节能型钯催化加氢反应除氧器的研究

本文以钯为催化剂，进行了新型除氧方法——催化加氢除氧的试验研究。研究了催化加氢除氧的影响因素和运行参数，试验结果表明：除去单位质量溶解氧的加氢量与水中残留溶解氧浓度有关，出水DO越低，除去单位质量DO的加氢量越大；上向流运行方式的除氧效果好于下向流方式；在pH为5．10、水温为6．6．29．2℃、运行滤速小于60m／h的条件下。对水中溶解氧的去除率达99．9％，出水DO降至0．01rag／L以下。催化加氢除氧在运行成本、操作管理、节能环保等方面均比其它除氧方式优越。

纳米Ru催化剂催化喹啉加氢反应

制备了高分散性负载型5%Ru/C催化剂,采用X射线衍射、X射线光电子能谱和高分辨透射电镜对催化剂进行了表征.结果表明,所制得的5%Ru/C催化剂分散度高,金属钌的平均粒径小于5nm.在喹啉加氢反应中,催化剂显示出很高的催化活性和生成1,2,3,4-四氢喹啉的选择性,但未检测到十氢喹啉生成.补加新鲜催化剂后,1,2,3,4-四氢喹啉可全部转化为十氢喹啉.对喹啉加氢机理进行了探讨.

一种新型节能环保除氧方式——催化加氢除氧

介绍催化加氢除氧方式的原理、工艺流程、设备运行布置特点,并与其它除氧方式进行了比较.

灵活高中油型加氢裂化方案及适用催化剂

加氢裂化过程是一种操作灵活并适合于处理劣质重质原料来生产轻质燃料油和化工原料的炼油工艺,性能良好的加氢裂化催化剂可促进工艺的创新并提升操作的灵活性。采用一种典型工业加氢裂化催化剂实验室研究了高氮进料苛刻条件加氢裂化,并在工业试验了多种加氢裂化方案。结果表明:该催化剂具有抗氮性能强,活性稳定性优良,多产中油,氢耗低的特点,实验室研究和工业试验的方案可供炼厂加氢裂化装置借鉴。

离子液体及其在有机合成和生物催化中的应用

离子液体是指在室温或附近温度下成液态的，完全由阳离子和阴离子构成的盐，也称低温熔融盐。由于构成离子液体的这两种成分选择余地很大，因此可以按照使用者的需要，通过简单地变换离子构成的方法来控制它的熔点、粘度、密度、溶解性等，所以又被称为”设计者溶剂”。一般说来，离子液体具有良好的热稳定性、不可燃性、不挥发、不爆炸及低毒性，

Chemoselective Transfer Hydrogenation of Cinnamaldehyde over Activated Charcoal Supported Pt/Fe3O4 Catalyst

A variety of spherical and structured activated charcoal supported Pt/Fe3O4 composites with an average particle size of ~100 nm have been synthesized by a self-assembly method using the difference of reduction potential between Pt （Ⅳ） and Fe （Ⅱ） precursors as driving force. The formed Fe3O4 nanoparticles （NPs） effectively prevent the aggregation of Pt nanocrystallites and promote the dispersion of Pt NPs on the surface of catalyst, which will be favorable for the exposure of Pt active sites for high-efficient adsorption and contact of substrate and hydrogen donor. The electron-enrichment state of Pt NPs donated by Fe304 nanocrystallites is corroborated by XPS measurement, which is responsible for promoting and activating the terminal C=O bond of adsorbed substrate via a vertical configuration. The experimental results show that the activated charcoal supported Pt/Fe3O4 catalyst exhibits 94.8% selectivity towards cinnamyl alcohol by the transfer hydrogenation of einnamaldehyde with Pt loading of 2.46% under the optimum conditions of 120 ℃ for 6 h, and 2-propanol as a hydrogen donor. Additionally, the present study demonstrates that a high-efficient and recyclable catalyst can be rapidly separated from the mixture due to its natural magnetism upon the application of magnetic field.

Pd/ZnO catalysts with different origins for high chemoselectivity in acetylene semi-hydrogenation

The heterogeneity of active sites is the main obstacle for selectivity control in heterogeneous catalysis.Single atom catalysts（SACs） with homogeneous isolated active sites are highly desired in chemoselective transformations. In this work, a Pd1/ZnO catalyst with single‐atom dispersion of Pd active sites was achieved by decreasing the Pd loading and reducing the sample at a relatively low temperature. The Pd1/ZnO SAC exhibited excellent catalytic performance in the chemoselective hydrogenation of acetylene with comparable chemoselectivity to that of PdZn intermetallic catalysts and a greatly enhanced utilization of Pd metal. Such unusual behaviors of the Pd1/ZnO SAC in acetylene semi‐hydrogenation were ascribed to the high‐valent single Pd active sites, which could promote electrostatic interactions with acetylene but restrain undesired ethylene hydrogenation via the spatial restrictions of σ‐chemical bonding toward ethylene.

Highlights of the major progress in single-atom catalysis in 2015 and 2016

The idea that single metal atoms dispersed on a solid support can act as an efficient heterogeneous catalyst was raised in2011when single Pt atoms on an FeOx surface were reported to be active for CO oxidation and preferential oxidation of CO in H2.The last six years have witnessed tremendous progress in the field of single‐atom catalysis.Here we introduce the major achievements on this topic in2015and2016.Some particular aspects of single‐atom catalysis are discussed in depth,including new approaches in single‐atom catalyst(SAC)synthesis,stable gold SACs for various reactions,the high selectivity of Pt and Pd SACs in hydrogenation,and the superior performance of non‐noble metal SACs in electrochemistry.These accomplishments will encourage more efforts by researchers to achieve the controllable fabrication of SACs and explore their potential applications.

Copper-ceria solid solution with improved catalytic activity for hydrogenation of CO to CHOH

A copper-ceria solid solution and ceria-supported copper catalysts were prepared and used for the catalytic hydrogenation of CO2 to CH3OH.According to site-specific classification and quantitative analyses(X-ray diffraction,Raman spectroscopy,X-ray photoelectron spectroscopy,H2 temperature-programmed reduction,and CO adsorption),the interfaces of the prepared catalysts were classified as Cu incorporated into ceria(Cu-Ov-Cex),dispersed Cu O(D-Cu O-Ce O2),and bulk Cu O(B-Cu O-Ce O2)over the Ce O2 surface.These results,together with those of activity tests,showed that the Cu-Ov-Cex species was closely related to the CO2 hydrogenation activity and resulted in a much higher turnover frequency of CH3OH production than that observed with the D-Cu O-Ce O2 and B-Cu O-Ce O2 species.Thus,the copper-ceria solid solution exhibited improved activity due to the higher Cu-Ov-Cex fraction.

Hydrodeoxygenation of Phenolic Model Compounds over MoS2 Catalysts with Different Structures

Several MoS2 catalysts of different structure, prepared by in situ decomposition of ammonium heptamolybdate （AHM） and molybdenum naphthenate （MoNaph）, and by MoS2 exfoliation （TDM）, were characterized by BET, X-ray diffraction （XRD）, Energy Dispersive X-ray （EDX） and transmission electron microscopy （TEM）. The analysis showed that MoS2 structure was dependant upon the preparation procedure. The activity of the catalysts was determined by measuring the hydrodeoxygenation （HDO） of phenol, 4-methylphenol and 4-methoxyphenol using a batch autoclave reactor operated at 2.8 MPa of hydrogen and temperatures ranging from 320-370℃. By comparing the conversion, the reactivity order of the catalysts was： AHM〉TDM-D〉MoNaph〉thermal〉MoS2 powder〉 TDM-W. Also, the effect of reaction temperature on the HDO conversion was explained in terms of equilibrium of reversible reaction kinetics. The main products of the HDO for phenolic compounds were identified by gas chromatography/mass spectrometry （GC/MS）. The results showed that the product distribution and the HDO selectivity were correlated with the reaction temperature. Two parallel reaction routes, direct hydrogenolysis and combined hydrogenation-hydrogenolysis, were confirmed by the analysis of the product distribution. High temperature favored hydrogenolysis over hydrogenation for HDO of phenol and 4-methoxyphenol, whereas for 4-methylphenol the reverse was true.

Visible light-enhanced photothermal CO2 hydrogenation over Pt/Al2O3 catalyst

Light illumination has been widely used to promote activity and selectivity of traditional thermal catalysts. Nevertheless, the role of light irradiation during catalytic reactions is not well understood. In this work, Pt/Al2 O3 prepared by wet impregnation was used for photothermal CO2 hydrogenation, and it showed a photothermal effect. Hence, operando diffuse reflectance infrared Fourier-transform spectroscopy and density functional theory calculations were conducted on Pt/Al2 O3 to gain insights into the reaction mechanism. The results indicated that CO desorption from Pt sites including step sites(Ptstep) or/and terrace site(Ptterrace) is an important step during CO2 hydrogenation to free the active Pt sites. Notably, visible light illumination and temperature affected the CO desorption in different ways. The calculated adsorption energy of CO on Ptstep and Ptterrace sites was-1.24 and-1.43 e V, respectively. Hence, CO is more strongly bound to the Ptstep sites. During heating in the dark, CO preferentially desorbs from the Ptterrace site. However, the additional light irradiation facilitates transfer of CO from the Ptstep to Ptterrace sites and its subsequent desorption from the Ptterrace sites, thus promoting the CO2 hydrogenation.

Zinc single atoms on N-doped carbon: An efficient and stable catalyst for CO2 fixation and conversion

The cycloaddition of epoxides and carbon dioxide represents a straightforward and atom-efficient method for synthesis of cyclic carbonates and utilization of CO2. So far, homogeneous metal complexes have been mainly applied for such transformations. Here, we describe the synthesis of novel heterogeneous Zn-based catalysts, which were conveniently prepared by pyrolysis of an active- carbon-supported phenanthroline-ligated Zn(OAc)2 complex. Detail structural characterizations proved the existence of single zinc sites in the active material. Compared to a Zn-based nanoparticle (Zn-NP) catalyst, the resulting single metal atom catalyst (SAC) displayed improved activity and stability for the cycloaddition of epoxides. By applying the optimal catalyst, a variety of carbonates were successfully obtained in high yields with good functional group tolerance.

CO_2 hydrogenation to methanol over Cu/Zn/Al/Zr catalysts prepared by liquid reduction

Cu/Zn/Al/Zr catalysts containing Cu in three valence states(Cu2+,Cu+and Cu0)were prepared usinga liquid reduction method and subsequently calcined at different temperatures.The effects of thecalcination temperature on the catalyst structure,interactions among components,reducibility anddispersion of Cu species,surface properties and exposed Cu surface area were systematically investigated.These materials were also applied to the synthesis of methanol via the hydrogenation ofCO2.The results show that a large exposed Cu surface area promotes catalytic CO2conversion andthat there is a close correlation between the Cu+/Cu0ratio and the selectivity for methanol.A calcinationtemperature of573K was found to produce a Cu/Zn/Al/Zr catalyst exhibiting the maximumactivity during the synthesis of methanol.

Determining number of sites on ceria stabilizing single atoms via metal nanoparticle redispersion

Single atom catalysts have recently attracted interest due to their maximization of the utilization of expensive noble metals as well as their unique catalytic properties. Based on its surface atomic properties, CeO2 is one of the most common supports for stabilizing single metal atoms. Many single atom catalysts are limited in their metal contents by the formation of metal nanoparticles once the catalyst support capacity for single atoms has been exceeded. Currently, there are no direct measurements to determine the capacity of a support to stabilize single atoms. In this work we develop a nanoparticle-based technique that allows for quantification of that capacity by redispersing Ru nanoparticles into single atoms and taking advantage of the different catalytic properties of Ru single atoms and nanoparticles in the CO2 hydrogenation reaction. This method avoids complications in metal loading caused by counterions in incipient wetness impregnation and can eventually be applied to a variety of different metals. Results using this technique follow trends in oxygen vacancy concentration and surface oxygen content and show promise as a new method for quantifying support single atom stabilization capacity.

Effects of indium on Ni/SiO_2 catalytic performance in hydrodeoxygenation of anisole as model bio-oil compound: Suppression of benzene ring hydrogenation and C–C bond hydrogenolysis

SiO2‐supported monometallic Ni and bimetallic Ni‐In catalysts were prepared and used for hydrodeoxygenation of anisole,which was used as a model bio‐oil compound,for BTX(benzene,toluene,and xylene)production.The effects of the Ni/In ratio and Ni content on the structures and performances of the catalysts were investigated.The results show that In atoms were incorporated into the Ni metal lattice.Although the Ni‐In bimetallic crystallites were similar in size to those of monometallic Ni at the same Ni content,H2uptake by the bimetallic Ni‐In catalyst was much lower than that by monometallic Ni because of dilution of Ni atoms by In atoms.Charge transfer from In to Ni was observed for the bimetallic Ni‐In catalysts.All the results indicate intimate contact between Ni and In atoms,and the In atoms geometrically and electronically modified the Ni atoms.In the hydrodeoxygenation of anisole,although the activities of the Ni‐In bimetallic catalysts in the conversion of anisole were lower than that of the monometallic Ni catalyst,they gave higher selectivities for BTX and cyclohexane as a result of suppression of benzene ring hydrogenation and C–C bond hydrogenolysis.They also showed lower methanation activity.These results will be useful for enhancing carbon yields and reducing H2consumption.In addition,the lower the Ni/In ratio was,the greater was the effect of In on the catalytic performance.The selectivity for BTX was primarily determined by the Ni/In ratio and was little affected by the Ni content.We suggest that the performance of the Ni‐In bimetallic catalyst can be ascribed to the geometric and electronic effects of In.

石家庄炼油厂35×10~4t/a重整装置扩容改造及标定分析

本文介绍了石家庄炼油厂重整车间由 15万t·a-1装置改造为 35万t·a-1的改造状况 ,及首次在我厂使用的新型预加氢催化剂DN - 2 0 0和重整催化剂CB - 6 0 ,CB - 70的标定情况。这些新技术的应用为重整装置的优化操作。

Ru nanoparticles supported on hydrophilic mesoporous carbon catalyzed low-temperature hydrodeoxygenation of microalgae oil to alkanes at aqueous-phase

The processing of an energy carrier such as microalgae oil into valuable fuels and chemicals is quite promising.Aqueous-phase processing is suitable for this purpose because the separation of intrinsic water from the algae cell is difficult.In this study,we synthesized ruthenium(Ru)nanoparticles supported on highly hydrophilic mesoporous carbon to catalyze the quantitative hydrodeoxygenation(HDO)of microalgae oil to alkanes in a one-pot process at a low temperature(140℃)in the aqueous phase.The mesoporous carbon was obtained by single-step calcination of starch and zinc chloride in nitrogen.The as-obtained carbon showed high surface areas and pore volumes,allowing high dispersion of Ru nanoparticles.The surface of the carbon material was rich in hydroxyl groups,as evidenced by X-ray photoelectron spectroscopy(XPS),infrared(IR)spectroscopy,and thermogravimetric analysis(TGA)measurements.As a result,the carbon material contacted preferably with the water phase versus the organic phase,improving the accessibility of substrates.On the other hand,the contact angle test results speculated the superior hydrophilic nature of mesoporous Ru/C(ZnCl2,starch)than commercial Ru/C.Both kinetics modeling and in situ IR monitoring in water revealed the superior performance of the hydrophilic mesoporous and hydrophilic Ru/C compared to a commercial Ru/C for the tandem hydrogenation of stearic acid and decarbonylation of stearyl alcohol.The herein designed hydrothermal carbon material was highly active,environmentally benign,sustainable,and recyclable material,and could be potentially used for other hydrogenation reactions in the aqueous phase.

Catalytic hydrolysis of carbonyl sulfide over modified coal-based activated carbons by loading metal

A novel type of metal oxide/activated carbon catalyst was prepared by sol-gel method for the hydrolysis of carbonyl sulfide （COS）. The influences of the calcination temperature, additive content （2.5%-10.0% Fe2O3, mass fraction） and the basic density of the activation process were thoroughly investigated. The surface of catalysts was characterized by Boehm titration. The products were characterized by scanning electron microscopy （SEM）, X-ray diffractometry （XRD） and X-ray photoelectron spectroscopy （XPS）. The results show that catalysts with 2.5%-5.0% Fe2O3 after calcining at 500 ℃ have superior activity. The conversion rate of COS increases with increasing the relative density of basic capacity loaded onto activated carbon（AC）, and the activity follows the order： KOH〉Na2CO3 〉NaHCO3. Boehm titration data clearly show that the total acidity increases （from 0.06 to 0.48 mmol/g） and the basic groups decrease （from 0.78 to 0.56 mmol/g） after COS hydrolysis and H2S adsorption. The XPS results show that the product of HzS may be absorbed by the interaction with metal compounds and 02 to form sulfate （171.28 eV） and element sulfur （164.44 eV）, which lead to catalysts poisoning.

Effect of In_(2)O_(3)particle size on CO_(2) hydrogenation to lower olefins over bifunctional catalysts

A reaction-coupling strategy is often employed for CO_(2)hydrogenation to produce fuels and chemicals using oxide/zeolite bifunctional catalysts.Because the oxide components are responsible for CO_(2)activation,understanding the structural effects of these oxides is crucial,however,these effects still remain unclear.In this study,we combined In_(2)O_(3),with varying particle sizes,and SAPO‐34 as bifunctional catalysts for CO_(2)hydrogenation.The CO_(2)conversion and selectivity of the lower olefins increased as the average In_(2)O_(3)crystallite size decreased from 29 to 19 nm;this trend mainly due to the increasing number of oxygen vacancies responsible for CO_(2) and H_(2) activation.However,In_(2)O_(3)particles smaller than 19 nm are more prone to sintering than those with other sizes.The results suggest that 19 nm is the optimal size of In_(2)O_(3)for CO_(2)hydrogenation to lower olefins and that the oxide particle size is crucial for designing catalysts with high activity,high selectivity,and high stability.

Catalytic ozonation of thymol in reverse osmosis concentrate with core/shell Fe_3O_4@SiO_2@Yb_2O_3 catalyst:Parameter optimization and degradation pathway

In this work, a novel catalyst of Fe_3O_4@SiO_2@Yb_2O_3 was prepared and the degradation of thymol in reverse osmosis concentrate using ozonation was explored. The operational parameters, such as ozone dosage(8–48 mg·min^(-1)),initial thymol concentration(20–100 mg·L^(-1)), initial pH value(3–11), and catalyst Fe_3O_4@SiO_2@Yb_2O_3dosage(0.2–1.0 g), were studied focusing on the thymol degradation and COD removal. The results indicated that the increase in ozone dosage, initial p H value, and Fe_3O_4@SiO_2@Yb_2O_3dosage accelerated the thymol degradation and COD removal, while the increase in initial thymol concentration hampered the effect of ozonation. A pathway of thymol degradation by catalytic ozonation was proposed based on the intermediates detected by gas chromatography-mass spectrometer and ion chromatography. This paper can provide basic data and technical alternative for pollutant removal from reverse osmosis concentrate by ozonation.