Liquefaction of municipal waste plastics in VGO over acidic and non-acidic catalysts

Co-processing of municipal waste plastics (MWP) with vacuum gas oil (VGO) over HZSM-5, DHC-8 (commercial silica-alumina catalyst) and cobalt loaded active carbon catalyst has been comparatively studied. Co-processing experiments were carried out under hydrogen atmosphere at temperatures between 425 and 450 °C. The composition, sulphur and chlorine amount of liquid products were determined. The product distribution and the composition of liquids were changed depending upon the temperature and the catalyst type. As expected temperature led to increase in cracking activity of catalysts. DHC-8 and HZSM-5 showed substantially different activities in co-processing due to the difference in their acidity. HZSM-5 gave highest gas yield at all temperatures and highest liquid yield (38.3) at low temperature. Although Co-AC was a neutral catalyst, it showed the cracking activity as well as HZSM-5 and more than DHC-8. No chlorine compound was observed in liquid products. The sulphur amount in liquid products varied with the catalyst type. Although HZSM-5 showed good cracking activity at low temperatures, it gave the liquid product containing highest sulphur amount. By considering both the quantity and quality of liquid fuel obtained from co-processing, it may be concluded that Co-AC gave the best result in the co-processing of the MWP/VGO blend. To observe the effect of metal type loaded on active carbon on catalyst activity, a series of co-processing experiments was also carried out.     

中低温煤焦油全馏分加氢改质技术研究

以中低温煤焦油全馏分为原料,采用加氢精制-加氢裂化两段串联工艺在中试装置上开展加氢改质实验,结果表明,石脑油产品可作为优质的催化重整预加氢原料,柴油产品可用来生产优质低凝点国Ⅴ柴油,尾油馏分可作为优质的加氢裂化原料、催化裂化原料或乙烯裂解原料。中低温煤焦油全馏分加氢改质技术可以最大限度地提高轻油收率,具有技术合理可行、液体收率高、产品质量好等特点,具有良好的工业应用前景。     

Comparison of product selectivity during hydroprocessing of bitumen derived gas oil in the presence of NiMo/Al2O3 catalyst containing boron and phosphorus

A detailed experimental study was performed in a trickle-bed reactor using bitumen derived gas oil. The objective of this work was to compare the activity of NiMo/Al₂O₃ catalyst containing boron or phosphorus for the hydrotreating and mild hydrocracking of bitumen derived gas oil. Experiments were performed at the temperature and LHSV of 340-420 °C and 0.5-2 h⁻¹, respectively, using NiMo/Al₂O₃ catalysts containing 1.7 wt% boron or 2.7 wt% phosphorus. In the temperature range of 340-390 °C, higher nitrogen conversion was observed from boron containing catalyst than that from phosphorus containing catalyst whereas in the same temperature range, phosphorus containing catalyst gave higher relative removal of sulfur than boron containing catalyst. Phosphorus containing catalyst showed excellent hydrocracking and mild hydrocracking activities at all operating conditions. Higher naphtha yield and selectivity were obtained using phosphorus containing catalyst at all operating conditions. Maximum gasoline selectivity of ∼45 wt% was obtained at the temperature, pressure, and LHSV of 400 °C, 9.4 MPa and 0.5 h⁻¹, respectively, using catalyst containing 2.7 wt% phosphorus.     

DHC-32LT加氢裂化催化剂的首次应用

系统介绍了DHC-32LT 加氧裂化催化剂在中国石油长庆石化分公司120万t/a加氢裂化装置的首次应用情况,并对装置的试运行情况、原料油和产品的性质、物料平衡进行了详细分析.     

石脑油催化加氢工艺研究

介绍了石脑油催化加氢处理和加氢裂化工艺技术,重点介绍了石脑油加氢裂化技术,包括单段加氢裂化工艺、两段加氢裂化工艺、单段串联工艺;描述了国内外石脑油催化加氢催化剂的种类、研究和开发,国外以UOP和Chevron公司为代表,国内以抚顺石油化工研究院(FRIPP)为代表;探讨了石脑油催化加氢工艺现存问题—石脑油加氢反应器降压升高的原因及目前根据实际工艺情况可采取的部分解决方案。     

中油型加氢裂化催化剂的研制及其性能评价

以改性Y分子筛、Beta分子筛和无定形硅酸铝为酸性组分,W-Ni为活性金属组分,采用等体积浸渍法制备中油型加氢裂化催化剂。采用XRD、SEM-EDS、BET和XRF等对催化剂进行表征,在200 mL加氢评价装置上评价加氢裂化性能和活性稳定性。结果表明,催化剂具有较强的加氢裂化活性、良好的活性稳定性和中油选择性。在反应压力14.5 MPa、氢油体积比1 500∶1、体积空速1.5 h^-1和原料油＞370 ℃馏分转化率70%条件下,中油选择性为78.5%,C₅⁺液体收率为98.40%。（65~140） ℃重石脑油芳潜45.06%,（140~370） ℃柴油十六烷值61.2,＞370 ℃尾油BMCI值7.6,分别可作为优质的重整装置进料、柴油调和组分及乙烯裂解原料。     

新型介孔分子筛加氢裂化催化剂的研制

研究了一种最大量生产中间馏分油的新型介孔分子筛加氢裂化催化剂,200 mL一段串联加氢装置评价结果表明,在控制原料＞350 ℃馏分油75%的高转化率条件下,C_⁺⁵液收98.6%,加氢裂化生成油中最大量柴油馏分收率为67.36%,中油选择性79.2%,能满足工业装置最大量生产中间馏分油的需要。重石脑油芳潜收率为41.16%,尾油BMCI值5.9,是理想的重整原料和蒸汽裂解制乙烯原料。     

Container molecules and their guests. By Donald J. Cram & Jane M. Cram,Royal Society of Chemistry,Cambridge, 1994, xiv + 223 pp., price £49.50. ISBN 0 85186 972 6

Hydroconversion of n-heptane and toluene has been studied over a commercially proven Ni–W/SiO₂–Al₂O₃ amorphous base hydrocracking catalyst (suitable for maximizing middle distillates production from heavier feedstocks) under a wide range of operating conditions (pressure: 400–1200 psig; temperature: 315–360°C, liquid hourly space velocity (LHSV) ? 1 h^?1 and molar hydrogen/hydrocarbon feed ratio: 6–8) to assess the hydrogenation and cracking activities of the catalyst screening. Hydroisomerization followed by hydrocracking, ad hydrogenation followed by isomerization have been found to be the major reaction with n-heptane and toluene respectively as the feeds. The hydroconversion of toluene gives a very high selectivity of hydrogenated product. With n-heptane, a very high selectivity of hydroisomerized product, together with a high ratio of hydroisomerized to hydrocracked product, is obtained.     

Hydrogenation of brown coal: 6. Reactions of coal-derived products with hydrogen in the presence of metal-based catalysts

The product from the hydrogenation of an iron-tin treated Morwell, Victorian coal was separated into a number of fractions by solvent separation. Each of these fractions (tetrahydrofuran-insoluble materials, asphaltols, asphaltenes and oils) was reacted separately with hydrogen in tetralin both with and without added catalysts. The effect of added catalyst and of temperature, pressure, time and solvent on the hydrocracking and repolymerization reactions is discussed. The interconvertibility of the brown coal-derived products is clearly established, reinforcing the importance of incorporating reversibility of reactions in mechanistic models developed to describe coal hydroliquefaction.     

逆流等温-绝热烯烃饱和技术在制氢原料精制中的应用

介绍逆流等温-绝热加氢工艺流程在高烯烃含量的炼厂气用作制氢装置原料时,有效控制原料烯烃饱和过程中加氢反应器催化剂床层的温度的原理以及该工艺在中石油辽河石化焦化富气制氢中的使用情况,结果表明,该工艺解决了烯烃加氢饱和过程中的放热取出问题,实现了焦化富气用作制氢原料,拓宽了制氢原料来源.     

Transformation of olefin over Ni/HZSM-5 catalyst

Olefins in the cracked naphtha can be transformed into aromatics and isoparaffin to reduce the olefin content as well as to improve the octane number. In this work, Ni/HZSM-5 bifunctional catalyst was prepared and was characterized by nitrogen adsorption, FT-IR analysis with adsorbed pyridine as well as by X-ray powder diffraction analysis. The activity of the catalyst was investigated with the transformation of 1-hexene. The experimental results show that the main reactions occurring over Ni/HZSM-5 at relatively low temperature are cracking and isomerization of 1-hexene, which results in the high concentration of olefin in the hydrotreated product. The double-bond isomerization of 1-hexene is dominant at low temperature (<220 °C) while the skeletal isomerization is elevated at high temperature, and the aromatization activity of the Ni/HZSM-5 catalyst is promoted by high temperature. The sulfided Ni/HZSM-5 catalyst shows higher aromatization activity than the reduced one and the zeolite supported Ni catalysts show comparatively better stability than that without metal components.     

Bio-oil derived from empty fruit bunches

The fast pyrolysis of washed and unwashed empty fruit bunches (EFB), a waste of the palm oil industry, is investigated in this study. Firstly, the composition and particle size distribution of the washed and unwashed feedstock were determined and the thermal degradation behaviour was analysed by TGA. Then a 150 g/h fluidised bed bench scale fast pyrolysis unit was used to study the impact of key variables: reactor temperature in the range 425-550 °C and feedstock ash content in the range 1.03-5.43 mf wt%. The properties of the liquid product were analysed and compared with wood derived bio-oil and petroleum fuels. It was found that the maximum ash content of washed feedstock that still yields homogenous liquids is less than about 3 mf wt%. The experiments also indicated that the fast pyrolysis of washed EFB with a low ash content gave similar yields as commonly obtained for wood.     

260万t/a两段加氢裂化装置催化剂硫化过程与分析

该蜡油加氢裂化装置引进美国UOP公司加氢裂化专利技术。催化剂采用UOP公司开发的KF-848加氢精制剂和HC-115LT加氢裂化催化剂,设计原料为科威特减压蜡油,经过加氢脱硫、加氢脱氮、以及加氢裂化等反应,生产优质的轻石脑油、重石脑油、航煤、柴油和加氢尾油。该装置于2014年6月建成,7月31日进行催化剂预硫化,硫化期间由于循环氢加热炉进料流量孔板仪表引出线焊缝多次出现裂纹泄漏,被迫中断三次,至8月20日12:00完成硫化。     

降低轻石脑油收率在加氢裂化装置中的应用与探讨

乌石化炼油厂加氢裂化装置主要产品是柴油、重石脑油,副产品是轻石脑油、液化气、干气、低分气,轻石脑油属于加氢裂化副产品。本文就降低轻石脑油收率在加氢裂化装置中的应用进行分析和探讨,为进一步提高产品收益最大化提供一定的生产依据。     

催化裂化汽油改质降烯烃反应规律及反应热

利用催化裂化催化剂在小型固定流化床实验装置上对催化裂化汽油催化改质降烯烃过程的反应规律进行了实验研究,详细考察了反应温度、剂油比和重时空速对产物收率和汽油辛烷值的影响,得到了催化裂化汽油改质过程的最佳实验操作条件：反应温度为400～430℃,剂油比为7左右,重时空速为20～30 h-1。在此基础上,计算了汽油改质过程的反应热,分析了反应条件对反应热的影响,揭示了反应热的变化规律。结果表明,低温改质为放热过程,高温改质为吸热过程。改质条件对反应热影响的强弱顺序为反应温度>剂油比>重时空速。     

催化裂化汽油临氢异构化/芳构化改质过程的反应特性

采用工业Ni-Mo/Al₂O₃-HZSM-5催化剂在小型固定床加氢微反装置上对催化裂化（FCC）汽油临氢改质过程的反应特性进行了研究,通过考察反应温度、压力、空速和氢油体积比对改质后的FCC汽油烃类组成的影响,分析了汽油中不同烃类的转化性能。结果表明,氢油比对产物组成影响不大,高温、低压、低空速有利于增加芳烃的选择性,低温、高压、高空速则有利于增加异构烷烃的选择性;临氢改质后,FCC汽油的烯烃含量明显降低,芳烃和异构烷烃含量增加,因而产品汽油的辛烷值基本保持不变;全馏分、轻馏分和重馏分FCC汽油临氢改质实验结果表明,烯烃含量较高的轻馏分具有更高的转化活性;在FCC汽油临氢改质过程中,同碳数的端烯烃反应活性高于内烯烃,直链烯烃的反应活性高于支链烯烃。     

Feedstock recycling from plastics and thermosets fractions of used computers. II. Pyrolysis oil upgrading

Liquid products obtained from pyrolysis of plastics and thermosets fractions (keyboard, casings and printed circuits board and their mixture) of used computers were upgraded by thermal and catalytic hydrogenation. The effect of thermal hydrogenation was improved by using catalysts such as commercial hydrogenation DHC-8 catalyst and metal loaded activated carbon. The upgraded degradation products were separated in three fractions (residue, liquids and gases) and characterized by suitable methods such as gas chromatography (GC-MSD, GC-AED), infrared (FT-IR) and ¹H-NMR spectroscopy, elemental analysis, etc. Using of catalyst mainly affected the product distribution of upgrading process. Liquids having high amount of aromatics were obtained by upgrading. Most of hazardous toxic compounds in liquids were eliminated after hydrogenation (e.g., halogens were removed mainly by converting them into gaseous hydrogen chloride and bromide). It has been established that the hydrogenation led to elimination of the most of hazardous toxic compounds, mainly those containing bromine.     

Effect of Temperature in Hydrocracking of Light Cycle Oil on a Noble Metal‐Supported Catalyst for Fuel Production

The effect of temperature has been studied in hydrocracking of light cycle oil (LCO), byproduct of fluidized catalytic cracking (FCC) units on a bifunctional catalyst (Pt‐Pd/HY zeolite). The increase in both temperature and H₂ partial pressure have an important attenuating effect on catalyst deactivation, given that they decrease sulfur equilibrium adsorption and enhance hydrocracking of coke precursors. Therefore, the catalyst maintains significant hydrodesulfurization and hydrocracking activity. As the temperature is increased, hydrocracking conversion and naphtha selectivity increase, although there is no significant dearomatization of the medium distillate fraction in the range of the studied experimental conditions. 400 °C is the more suitable temperature for obtaining a high yield of naphtha with a high content of i‐paraffins.     

Hydroliquefaction of Sulcis low-rank coal. 1. Conversion to low-sulphur fuel oil

A low-rank Italian coal was subjected to high-pressure and high-temperature hydroliquefaction with and without a hydrogenation catalyst. A low-sulphur oil was produced, showing properties similar to those of a standard fuel oil. The hydroliquefaction product may be used directly either as a fuel or as raw material for petrochemical processes. Sulcis coal displayed particular reactivity towards hydrogen, as shown also by comparison with a widely used North American coal.     

Hydrogenation and Ring Opening of Aromatic and Naphthenic Hydrocarbons Over Noble Metal (Ir,Pt, Rh)/Al<Subscript>2</Subscript>O<Subscript>3</Subscript> Catalysts

Abstract  

The hydrogenation and ring opening of model hydrocarbons and of naphtha was studied over commercial noble metal (Ir, Pt, Rh)/Al₂O₃ catalysts. The experiments were performed in a fixed bed reactor at temperatures between 220 and 350 °C and pressures of 1.1 and 5.0 MPa, respectively. The product distribution was determined and the cetane number was calculated. The Pt catalyst is very active for hydrogenation of aromatics but does not catalyse the ring opening of naphthenes. The Ir and Rh catalysts are active for both hydrogenation of aromatics and ring opening of naphthenes. Experiments with toluene, m-xylene, propyl-benzene, and methylcyclohexane indicate that ring opening follows a selective mechanism, where the cleavage of bisecondary carbon bonds is favoured. This results in predominant formation of branched paraffins. The product distribution as well as cracking of long-chain hydrocarbons, which increase at temperatures above 260 °C, lead to an insignificant boost in the cetane number, as confirmed by experiments using real naphtha as feedstock.