CHZ—3渣油裂化催化剂的工业应用

ＣＨＺ－３是由长岭炼油化工总厂与北京石油化工科学研究院合作开发的一种新型渣油裂化催化剂。具有活性适中、渣油裂解能力强、焦炭选择性好等特点。在工业应用中取得了良好的效果。     

渣油催化裂化装置消除剂油比瓶颈的方法

介绍了渣油裂化催化剂的性能要点 ,讨论了渣油裂化催化剂性能的发挥、产品分布、汽油辛烷值等与剂油比的关系。指出渣油裂化一般采用氢转移活性低的催化剂 ,这种催化剂需要在高剂油比下操作 ;对渣油的裂化和提高汽油辛烷值也需要高的剂油比。现有一些催化剂循环量受到限制剂油比较低的装置可采用分段进料的方法 ,着重提高对渣油的剂油比。提出了现有几种装置提高剂油比的方法。     

重油催化裂化催化剂RCH的开发与工业应用

RCH催化剂是继我国第一代超稳Y型催化裂化催化剂之后，开发研制的新型渣油裂化催化剂。该剂沸石含量低，而在裂化性能、产品收率、焦炭选择性等方面均与国内外同类型催化剂相当，可替代进口催化剂在重油催化裂化（RFCC）装置上使用；该剂更具有平衡活性和轻质油收率高、稳定性好、裂化重质油能力和抗重金属污染能力强等特点，同时制备工艺先进，流程简单，属国际先进水平。     

渣油裂化催化剂的共性与特性

以两种渣油裂化催化剂为例，讨论了在渣油裂化催化剂研制中应如何考虑它们的共性与特性。渣油裂化催化剂的基本共性为：对重油大分子的裂化能力、抗金属污染能力以及良好的焦炭选择性、汽提性能和水热稳定性，而特性则表现了催化剂适应不同裂化产品分布的能力。认为在市场经济条件下，由于产品的需求经常发生变化，催化剂应该具有一定的应变能力，以适应不同的产品分布方案，同时应与工艺技术相配合，充分发挥催化剂的作用。     

新型孔结构重油催化裂化催化剂的制备及评价

针对目前裂化催化剂孔径小、贯通性不够理想的情况下,研究了在不改变催化剂组成的前提下,通过以聚苯乙烯颗粒为模板剂在催化剂基质中增加适量的、尺寸可控的大孔,以改善催化剂的孔结构,减小重油大分子在反应过程中的扩散阻力.最后将所得到的裂化催化剂用于大庆常压渣油的微反实验中.活性评价结果表明,在相同工艺条件下,大庆常压渣油在具有大孔的裂化催化剂上的转化率较不具有大孔的催化剂提高了10.8%.     

中东渣油悬浮床加氢裂化反应产物及总硫分布的研究

以中东含硫渣油为原料，在高压釜中进行不同反应类型和不同分散型催化剂的悬浮床加氢裂化反应，分析产物分布及其中总硫分布。加氢活性高的催化剂具有较强的抑制反应产物二次裂解的能力，并且有较强的硫元素脱除能力。反应添加硫化剂对于含硫渣油的裂化产物及总硫分布没有明显的影响；加入供氢剂抑制了缩合反应及裂化反应，同时促进了硫的脱除。     

OB—3000裂化催化剂工业应用试验

介绍ＯＢ－３０００裂化催化剂在九江石油化工总厂１Ｍｔ／ａ掺渣油催化裂化装置上的应用情况。结果表明，和原来使用的ＲＨＺ－３００裂化催化剂相比，ＯＢ－３０００裂化催化剂具有更强的重油裂化能力，可降低焦炭产率约１０％，提高液化气产率２０％，提高汽油辛烷值１～２个单位     

高掺渣油比催化裂解催化剂RMMC-1的开发

为提高多产低碳烯烃催化剂应对装置掺炼渣油的能力,开发了新一代催化裂解催化剂RMMC-1。RMMC-1采用大孔结构（9～13 nm）的基质,改善催化剂孔分布,强化基质的炭捕集区来提高催化剂活性中心可接近性,增加对渣油等大分子烃的一次裂化。RMMC-1催化剂对渣油等重质油的催化裂解能力强,实现多产丙烯目的的同时,液态产品质量略有改善。     

催化剂的大分子裂化性能与渣油裂化

以渣油的催化裂化反应化学为基础,详细论述催化剂孔结构及其酸性、基质活性、沸石晶粒度、基质与沸石的相互作用等因素对重油催化裂化催化剂大分子裂化性能的影响。重油特别是渣油的组成特征要求催化剂必须具有合适的大、中、小孔比例及适度的酸性分布,以解决大分子烃在沸石催化剂中的活性可接近性问题,其中大、中孔尤其是中孔及其活性起着十分关键的作用;活性基质不但能大幅度提高催化剂的重油裂化能力,且对催化剂的抗重金属、抗碱氮、脱硫、脱氮等性能及产品质量产生重要影响;此外,针对不同装置催化剂的设计要求,提高沸石外表面、充分利用沸石与基质的相互作用等因素在大分子的催化裂解中也起着非常重要的作用。     

纳米自组装催化剂渣油加氢脱残炭性能

根据纳米自组装机理,以γ-Al_2O_3为载体,Mo-Ni为活性组分,制备了正向胶束法和反应胶束法Mo-Ni纳米自组装催化剂。结果表明:以残炭质量分数为4.78%的渣油为原料,在Mo/Ni(质量比)为6∶1的条件下,当精制催化剂和裂化催化剂活性组分负载质量分数分别为30%,25%时,催化剂的残炭脱除效果为最佳;将正向胶束法制备的精制和裂化催化剂复配使用,在反应压力为14 MPa,体积空速为0.20 h~(-1),反应温度为350℃,氢气/原料油(体积比)为850的最佳条件下,渣油加氢脱残炭率最高达到53.82%。     

Preparation,Characterization, Evaluation,and Regeneration of a Novel Hydro-upgrading Catalyst

A non–noble metal hydro-upgrading catalyst was prepared using modified zeolites as acidic component, and catalytic performance evaluation was also carried out between the hydro-upgrading catalyst and the reference catalyst, which is a commercial catalyst. The evaluation results revealed that under the pressure of 8.0 MPa, the diesel product yield of the hydro-upgrading catalyst was 98.8 m%, cetane index increment was 7.3 units, diesel yield of the reference catalyst was 98.3 m%, and the cetane index increment was 7.2 units; under the pressure of 6.0 MPa, the diesel product yield of the hydro-upgrading catalyst was 99.1 m%, cetane index increment was 6.1 units, diesel yield of the reference catalyst was 98.7m%, and the cetane index increment was 5.3 units. In addition, preparation repeatability, activity stability, and regeneration performance tests of the hydro-upgrading catalyst were carried out.     

Study on the Performance and Commercial Application of New Generation DMMC-1 Type Catalyst for Deep Catalytic Cracking

Over the past decades SINOPEC has been uninterruptedly engaging in the development and upgrading of deep catalytic cracking （DCC） technology for manufacturing propylene from heavy oil. Recently SINOPEC after having made a lot of progress in the area of oil refining at the molecular level has developed a new generation DMMC-1 type catalyst designed for the DCC process. The laboratory evaluation tests have shown that compared to the existing MMC-2 type catalyst that features the best comprehensive performance, the DMMC-1 type catalyst has increased the propylene yield by 2.2% with the propylene selectivity increased by 10%. The said catalyst has improved its ability for heavy oil cracking and coke selectivity along with reduction of olefin content in gasoline to achieve a better product distribution and improve the product quality. The results of application of the said catalyst in a 650-kt/a commercial DCC unit at SINOPEC Anqing Branch Company have revealed that the DMMC- 1 catalyst demonstrated an enhanced capability for heavy oil cracking and could increase the total liquid yield to 84.56 m% from 83.92 m%, the LPG yield to 38.90 m % from 34.60 m %, the propylene yield to 17.80 m% from 15.37 m% and the propylene concentration to 45.91 m% from 44.91 m%, and reduce the coke yield from 7.61 m% to 7.05 m% and the olefin content in gasoline from 42.3 v% to 37.5 v%, resulting in an incremental profit amounting to 52.19 million RMB a year. This technology has further upgraded and developed the DCC technology which has been commanding a leading position among the industry peers.     

First Commercial Application of Upflow Residuum Hydrotreating Catalyst

This article refers to the first commercial application of upflow residuum hydrotreating serial catalyst, developed by Fushun Research Institute of Petroleum and Petrochemicals (FRIPP), in the residuum hydrotreating unit at Shengli refinery of Qilu Petrochemical Company. This catalyst features large pore volume and large pore diameter. The production practice for more than one year has revealed that the domestic upflow residuum hydrotreating catalyst has shown good performance and stability over the whole period of operation despite its high activity at the start of run, and has basically reached the level of similar imported catalyst.     

催化裂化原料预处理催化剂FF-18的性能和应用

介绍了催化裂化原料加氢预处理催化剂FF-18的反应性能评价及首次工业应用情况.该催化剂采用镍和钨作为活性金属组分.评价中采用了硫质量分数约1.5%的伊朗VGO,工业应用中采用了硫质量分数约2.0%的由VGO,CGO和DAO混合成的混合油,评价和工业应用表明,FF-18催化剂具有较好的加氢脱硫性能及原料适应性,加氢处理得到的蜡油是优质催化裂化原料.     

渣油固定床加氢处理催化剂中试评价与工业应用

介绍了渣油加氢处理催化剂中试评价和工业实验情况，结果表明：国产渣油加氢处理系列催化剂在处理孤岛减压渣油时，具有良好的活性稳定性，使用性能好，产品质量、收率及其运转周期与进口催化剂相近。     

焦炭选择性渣油裂化催化剂可改善FCC装置效益

新型焦炭选择性渣油裂化催化剂可将康氏残炭对FCC性能的影响减少50％;允许平衡剂上镍含量高达10000ppm,而不需加钝化剂;抗钒性好,裂化性能适宜,可掺炼更多的渣油而不增加催化剂单耗和油浆产率.4个工业应用实例表明,采用此种新型催化剂,可较大幅度地提高经济效益.     

EVALUATION OF THE ACTIVITY OF NICKEL IN COPROCESSING USING MODEL SYSTEMS

The catalytic activity of nickel, a trace metal indigenous to residuum used in coprocessing of coal and petroleum residuum, was investigated in hydrogenation and heteroatom removal reactions using model systems at coprocessing conditions. Hydrocarbons and heteroatomic species of S, N, and O having similar chemical structures to some compounds present in coal and residuum were used as models. The active Ni catalyst was generated in situ by thermal decomposition of organic nickel complexes, all of which were active for hydrogenation of the models selected except for nickel naphthenate. The active Ni promoted ring saturation in aromatic and heteroatomic compounds rather than ring hydrogenolysis or heteroatom removal. In the presence of either elemental sulfur or organic sulfur compounds, the catalytic activity of Ni for hydrogenation and heteroatom removal was eliminated. Because of the high sulfur content in coal and residuum, inherent catalytic activity from the nickel indigenous to residuum for hydrogenation and heteroatom removal reactions during coprocessing may be hindered.     

固体酸催化剂在对羟基苯甲酸酯合成中的应用

考察了SO_4~(2-)/膨润土固体酸催化剂在对羟基苯甲酸与甲醇、乙醇、正丁醇酯化反应中的作用,以及反应时间,催化剂用量和溶剂对酯化反应的活性的影响。实验发现,在以甲苯作溶剂,反应温度95～110℃,反应时间3～4h,催化剂用量0.4m％条件下,催化效果最佳,表明该催化剂是一种有效的对羟基苯甲酸酯化催化剂。     

MGD Technology Development and Its Commercial Application

MGD, a FCC technology that can maximize both the LPG and LCO production, has been developed. The effects of reaction temperature and catalyst to oil ratio on naphtha re-cracking and the resulted naphtha compositions were investigated. The commercial performances show that relative to conventional FCC, the LPG and LCO yields increased by 1.3%-5.0 m% and 3%-5 m%, respectively.     

DCC Technology and Its Commercial Experience

DCC is a new technology derived from FCC for propylene production. The propylene yields can reach 23m% with paraffinic feed and around 17m% with intermediate base feed. A portion of DCC cracked naphtha recycled in a commercial unit resulted in a propylene yield increment of 3.5m% at some expense of naphtha. The total BTX in the 75 - 150℃ naphtha fraction was 57. 6v%, in which toluene and xylenes were 21.9v% and 30.3v%, respectively. DCC catalyst consists of a modified mesopore zeolite with pentasil structure for primary product of naphtha range to undergo secondary cracking for producing light olefins. A series of DCC catalysts was formulated for various objectives, such as maximum propylene, maximum isoolefins, and metal tolerance for residual oil processing, etc. Seven commercial units have been put into production since 1990 inside and outside China, in which three of them were revamped from existing FCCUs, and the other four were grassroots units including a 750kt/a unit in TPI Company, Thailand. Currently, the TPI unit is running in full design capacity with about 40m% of atmospheric residual oil in the feedstock. Although the feedstock is much heavier than design, the propylene yield still keeps around the design value. The commercial experiences of some units are presented.