需要,催化剂的活性、选择性和稳定性均能够满足工业应用的需要,该催化剂在中国石化长城能源(宁夏)化工有限公司的10万t 1,4-丁炔二醇催化剂BDO工业装置上进行了工业应用,结果表明国产合成1,4-丁炔二醇催化剂的性能与进口催化剂基本一致,国产催化剂的过滤性能要优于进口催化剂的过滤性能。催化剂寿命较进口催化剂长17.5%,每批次20 t催化剂BDO产量达到了2.4万吨,国产催化剂的性能完全能够满足工业装置的需要。     

聚丙烯EPS30R产品的三种催化剂对比评价

在单环管聚丙烯(PP)装置上使用三种催化剂生产抗冲共聚PP EPS30R产品,对比评价了三种催化剂的活性、操作稳定性、物耗、能耗、产品质量、细粉含量及生产成本。国产催化剂A在气相反应器中活性较好,产品质量稳定,催化剂成本比国产催化剂B高6.91元/t;国产催化剂B活性最高,细粉少,但气相反应活性偏弱,产品质量波动大,催化剂成本最低;进口催化剂C活性居中,细粉最少,气相反应稳定,但成本比国产催化剂B高108.64元/t。     

国产钯碳催化剂的工业应用

介绍了国产钯碳催化剂的工业应用情况，分别从活性，寿命等方面对比国产和进口催化剂的性能，确认目前国产钯碳催化剂已达到了工业装置应用标准。     

国产CN-31催化剂与ICI65/2催化剂工业应用的比较

国产轻油预转化催化剂与进口催化剂相比 ,具有性能相当 ,价格低廉 ,供应方便等优势。采用国产催化剂能明显反映性能价格比。对两种催化剂进行了工业应用比较和分析     

Effect of phospholipid structure on kinetics and chemistry of soybean oil hydrogenation with nickel catalysts

Phospholipids (PL) are one of the compounds which poison nickel catalysts during the hydrogenation process. It was affirmed that even trace amounts of PL (5—10 ppm P) cause a decrease in catalyst activity. Quantities over 50 ppm P almost totally inhibit the reaction. In bleached oils used for hydrogenation, PL exist as native compounds as well as products of their transformation. In the present work, the effect of native phospholipids, lysophospholipids (LPL) and phosphatidic acids (PA) on the kinetics and chemistry of soybean oil hydrogenation was investigated. It was found that PA were more toxic to nickel catalysts than LPL and native PL. Fine‐grained catalyst was more active and resistant to the poisoning effect of phospholipids than moderate‐grained catalyst. No changes in the oil hydrogenation chemistry were observed in the presence or absence of PL; thus, linoleic and linolenic selectivity and specific isomerization did not undergo any change.     

Activity of hydroprocessing catalysts prepared by reprocessing spent catalysts

In this study, two spent catalysts from the 3rd and 4th fixed beds of the atmospheric residue desulfurization (ARDS) process and one spent catalyst from the H-Oil process employing the expanded bed were used as the starting material for preparation of hydroprocessing catalysts. The spent catalysts were used either in a coked or decoked form. The procedures involved pulverizing the spent catalysts before mixing, kneading and extruding with boehmite in the presence of peptizing agent such as HNO₃. The hydrodesufurization (HDS) and hydrodemetallization (HDM) activities of the new catalysts were evaluated in the microreactor using the atmospheric residue derived from Kuwait crude. The new catalysts prepared from the spent catalysts used in the fixed bed reactors exhibited higher activity than that of commercial catalysts. The HDS activity of the new catalysts prepared from spent catalysts used in the ebullated bed reactor was much lower than that of the other catalysts. This was attributed to a high content of vanadium in the former spent catalyst. At the same time, the adverse effect of vanadium on HDM was much less evident.     

The role of methyl radicals in the reduction of NO by CH4 over a Ba/MgO catalyst

The coproduction of methanol and isobutanol from synthesis gas over new catalysts based on coprecipitated solid solutions of alkaline earth oxides and rare earth oxides promoted by copper has been investigated. It is shown that the catalysts are active and selective to isoalcohol synthesis at temperatures and pressures lower than those required by prior art catalysts.     

柴油催化加氢脱芳烃研究进展

论述了柴油加氢脱芳烃的催化剂体系、芳烃加氢反应机理和工艺方法。该催化剂体系包括贵金属催化剂和非贵金属催化剂两种类型,其中贵金属催化剂的脱芳烃效果较非贵金属催化剂要好。柴油加氢脱芳烃大多采用两段加氢工艺,将贵金属和非贵金属催化剂结合使用可以取得良好的脱芳烃效果。增强脱芳烃催化剂的抗硫性能也成为现今研究重点,载体的性质对加氢脱芳烃催化剂的催化性能有很大的影响,开发新载体和新材料成为今后加氢脱芳烃催化剂的研究趋势。     

Synthesis of methanol and ethanol over CuZnAl slurry catalyst prepared by complete liquid-phase technology

A new method, named the complete liquid-phase technology, has been applied to prepare catalysts for methanol synthesis. Its main innovative thought lies in preparing slurry catalysts directly from raw solution. Activity tests indicate that the CuZnAl slurry catalyst prepared by the new method can efficiently catalyze conversion of syngas to ethanol in a slurry reactor, while CO conversion reaches 35.9% and ethanol selectivity is more than 20%, with a total alcohol selectivity of more than 87%. No deactivation was found during the 192 h reaction.     

Improving the catalytic nitrate reduction

Technologies for the nitrate removal from drinking water and waste water will be required in the near future and the catalytic nitrate reduction is one of the most promising ones. To establish a technical-scale nitrate reduction a further improvement of the catalyst is necessary and new concepts should be introduced in the process. It is shown, that palladium–tin and palladium–indium catalysts can be much more suited for an efficient nitrate reduction than palladium–copper catalysts. Furthermore, two new innovative concepts are presented — the use of in situ buffering formic acid as reductant instead of hydrogen and the application of PVAL-encapsulated catalysts with superior diffusional properties — which may contribute to solve selectivity problems.     

碱性电解水析氢中的异质结构催化剂

碱性环境下单相金属催化剂的电催化产氢的动力学过程普遍缓慢远不及其在酸性条件,且存在易腐蚀等问题。近期很多异质结构催化剂被报导在碱性条件下表现出优异的析氢性能或长时间的耐用性,其中一些非贵金属催化剂达到了与贵金属基催化剂类似的高催化活性,为碱性条件下产氢催化剂的设计与开发提供了新思路。首先,介绍了异质结构相较于单一材料在产氢催化中的优势,并补充说明了碱性产氢理论相关背景。然后,追溯异质结构在碱性产氢催化剂中的研究路径,主要介绍了异质结构催化剂中极其重要且报导众多的过渡金属氢氧化物基、氧化物基以及硫化物基的异质结构催化剂,通过实例展示异质结构催化剂的制备方法、表征策略以及相应的设计思路。最后,分析了异质结构催化剂在固有活性比较中的困难并对异质结构催化机理的未来研究进行了展望。     

New type of tin support for hydroprocessing catalyst

TiN supported molybdenum sulfide catalysts showed much higher activity for cleavage of C-C bonds than oxide supported molybdenum sulfide catalysts, indicating the possibility of a new generation of supports for hydroprocessing catalysts.     

Non‐natural Olefin Cyclopropanation Catalyzed by Diverse Cytochrome P450s and Other Hemoproteins

Recent work has shown that engineered variants of cytochrome P450_BM3 (CYP102A1) efficiently catalyze non‐natural reactions, including carbene and nitrene transfer reactions. Given the broad substrate range of natural P450 enzymes, we set out to explore if this diversity could be leveraged to generate a broad panel of new catalysts for olefin cyclopropanation (i.e., carbene transfer). Here, we took a step towards this goal by characterizing the carbene transfer activities of four new wild‐type P450s that have different native substrates. All four were active and exhibited a range of product selectivities in the model reaction: cyclopropanation of styrene by using ethyl diazoacetate (EDA). Previous work on P450_BM3 demonstrated that mutation of the axial coordinating cysteine, universally conserved among P450 enzymes, to a serine residue, increased activity for this non‐natural reaction. The equivalent mutation in the selected P450s was found to activate carbene transfer chemistry both in vitro and in vivo. Furthermore, serum albumins complexed with hemin were also found to be efficient in vitro cyclopropanation catalysts.     

From Native Starch to Hydrophilic and Hydrophobic Products: A Catalytic Approach

Two new catalytic processes have been developed to modify the hydrophilic/hydrophobic properties of insoluble, native starch. Soluble metal catalysts under proper reaction conditions were used to prepare tailor-made products suitable for various technological applications. Selective, clean oxidation of native starch by hydrogen peroxide in the presence of 0.003–0.016 mol% of iron tetrasulfonatophthalocyanine catalyst (FePcS) provided hydrophilic starch having 0.5–7 carboxyl and 1–11 carbonyl functions per 100 AGU (anhydroglucose units). The oxidation reaction was performed either with starch suspended in catalyst solution or by impregnation of starch powder with catalyst solution (dry process). Only small amounts of water, hydrogen peroxide and cheap FePcS catalysts were needed in the dry process to achieve a successful modification of starch in one step with almost quantitative yields. Hydrophobic starches with degree of substitution ranging from 0.08 to 0.43 per AGU have been prepared by butadiene telomerization in the presence of soluble palladium complexes. The best results in terms of degree of substitution at 50 °C have been obtained with Pd/TPPTS catalyst. The telomerization of starch with isoprene was also demonstrated. The etherified starch can be further transformed by hydrogenation using Wilkinson-type catalyst in EtOH/H₂O.