用H_2O_2-有机酸氧化脱除催化裂化柴油中的硫化物

用 30 %H2 O2 HCOOH对催化裂化柴油中的含硫化合物 (主要为苯并噻吩类 )进行了氧化 ,然后用溶剂萃取法脱除柴油中的硫化物的氧化产物。所用萃取剂包括N甲基吡咯烷酮、N ,N二甲基甲酰胺、二甲亚砜、乙腈、硝基甲烷 ,其中 ,N ,N二甲基甲酰胺和二甲亚砜效果最好 ,在剂油 (体积 )比为 1∶2、溶剂含水量为 5 %及萃取时间为 10min的条件下 ,柴油总硫含量从 0 .8%降至 0 .3% ,柴油收率为 70 %～ 80 %。对未处理柴油、氧化柴油及氧化萃取柴油进行了GC/FPD分析 ,发现催化裂化柴油中苯并噻吩的脱除率为 6 0 %。GC/MS分析表明 ,氧化产物主要为以 1,1二氧苯并噻吩类为主的砜类 ,共鉴定出了 2

Design of Multiple Metal Doped Ni Based Catalyst for Hydrogen Generation from Bio-oil Reforming at Mild-temperature

A new kind of multiple metal （Cu, Mg, Ce） doped Ni based mixed oxide catalyst, synthesized by the co-precipitation method, was used for efficient production of hydrogen from bio-oil reforming at 250-500℃. Two reforming processes, the conventional steam reforming （CSR） and the electrochemical catalytic reforming （ECR）, were performed for the bio-oil reforming. The catalyst with an atomic mol ratio of Ni：Cu：Mg：Ce：AI=5.6：1.1：1.9：1.0：9.9 exhibited very high reforming activity both in CSR and ECR processes, reaching 82.8% hydrogen yield at 500℃ in the CSR, yield of 91.1% at 400℃ and 3.1 A in the ECR, respectively. The influences of reforming temperature and the current through the catalyst in the ECR were investigated. It was observed that the reforming and decomposition of the bio-oil were significantly enhanced by the current. The promoting effects of current on the decomposition and reforming processes of bio-oil were further studied by using the model compounds of bio- oil （acetic acid and ethanol） under 101 kPa or low pressure （0.1 Pa） through the time of flight analysis. The catalyst also shows high water gas shift activity in the range of 300-600 ℃. The catalyst features and alterations in the bio-oil reforming were characterized by the ICP, XRD, XPS and BET measurements. The mechanism of bio-oil reforming was discussed based on the study of the elemental reactions and catalyst characterizations. The research catalyst, potentially, may be a practical catalyst for high efficient production of hydrogen from reforming of bio-oil at mild-temperature.

Propene and CO oxidation on Pt/Ce-Zr-SO_4^(2-) diesel oxidation catalysts:Effect of sulfate on activity and stability

Platinum/cerium-zirconium-sulfate（Pt/Ce-Zr-SO_4^（2-）） catalysts were prepared by wetness impregnation.Catalytic activities were evaluated from the combustion of propene and CO.Sulfate（SO_4^（2-））addition improved the catalytic activity significantly.When using Pt/Ce-Zr-SO_4^（2-） with 10 wt%SO_4^（2-）,the temperature for 90%conversion of propene and CO decreased by 75℃ compared with Pt/Ce-Zr.The conversion exceeded 95%at 240℃ even after 0.02%sulfur dioxide poisoning for 20 h.Temperature-programmed desorption of CO and X-ray photoelectron spectroscopy analyses revealed an improvement in Pt dispersion onto the Ce-Zr-SO_4^（2-） support,and the increased number of Pt particles built up more Pt^（-）-（SO_4^（2-））^（-） couples,which resulted in excellent activity.The increased total acidity and new Bronsted acid sites on the surface provided the Pt/Ce-Zr-SO_4^（2-） with good sulfur resistance.

Hydrogen Production From Crude Bio-oil and Biomass Char by Electrochemical Catalytic Reforming

We reports an efficient approach for production of hydrogen from crude bio-oil and biomass char in the dual fixed-bed system by using the electrochemical catalytic reforming method. The maximal absolute hydrogen yield reached 110.9 g H2/kg dry biomass. The product gas was a mixed gas containing 72%H2, 26%CO2, 1.9%CO, and a trace amount of CH4. It was observed that adding biomass char （a by-product of pyrolysis of biomass） could remarkably increase the absolute H2 yield （about 20%-50%）. The higher reforming temperature could enhance the steam reforming reaction of organic compounds in crude bio-oil and the reaction of CO and H20. In addition, the CuZn-Al2O3 catalyst in the water-gas shift bed could also increase the absolute H2 yield via shifting CO to CO2.

Research of Pyrolysis Oil and Catalysts of Garlic Stalks

We undertook a pyrolysis research on garlic stalks to solve its difficulty in use. We found that the inorganic salts in biomass played an important role in catalytic pyrolysis. Moreover, we studied the pyrolysis behavior under catalyst and catalyst-free conditions. The results showed that the weightlessness rate of garlic stalks was the highest at 550 ℃ under catalyst-free condition. The oil production rate increased with the increase of temperature and reached the peak at 550 ℃. Subsequently, as the temperature increased, the secondary cracking was intensified and oil production rate was decreased. The oil production rate increased significantly （almost 15%） under catalysis of KOH. However, the oil production rate was the highest at 500-600℃. What＇s more, we found that KOH played a major role in promoting decomposition of surface skin cells and subcutaneous fibrous layer of garlic stalks.

Commercial Application of the ICR Series Lube Isodewaxing Catalysts

This article illustrates the application of the ICR series lube oil isodewaxing catalysts in commercial scale and proposes the strategy on long cycle operation and optimization of catalysts. The results of commercial application of the catalyst have revealed that the catalyst after pretreatment including drying, sulfidation and reduction can process VGO into base oils meeting the HVI II and HVI II+ standards, and can manufacture base oils meeting the HVI III standard after incorporating the filtrate oil or gatch from acetone-benzene solvent dewaxing unit. The nitrogen content of the feed oil to the IDW reactor should be controlled at 1.0—1.5 ppm, while the CO and CO2 contents in fresh hydrogen is strictly controlled to avoid poisoning of the IDW-HDF catalysts.

Commercial Application of Novel FDFCC Grid Packing Type Stripper

The novel FDFCC grid packing stripper is used to raise the stripping efficiency of the equipment. This technology aims to increase the gas-solid contact area and improve the gas-solid contact efficiency. This technology has been applied in the revamped 1.05 Mt/a No. 1 FCC unit at the SINOPEC Changling Branch Company. The outcome on application of this equipment has revealed that the fluidization of the stripper was stable coupled with smooth operation. At a steam stripping load of less than 50% of the design value the spent catalyst had a lower H/C ratio, and the hydrogen content in the coke after revamp of the FCC unit decreased by 8.1% compared to the case before the equipment revamp. The spent catalyst had higher activity with the dry gas and coke yields reduced by over 0.5%, resulting in goodeconomic benefits.

Co-processing petroleum catalytic slurry with coal

It is studied that reactivity of petroleum catalytic slurry （PCS） and coal with Fe catalyst in 1 L autoclave, the fol- lowing is mainly discussed, coal conversion and asphalt properties, especially related with petroleum cracking slurry （PCS） properties. The results show that co-processing conversion and asphalt yield increase with the increase of PCS ratio. PCS prop- erties have important effect on coal conversion and asphalt properties. One kind of PCS shows negative effect on coal conver- sion. High aromatic PCS can lead to high ductility asphalt with good colloid properties. Coal and the PCS can lead to a strong matching effect.

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.

Optimized Technology for Residuum Processing in the ARGG Unit

The influence of feedstock property on operation in the FCC unit was studied to identify the cause leading to deteriorated products distribution related with increasingly heavier feedstock for the ARGG unit. In order to maximize the economic benefits of the ARGG unit a string of measures, including the modification of catalyst formulation, retention of high catalyst activity, application of mixed termina-tion agents to control the reaction temperature and once-through operation, and optimization of catalyst regeneration technique, were adopted to adapt the ARGG unit to processing of the heavy feedstock with its carbon residue equating to 7 % on an average. The heavy oil processing technology has brought about apparent economic benefits.

Synthesis of Petroleum Sulfonate Surfactant by Different Sulfonating Agent with Application of HIGEE Technology

With the application of HIGEE process intensification technology, petroleum sulfonate surfactant used for enhanced oil recovery was synthesized from petroleum fraction of Shengli crude oil with three sulfonating agents, including diluted liquid sulfur trioxide, diluted gaseous sulfur trioxide and fuming sulfuric acid. For each sulfonating agent, different operation modes (liquid-liquid or gas-liquid reaction with semi-continuous or continuous operation) were applied. The effects of various experimental conditions, such as solvent/oil mass ratio, sulfonating agent/oil mass ratio, gas/liquid ratio, gas concentration, reaction temperature, rotating speed, circulation ratio, reaction time and aging time, on the content of active matter and unsulfonated oil were investigated. Under relatively optimal reaction conditions, the target product was prepared with high mass content of active matter (up to 45.3%) and extremely low oil/water interfacial tension (4.5×10 –3 mN·m –1 ). The product quality and process efficiency are higher compared with traditional sulfonation technology.

The FCC Flue Gas SOx Transfer Additive RFS Developed by RIPP

The present paper introduces the development of FCC flue gas SOx transfer additives by RIPP with a brief discussion of SOx transfer mechanism. The second-generation SO transfer additives of the RFS series are RIPP＇s proprietary additives with significantly improved performances. The results of commercial tests indicate that the RFS additive can effectively control SO emission of the FCC regenerator while maintaining product yields and product quality when the additive is used in a proper concentra- tion range.

Development and Commercial Application of RFCC Catalyst for Reducing Sulfur Content in Gasoline

The sulfur-reducing functional component the Lewis acid-base pair compound and associated active zeolite component were developed to prepare the RFCC catalyst DOS for reducing sulfur content in gasoline. The results of catalyst evaluation have revealed that the Lewis acid-base pair compound developed hereby could enhance the conversion of macromolecular sulfur compounds by the catalyst to promote the proceeding of desulfurization reactions, and the synergetic action of the selected zeolite and the Lewis acid-base pair compound could definitely reduce the olefins and sulfur contents in gasoline. The heavy oil conversion capability of the catalyst DOS thus developed was higher coupled with an enhanced resistance to heavy metals contamination to reduce the sulfur content in gasoline by over 20%. The commercial application of this catalyst at the SINOPEC Jiujiang Branch Company has revealed that compared to the GRV-C catalyst the oil slurry yield obtained by the catalyst DOS was reduced along with an improved coke selectivity, an increased total liquid yield, and a decreased olefin content in gasoline. The ratio of sulfur in gasoline/sulfur in feed oil could be reduced by 20.3 m%.

ZnxCd1–xS quantum dot with enhanced photocatalytic H2-production performance

H2 is an important energy carrier for replacing fossil fuel in the future due to its high energy density and environmental friendliness.As a sustainable H2-generation method,photocatalytic H2 production by water splitting has attracted much interest.Here,oil-soluble ZnxCd1-xS quantum dot(ZCS QD)with a uniform particle size distribution were prepared by a hot-injection method.However,no photocatalytic H2-production activity was observed for the oil-soluble ZCS QD due to its hydrophobicity.Thus,the oil-soluble ZCS QD was converted into a water-soluble ZCS QD by a ligand-exchange method.The water-soluble ZCS QD exhibited excellent photocatalytic H2-production performance in the presence of glycerin and Ni^2+,with an apparent quantum efficiency of 15.9%under irradiation of 420 nm light.Further,the photocatalytic H2-generation activity of the ZCS QD was~10.7 times higher than that of the ZnxCd1-xS relative samples prepared by the conventional co-precipitation method.This work will inspire the design and fabrication of other semiconductor QD photocatalysts because QD exhibits excellent separation efficiency for photogenerated electron-hole pairs due to its small crystallite size.

Development of FCC Naphtha Hydrodesulfurization and Aromatization Process

This articles refers to the development of the technology for hydrodesulfurization (HDS) and aromatization of FCC naphtha This technology adopts a catalyst with aromatization performance, which does not reduce the octane rating of gasoline in the course of HDS of FCC naphtha. Experimental results have shown that the sulfur removal rate of FCC naphtha could reach over 85%, with the RON of gasoline increased by 0.2-0.6 units, the MON increased by 1.3-1.8 units and the antiknock index of the gasoline increased by around one unit. The total C5+ liquid yield was over 95%. The activity of regenerated catalyst could be restored to be equal to that of fresh one after coke burning on the spent catalyst.

Development of New Generation Catalysts for Selective Hydrodesulfurization of FCC Naphtha

The influence of active metal components of catalyst, additives and catalyst preparation method on the reactivity of catalyst for selective hydrodesulfurization (HDS) of FCC naphtha was investigated, and the RSDS-21 catalyst with high HDS performance and the RSDS-22 catalyst with high selectivity were developed by RIPP. The composite loading of a new series of catalysts for selective HDS of FCC gasoline has demonstrated excellent desulfurization activity and selectivity and can under conventional hydrotreating conditions manufacture clean gasoline product meeting the national IV emission standard and the Euro V emission standard with less loss in antiknock index. The finalized new series of FCC catalysts upon being adopted for selective HDS of FCC naphtha have good adaptability to different feedstocks along with good stability.

Oxidation of glycerol with H_2O_2 on Pb-promoted Pd/γ-Al_2O_3 catalysts

A series of bimetallic Pd-Pb catalysts with a constant Pd content of 1 wt%and Pb/Pd atomic ratio from 0 to 1.6 supported on γ-Al2O3 were prepared and used for glycerol oxidation with H2O2 as the oxidizing agent at atmospheric pressure,45℃ and pH =11.The morphology and dispersion of the catalysts were characterized by scanning electron microscopy-energy dispersive X-ray spectroscopy（SEM-EDX） and transmission electron microscopy（TEM）.The presence of an alloy phase in the bimetallic catalyst was detected by X-ray photoelectron spectroscopy（XPS）.Glycerol conversion obtained with the monometallic Pd catalyst was 19%,which was increased to 100%with the addition of Pb.The four bimetallic PdPb catalysts were able to oxidize glycerol to dihydroxyacetone（DIHA） and the selectivity to DIHA reached 59%,58%,34%and 25%for PdPb0.25,PdPb0.50,PdPb1.00 and PdPbl.60 catalysts,respectively.

Research on New Silica Sol Matrix Used in Fluid Catalytic Cracking Reaction

A new silica sol binder was obtained by mixing the acid-modified aluminium sulfate and water glass. The effect of SiO2 concentration in sodium silicate, pH value and polymerization was investigated. The new silica sol binder, which possessed abundant pore volume and suitable acid amount, was an ideal component for preparing cracking catalyst. As a result, the corresponding catalyst comprising the new binder showed excellent performance. Compared with the reference sample, the liquefied petroleum gas(LPG) and propylene yield obtained over this catalyst increased by 3.49 and 1.20 percentage points, respectively. The perfect pore structure and suitable Lewis acid amount of new silica sol were the possible reason leading to its outstanding performance.

Advances in DCC Process and Catalyst for Propylene Production from Heavy Oils

In the past several decades,SINOPEC has devoted continuously great efforts to the development of DCC technology,the only commercial process using heavy feeds aiming at propylene production.Recently,a series of research breakthroughs have been achieved in molecular refining.Based on the detailed analysis on the complex DCC reaction network,an innovative catalyst technology has been developed to Optimize Catalysis Kinetics (OCK in brief).The deep-cracking process can be improved with optimizing the availability of the active sites.The updated MFI and beta zeolites are used to boost the propylene selectivity.The latest generation catalyst DMMC-1 has been applied commercially.Compared with the best historical records in the past,the propylene yield upon application of the catalyst DMMC-1 increases by 2.4 m% coupled with an improved distribution of products.The DCC technology continues to assume a leading position for manufacturing propylene from heavy feedstocks.

Application of Olefin-Reducing Catalyst in FCC Unit at Daqing Petrochemical Company

This article refers to the application of DOCO olefin-reducing catalyst developed by RIPP and manufactured by the Catalyst Factory of Changling Refining and Chemical Company in the 1.4 Mt/a RFCCU at Daqing Petrochemical Company. Results of operation over two months had revealed that this catalyst had good olefin-reducing ability and heavy oil converting ability adapted to paraffinic feedstock. The gasoline olefin yield had been reduced to 36.1 v% from 54.2 v% with gasoline RON rating decreased by 1.4 units. The induction period of gasoline had significantly increased to 952 mm, while the coke yield was increased by 0.05 percentage point with light oil yield dropping by only 0.02 percentage point. The FCC product distribution is favorable.