镍-钒催化剂作用下由苯直接氧化氨化合成苯胺H

设计并制备了Ni-V/γ-Al2O3催化剂，研究了其上苯用过氧化氢氧化氨化一步直接合成苯胺的性能和不同氨基源对合成苯胺的影响。

对甲苯腈生产工艺评析

简要叙述了对甲苯腈的用途、生产工艺 ,着重对各生产工艺的特点、技术经济进行评析。

Seed-induced synthesis of small-crystal TS-1 using ammonia as alkali source

Small-crystal TS-1 was synthesized via a seed-induced approach using ammonia as the alkali source and tetrapropylammonium bromide as an auxiliary structure-directing agent. The TS-1 samples were characterized using X-ray diffraction, N2 adsorption-desorption, Fourier-transform infrared spectroscopy, inductively coupled plasma atomic emission spectroscopy, scanning electron microscopy, and ultraviolet-visible spectroscopy. The use of the colloidal seed reduced the crystal size, and an appropriate amount of silicalite-1 seed assisted Ti incorporation into the TS-1 framework. This method reduces the cost of TS- 1 synthesis because a significantly smaller amount of tetrapropylammonium hydroxide is used. The catalytic performance of the synthesized small-crystal TS-1 samples in cyclohexanone ammoximation was better than that of bulk TS-1 as a result of improved diffusion and a larger number of active tetrahedral Ti centers.

吉化集团公司精细化工技术中心两项成果获国家专利

由吉化集团公司精细化工技术中心开发成功的二甘醇氨化合成吗啉催化剂及其工艺和二甘醇氮化制吗啉催化剂及其工艺两项成果，日前获国家发明专利。（专利号分别为：ZL200410010816．9；ZL200410010815．4） 二甘酵氮化合成吗啉催化剂及其工艺制备过程简单、成本低，催化剂活性组份含量低、其活性、强度均较高，选择性能好，特别适用于固定床二甘醇氨化制吗啉生产上应用。

中国石油吉林石化公司研究院技术转让或技术合作项目

羟基聚硅氧烷合成新工艺技术开发，溶剂法连续裂解二甲基二氯硅烷水解物工艺开发，脱肟交联剂生产技术，辛烯醛加氢氧化生产异辛酸技术，2000t／a二甘醇氨化法生产吗啉技术，2000t／a正（异）丁醇氨化法生产正（异）丁胺技术，5000t／a丁苯吡胶乳生产技术，A／O工艺处理化工混合废水，烷基苷生产技术，正辛醇加氢氨化合成正辛胺技术，千吨级高温硫化硅橡胶生产技术。

Germination Characteristics and Secondary Metabolism Regulation of Scutellaria baicalensis Georgi Seeds under Different Light Intensities

[Objective] This study aimed to investigate the primary and secondary metabolisms during the germination of Scutellaria baicalensis Georgi seeds under different light intensities. [Method] The activities of CHL, soluble sugar, PAL, C4H and CHS were determined with ultraviolet spectrophotometry. The secondary metabolites were detected by High Performance Liquid Chromatography （HPLC）. [Result] The results indicate that the germination of Scutellaria baicalensis Georgi seeds is not sensitive to light and the seedlings were very sensitive to light. The CHL, soluble sugar, PAL, C4H and CHS continuously increased with light intensity. The content of secondary metabolites also increased. [Conclusion] Light increased the formation of leaf photosynthetic pigment, thereby affecting the primary metabolites. The activities of PAL, C4H and CHS significantly increased with the development of light intensity. Finally the secondary metabolites of medicinal plants increased sharply. Therefore, the quality of Scutellaria baicalensis Georgi materials can be improved by increasing the light intensity moderately.

SAPO-34 synthesized with n-butylamine as a template and its catalytic application in the methanol amination reaction

SAPO-34 was synthesized with n-butylamine（BA） as a template for the first time.Crystallization temperature and initial Si amount were important factors leading to successful syntheses.Lamellar AlPO-kanemite tends to form as the major phase or as an impurity of SAPO-34 at lower crystallization temperatures,though a higher initial Si amount may offer a positive effect on the crystallization of SAPO-34 that mitigates the low temperature.Higher temperature（240℃） can effectively suppress the generation of lamellar materials and allow the synthesis of pure SAPO-34 with a wider range of Si incorporation.The crystallization processes at 200 and 240℃ were investigated and compared.We used the aminothermal method to synthesize SAPO-34-BA at 240℃ and also found n-propylamine is a suitable template for the synthesis of SAPO-34.The SAPO-34-BA products were characterized by many techniques.SAPO-34-BA has good thermal stability,crystallinity and porosity.BA remained intact in the crystals with ~1.8 BA molecule per chabazite cage.The catalytic performance of SAPO-34 was tested in the methanol amination reaction,which showed high methanol conversion and selectivity for methylamine plus dimethylamine under the conditions investigated,suggesting that this material is a good candidate for the synthesis of methylamines.

Solvothermal synthesis and characterization of nanocrystalline vanadium-chromium composite oxides and catalytic ammoxidation of 2,6-dichlorotoluene

Vanadium‐chromium oxides(VCrO)were usually prepared by high‐temperature solid‐state reactions;however,mixed phases were frequently produced and the morphology of the products was not well controlled.In this work,we prepared amorphous VCrO precursors by using V2O5 and CrO3 and alcohols or mixtures of alcohol and water via solvothermal reaction at 180°C.The precursors were then calcined under nitrogen at various temperatures.The products were characterized by powder X‐ray diffraction,transmission electron microscopy,and X‐ray photoelectron spectroscopy.It was revealed that pure‐phase nanocrystalline orthorhombic CrVO4 was obtained when methanol or methanol/water was used as the solvothermal medium and the precursor was calcined at 700°C.The size of the CrVO4 crystals was around 500 nm when methanol was used,whereas it reduced significantly to less than 50 nm when a mixture of methanol and water was used.The sizes could be effectively tuned from 10 to 50 nm by varying the methanol/water volume ratio.To the best of our knowledge,this is the first report on the synthesis of pure‐phase CrVO4 nanocrystals.The nano‐CrVO4 showed almost the highest catalytic activity for the ammoxidation of 2,6‐dichlorotoluene to 2,6‐dichlorobenzonitrile among the reported bi‐component composite oxides,owing to its smaller particle size,larger specific surface area,and more exposed active centers.

Recovery of Hydrogen from Ammonia Plant Tail Gas by Absorption-Hydration Hybrid Method

In this work, the absorption-hydration hybrid method was used to recover （hydrogen ＋ nitrogen） from （hydrogen ＋ nitrogen ＋ methane ＋ argon） tail gas mixtures of synthetic ammonia plant through hydrate formation/dissociation. A high-pressure reactor with magnetic stirrer was used to study the separation efficiency. The in-fluences of the concentration of anti-agglomerant, temperature, pressure, initial gas-liquid volume ratio, and oil-water volume ratio on the separation efficiency were systematically investigated in the presence of tetrahydro-furan （THF）. Anti-agglomerant was used to disperse hydrate particles into the condensate phase for water-in-oil emulsion system. Since nitrogen is the material for ammonia production, the objective production in our separation process is （hydrogen ＋ nitrogen）. Our experimental results show that by adopting appropriate operating conditions, high concentration of （hydrogen ＋ nitrogen） can be obtained using the proposed technology based on forming hydrate.

AmmAmmoximation of Cyclohexanone to Cyclohexanone Oxime Catalyzed by Titanium Silicalite-1 Zeolite in Three-phase System

An innovative green process of producing ε-caprolactam was proposed by integrating ammoximation and Beckmann rearrangement effectively. As a first part of the new process, TS-1 molecular sieve-catalyzed synthesis of cyclohexanone oxime from cyclohexanone, ammonia and hydrogen peroxide was carried out in a batch plant. Cyclohexane was used as the solvent in the three-phase reaction system. The influences of essential process parameters on ammoximation were investigated. Under the reaction conditions as catalyst content of 2.5% (by mass); H 2 O 2 /yclohexanone molar ratio of 1.10; NH 3 /cyclohexanone molar ratio of 2.20; reaction temperature of 343 K; reaction time of 5 h, high conversion of cyclohexanone and selectivity to oxime (both>99%) were obtained. Thus, the three-phase ammoximation process showed equal catalytic activity as TS-1 but much more convenient and simpler for the separation of catalyst in comparison to the industrial two-phase system with t-butanol used as solvent.

Photocatalytic nitrogen fixation: An attractive approach for artificial photocatalysis

Ammonia synthesis via the Haber-Bosch process, which has been heralded as the most important invention of the 20 th century, consumes massive amounts of energy, around 1%–2% of the world’s annual energy consumption. Developing green and sustainable strategies for NH3 synthesis under ambient conditions, using renewable energy, is strongly desired, by both industrial and sci-entific researchers. Artificial photosynthesis for ammonia synthesis, which has recently attracted significant attention, directly produces NH3 from sunlight, and N2 and H2O via photocatalysis. This has been regarded as an ideal, energy-saving and environmentally-benign process for NH3 produc-tion because it can be performed under normal temperature and atmospheric pressure using re-newable solar energy. Although sustainable developments have been achieved since the pioneering work in 1977, many challenging issues（e.g., adsorption and activation of nitrogen molecules on the surface of photocatalysts under mild conditions） have still not been well solved and the photocata-lytic activities are generally low. In this miniature review, I summarize the most recent progress of photocatalytic N2 fixation for ammonia synthesis, focusing specifically on two attractive aspects for adsorption and activation of nitrogen molecules： one is engineering of oxygen vacancies, and the other is mimicking natural nitrogenase for constructing artificial systems for N2 fixation. Several representative works focusing on these aspects in artificial systems have been reported recently, and it has been demonstrated that both factors play more significant roles in photocatalytic N2 re-duction and fixation under ambient conditions. At the end of the review, I also give some remarks and perspective on the existing challenges and future directions in this field.

Soft Sensor for Ammonia Concentration at the Ammonia Converter Outlet Based on an Improved Group Search Optimization and BP Neural Network

The ammonia synthesis reactor is the core unit in the whole ammonia synthesis production. The ammonia concentration at the ammonia converter outlet is a significant process variable, which reflects directly the production efficiency. However, it is hard to be measured reliably online in real applications. In this paper, a soft sensor based on BP neural network (BPNN) is applied to estimate the ammonia concentration. A modified group search optimization with nearest neighborhood (GSO-NH) is proposed to optimize the weights and thresholds of BPNN. GSO-NH is integrated with BPNN to build a soft sensor model. Finally, the soft sensor model based on BPNN and GSO-NH (GSO-NH-NN) is used to infer the outlet ammonia concentration in a real-world application. Three other modeling methods are applied for comparison with GSO-NH-NN. The results show that the soft sensor based on GSO-NH-NN has a good prediction performance with high accuracy. Moreover, the GSO-NH-NN also provides good generalization ability to other modeling problems in ammonia synthesis production.

Growth of Cu/SSZ-13 on SiC for selective catalytic reduction of NO with NH_3

Silicon carbide(SiC)was used as a support for SSZ‐13zeolite in an attempt to improve the high‐temperature stability and activity of Cu/SSZ‐13in the selective catalytic reduction(SCR)of NO with NH3.SSZ‐13was grown via a hydrothermal method using the silicon and silica contained in SiC as the source of silicon,which led to the formation of a chemically bonded SSZ‐13layer on SiC.Characterization using X‐ray diffraction,scanning electron microscopy,and N2adsorption‐desorption isotherms revealed that the alkali content strongly affected the purity of zeolite and the crystallization time affected the coverage and crystallinity of the zeolite layer.Upon ion exchange,the resulting Cu/SSZ‐13@SiC catalyst exhibited enhanced activity in NH3‐SCR in the high‐temperature region compared with the unsupported Cu/SSZ‐13.Thus,the application temperature was extended with the use of SiC as the support.?2018,Dalian Institute of Chemical Physics,Chinese Academy of Sciences.Published by Elsevier B.V.All rights reserved.

A highly stable and active mesoporous ruthenium catalyst for ammonia synthesis prepared by a RuCl_3/SiO_2-templated approach

Molecular nitrogen is relatively inert and the activation of its triple bond is full of challenges and of significance.Hence,searching for an efficiently heterogeneous catalyst with high stability and dispersion is one of the important targets of chemical technology.Here,we report a Ba‐K/Ru‐MC catalyst with Ru particle size of 1.5–2.5 nm semi‐embedded in a mesoporous C matrix and with dual promoters of Ba and K that exhibits a higher activity than the supported Ba‐Ru‐K/MC catalyst,although both have similar metal particle sizes for ammonia synthesis.Further,the Ba‐K/Ru‐MC catalyst is more active than commercial fused Fe catalysts and supported Ru catalysts.Characterization techniques such as high‐resolution transmission electron microscopy,N2 physisorption,CO chemisorption,and temperature‐programmed reduction suggest that the Ru nanoparticles have strong interactions with the C matrix in Ba‐K/Ru‐MC,which may facilitate electron transport better than supported nanoparticles.

Biomolecule-assisted, cost-effective synthesis of a Zn_(0.9)Cd_(0.1)S solid solution for efficient photocatalytic hydrogen production under visible light

A series of alloyed Zn‐Cd‐S solid solutions with a cubic zinc blende structure were fabricated hydrothermally with the assistance of L‐cystine under mild conditions.The products were characterized by XRD,TEM,HRTEM,XPS,UV‐vis,and BET techniques,and the photocatalytic performance for the reduction of water to H2on the solid solutions was evaluated in the presence of S2?/SO32?as hole scavengers under visible light illumination.Among all the samples,the highest photocatalytic activity was achieved over Zn0.9Cd0.1S with a rate of4.4mmol h?1g?1,even without a co‐catalyst,which far exceeded that of CdS.Moreover,Zn0.9Cd0.1S displayed excellent anti‐photocorrosion properties during the photoreduction of water into H2.The enhancement in the photocatalytic performance was mainly attributed to the efficient charge transfer in the Zn0.9Cd0.1alloyed structure and the high surface area.This work provides a simple,cost‐effective and green technique,which can be generalized as a rational preparation route for the large‐scale fabrication of metal sulfide photocatalysts.

A theoretical study of electrocatalytic ammonia synthesis on single metal atom/MXene

Electrocatalytic ammonia synthesis under mild conditions is an attractive and challenging process in the earth’s nitrogen cycle,which requires efficient and stable catalysts to reduce the overpotential.The N2 activation and reduction overpotential of different Ti3C2O2-supported transition metal(TM)(Sc,Ti,V,Cr,Mn,Fe,Co,Ni,Cu,Zn,Mo,Ru,Rh,Pd,Ag,Cd,and Au)single-atom catalysts have been analyzed in terms of the Gibbs free energies calculated using the density functional theory(DFT).The end-on N2 adsorption was more energetically favorable,and the negative free energies represented good N2 activation performance,especially in the presence Fe/Ti3C2O2(﹣0.75 eV).The overpotentials of Fe/Ti3C2O2,Co/Ti3C2O2,Ru/Ti3C2O2,and Rh/Ti3C2O2 were 0.92,0.89,1.16,and 0.84 eV,respectively.The potential required for ammonia synthesis was different for different TMs and ranged from 0.68 to 2.33 eV.Two possible potential-limiting steps may be involved in the process:(i)hydrogenation of N2 to*NNH and(ii)hydrogenation of*NH2 to ammonia.These catalysts can change the reaction pathway and avoid the traditional N–N bond-breaking barrier.It also simplifies the understanding of the relationship between the Gibbs free energy and overpotential,which is a significant factor in the rational designing and large-scale screening of catalysts for the electrocatalytic ammonia synthesis.

Study on the Carbon-Methanation and Catalytic Activity of Ru/AC for Ammonia Synthesis

The effects of promoters K, Ba, Sm on the resistance to carbon-methanation and catalytic activity of ruthenium supported on active carbon (Ru/AC) for ammonia synthesis have been studied by means of TG-DTG (thermalgravity-differential thermalgravity), temperature-programmed desorption, and activity test. Promoters Ba,K, and Sm increased the activity of Ru/AC catalysts for ammonia synthesis significantly. Much higher activity can be reached for Ru/AC catalyst with bi- or tri-promoters. Indeed, the triply promoted catalyst showed the highest activity, coupled to a surprisingly high resistance to methanation. The ability of resistance of promoter to methanation of Ru/AC catalyst is dependent on the adsorption intensity of hydrogen. The strong adsorption of hydrogen would enhance methanation and impact the adsorption of nitrogen, which results in the decrease of catalytic activity.