HCRL再活化催化裂化催化剂的工业应用试验

介绍了采用一种催化裂化废平衡催化剂活性改善技术生产的HCRL再活化催化剂在中国石化北京燕山分公司Ⅱ催化裂化装置的使用情况。工业试验结果表明:在催化剂消耗成本不变的情况下,采用置换的方法,当HCRL再活化催化剂达到装置催化剂藏量的40%时,系统微反活性提高近2个单位,平衡剂重金属含量维持在较低水平。产品组成分布得到改善,装置总液体收率提高了1.72百分点。

Chlorsorb技术在连续重整催化剂再生系统的运用

惠州炼油2.0 Mt/a连续重整装置的催化剂再生气排放量为1.417万吨/年,再生气中的氯含量为0.2%。为了减少了氯化氢的排放,连续重整装置催化剂再生系统引进UOP公司最新的再生工艺技术Chlorsorb,再生气通过催化剂吸附床吸附后直接排放到大气中。工业运用结果表明,chlorsorb技术能保护环境和减少再生设备的腐蚀,具有良好的环保效益和经济效益。

先进控制技术及其在催化反再系统上的应用

胜利炼油厂采用 SETPOINT公司的先进控制技术 ,成功地应用于工艺动态过程较为复杂的第二催化反再系统上。该技术是在 DCS常规控制的基础上 ,采用多变量预估控制器和约速控制器 ,同时对催化反应深度、再生器烧焦和装置压力平衡实施统一协调的在线自动控制。本文主要介绍该先进控制技术及其控制策略、技术特点和效益情况。

催化反再系统斜管上松动点的合理设置

简要论述了催化剂在斜管中的流动；结合一个斜管振动的成功改造实例，分析了斜管上松动点的布置对其振动的影响。提出将斜管上的松动点分为敏感松动点和一般松动点两类而分别加以对待，并指出了松动点的设置原则。这些设置原则不仅对减小或消除斜管振动，开好催化袋化装置，具有十分重要的意义，而且对其它气、固两相流的管线设计，也具有一定的借鉴作用。

V2O5-WO3/TiO2催化剂用于对二甲苯氧化去除实验研究

废弃V2O5-WO3/TiO2SCR催化剂已经成为燃煤电厂新的环保问题。开发废弃SCR催化剂用于催化氧化挥发性有机物(VOCs)的新方法。先对比了废弃和新鲜V2O5-WO3/TiO2催化剂催化氧化废气中对二甲苯的去除效果,发现两者的去除效果基本相同。然后重点研究了反应温度、氧气含量、对二甲苯初始浓度等关键工艺参数对对二甲苯去除效果的影响。研究结果表明:对二甲苯去除率受反应温度影响较大,在100℃以上时随反应温度的增加而增加;而氧化产物CO2选择性在200℃以上时才有显著增加;氧气体积分数的增加能够提升对二甲苯去除率,特别是氧气体积分数从0%增加到5%时,对二甲苯去除率明显提升。对二甲苯去除率和COx选择率随着对二甲苯初始浓度的增加而下降。

一种低不饱和度高活性聚醚多元醇的合成

研究了采用再催化法及自制的低不饱和度端仲羟基聚醚二醇(Mn=1 700)与环氧乙烷(EO)的封端反应,确定了合适的再催化反应催化剂为甲醇钾,其用量为起始聚醚质量的1%。分别采用A法(中和–吸附法)和B法(吸附剂法)对粗低不饱和度高活性聚醚多元醇进行后处理,确定该聚醚的精致工艺。合成的聚醚T220E的环氧乙烷封端含量为聚醚总质量的15%,该聚醚具有不饱和度低、活性高等优点,能用于聚氨酯胶黏剂及弹性体的生产。

低不饱和度聚醚多元醇封端技术进展

用双金属氰化物络合物(DMC)催化剂制备低不饱和度聚醚多元醇的封端方法包括再催化封端法和直接封端法2类，分别介绍其几种代表性工艺，并总结了2类方法的优缺点。

Production of Hydrogen from Bio-oil Using Low-temperature Electrochemical Catalytic Reforming Approach over CoZnAI Catalyst

High-efficient production of hydrogen from bio-oil was performed by electrochemical catalytic reforming method over the CoZnAl catalyst. The influence of current on the hydrogen yield, carbon conversion, and products distribution were investigated. Both the hydrogen yield and carbon conversion were remarkably enhanced by the current through the catalyst, reaching hydrogen yield of 70% and carbon conversion of 85% at a lower reforming temperature of 500 ℃. The influence of current on the properties of the CoZnAl catalyst was also characterized by X-ray diffraction, X-ray photoelectron spectroscopy, thermal gravimetric analysis, and Brunauer-Emmett-Teller measurements. The thermal electrons would play an important role in promoting the reforming reactions of the oxygenated-organic compounds in the bio-oil.

Characterization of Catalytic Cracking Catalysts Regenerated by Gasifying Deposited Coke

Partially or fully regenerated catalytic cracking catalysts were prepared by gasifying the coke deposited on coked catalysts with a gaseous mixture of oxygen and steam in a fixed fluidized bed （FFB）. The resultant samples were characterized by different methods such as the nitrogen adsorption-desorption analysis, the X-ray diffractometry, the infrared spectroscopy, the ammonia temperature-programmed desorption （NH3-TPD） method, the X-ray fluorescence （XRF） analysis, the transmission electron microscopy and energy dispersive X-ray spectroscopy （TEM-EDX）, the thermal-gravimetric analysis （TGA） and the differential thermal analysis （DTA）. The results showed that exposure of catalyst to steam for about 10 minutes at temperature ≥ 800 ℃ could not cause too much destruction of the catalysts, and an amount of coke equating to about 0.27 m% was enough to block approximately all acid sites in micro-pores of the zeolite catalyst. Coke didn＇t show equal reactivity during coke burning-off that could be accelerated by the catalytic action of nearby metal atoms. However, when the carbon content on the catalyst reached about 2.44 m%, the catalytic action of metals on the catalyst was not evident. The severe thermal and hydrothermal environment during exposure of the catalyst to steam at a temperature in the range of about 860--880 ℃ for 30 minutes could lead to collapse of pore structure and transformation of crystal phase and consequently decrease of the surface area and acid amount on the catalyst.

Development and Commercial Application of Ultra-Low Pressure Naphtha Reforming Technology with Continuous Catalyst Regeneration

The development history and major technological innovations of the ultra-low pressure naphtha reforming technology with continuous catalyst regeneration in China were introduced.This technology had been adopted by the 1.0 Mt/a CCR unit at the Guangzhou Company.The appropriate catalyst was selected to meet the demand of the unit capacity,the feedstock,and the product slate.The design parameters,including the reaction pressure,the octane number of C5+liquid product,the reaction temperature,the space velocity,the hydrogen/oil molar ratio,and the catalyst circulating rate,were chosen based on the study of process conditions and parameters.The commercial test results showed that the research octane number of C5+product reached 104 when the capacity of the CCR unit was 100%and 115%of the design value.The other technical targets attained or exceeded the expected value.

Regeneration of catalysts deactivated by coke deposition:A review

In industrial catalytic processes,coke deposition can cause catalyst deactivation by covering acid sites and/or blocking pores.The regeneration of deactivated catalysts,thereby removing the coke and simultaneously restoring the catalytic activity,is highly desired.Despite various chemical reactions and methods are available to remove coke,developing reliable,efficient,and economic regeneration methods for catalytic processes still remains a challenge in industrial practice.In this paper,the current progress of regeneration methods such as oxidation(air,ozone and oxynitride),gasification(carbon dioxide and water steam),and hydrogenation(hydrogen)is reviewed,which hopefully can shed some light on the design and optimization of catalysts and the related processes.

Advances in designing heterojunction photocatalytic materials

Under the background of increasing energy crisis and global warming,semiconductor-based photocatalysis has received tremendous attention due to its potential application in green energy production,CO_(2) reduction and pollutant degradation.The photocatalytic activity of semiconductors,however,remains low due to issues like fast recombination of photo-generated electron-hole pairs,limited electron mobility,restricted optical absorption or insufficient active sites.Designing appropriate heterojunctions is proved to be a promising method to address most of these issues and thus to improve the photocatalytic performance.In this review,the working mechanism of various heterojunctions is presented systematically.The most recent advances of strategies in designing and preparing efficient heterojunction photocatalysts are further summarized and some perspectives on the future directions in this field are provided.

Reliable, environmentally friendly method for the recycling of spent Ag/α-Al2O3 catalysts using (NH4)2Ce(NO3)6

Traditionally,Ag-containing solid wastes are leached by nitric acid in order to recycle the noble metal.However,the huge amounts of emission of toxic nitrogen oxides demand the development of a new method for silver recycling.Recently,considering the Ce(Ⅳ)solution could be regenerated with electrolyzation method,our group invented a novel environmentally friendly process by using Ce(Ⅳ)as the oxidant to dissolve silver from the spent Ag/ɑ-Al_2O_3 catalysts without NO_x emission.To find out the optimal parameters,in this work,the leaching reaction was thoroughly investigated with respect to the temperature,oxidant and HNO_3 concentrations,stirring speed,and time.The optimized leaching reaction gave the leaching silver rate 99.8% in 1 h.The kinetic plots suggested a shrinking core model with the internal diffusion-controlled process and the activation energy of 38.83 k J·mol^(-1).The order in which the experimental conditions influence the reaction was determined through orthogonal analysis:temperature N oxidant concentration N HNO_3 concentration N stirring speed.

Study on the Performance of Regenerated Catalyst for Ammonoximation of Cyclohexanone

The study on the deactivated catalyst and the regenerated catalyst for the 70 kt/a cyclohexanone ammonoximation commercial test unit had revealed that addition of a proper amount of silicon additive could suppress the solubilization-induced loss of silicon in catalyst while providing protection to the catalyst. Compared to the direct calcination method for catalyst regeneration, adoption of the regeneration method through pretreatment-calcination of catalyst could be more beneficial to the restoration of catalyst channels and enhancement of the performance of the regenerated catalyst, which could be repeatedly regenerated and utilized. The outcome of commercial scale testing of the catalyst had indicated the good performance of the regenerated catalyst, which could be used for four times, resulting in a reduction of the production cost of cyclohexanone-oxime in big chunks.

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.

Modeling and Simulation of Coke Combustion Regeneration for Coked Cr2O3/Al2O3 Propane Dehydrogenation Catalyst

A heterogeneous model is developed for the regeneration of the Cr2O3/Al2O3 catalyst for the propane dehydrogenation process by considering the internal mass transfer and external mass/heat transfer during the coke combustion.Simulation shows that under practical operating conditions,multi-steady states exist for the catalyst pellets and the catalyst temperature is sensitive to gas temperature.However,at increased mass flow rate or lowered oxygen concentration,multi-steady states will not appear.Under the strong influences of film diffusion,the coke in the packed bed reactor will first be exhausted at the inlet,while if the film diffusion resistance is decreased,the position of first coke exhaustion moves toward the outlet of the reactor.

Efficient C-N Formation for Preparing α-Branched Primary Amines by Recycled Intramolecular Reactions of 1,8-Naphthosultone Using Ammonia as Nitrogen Source

Amination of tertiary and secondary alcohols using aqueous ammonia as nitrogen source was carried out by a process with recyclable intramolecular reaction of 1,8-naphthosultone, which lead to α-branched primary amines. Sulfonic resin serves as the heterogeneous catalyst for C N bond formation and protects the neighboring hydroxyl group until the required hydrolysis starts in the alkaline solution. The process can be conducted under mild conditions, no additional solvent is needed and no overreaction to secondary or tertiary amines occurs.

Hydrodeoxygenation of Phenol on Beta Zeolite Catalysts

Biomass is considered the largest renewable energy source and an important alternative for biofuel production. The fast pyrolysis of biomass is an economical and advantageous to get bio-oil. However, bio-oil has a large amount of oxygenated compounds and needs upgrade. The catalytic process of HDO （hydrodeoxygenation） is the most efficient way to remove oxygen from the bio-oil. In this paper, it was studied the HDO phenol （300 ℃ and 35 atm） on catalysts based on cobalt or copper oxides supported on HBeta zeolite. The catalysts were characterized by XRD （X-ray diffraction）, FTIR （infrared spectroscopy） and NH3-TPD （desorption of ammonia）. The results showed the presence of CO304 （cobalt oxide） and CuO （copper oxide）. The measurements showed the presence of acid sites weak, moderate and strong and that the impregnation of the metal oxide modifying the acidity of the support. The results showed the following order HDO conversion： CoHBeta 〉 CuHBeta 〉 HBeta. The presence of the cobalt or copper catalysts contributes to the increase in conversion due to hydrogenation. All catalysts were selective to benzene, but only the impregnated catalysts showed selectivity to cyclohexane and cyclohexene.

Electron Beam Application for Regeneration of Catalysts Used in Refinery Cracking Units

A catalyst is a substance that alters the rate of a reaction. The process of catalysis is essential to the modem day manufacturing industry, mainly in FCC （Fluid Catalytic Cracking） process units. However, long-term exploitation of oil and gas processing catalysts leads to formation of carbon- and sulfur-containing structures of coke and dense products on the catalyst surface. They block reactive catalyst sites and reduce the catalytic activity. The main advantage of radiation processing by EB （electron beam） and gamma rays is chain cracking reaction in crude oil. Otherwise, under exposure to ionize radiation, considerable structure modification of equilibrium silica-alumina catalyst from FCC process may occur, in addition to the removal of impurities. The conditions applied in the irradiation range （20-150 kGy） of gamma rays and EB were not sufficient to alter the structure of the catalyst, whether for removal of the contaminant nickel, a major contaminant of the FCC catalyst, either to rupture of the crystalline structure either for the future reutilization of chemical elements. ATR-FTIR （Attenuated Total Reflectance-Fourier Transform Infrared Spectroscopy and EDXRFS （Energy Dispersive X-Ray Fluorescence Spectrometry） analysis were used to characterize and evaluate effects of radiation processing on equilibrium catalysts purification. To evaluate and comprehend the reactive catalyst sites, SEM （Scanning Electron Microscopy） and particle size distribution analyses were carried out.