CGP-2催化剂的开发及其在MIP-CGP装置中的应用

阐述了降低催化裂化汽油烯烃、硫含量，同时多产丙烯的催化剂CGP-2的研究开发与工业应用结果。CGP-2催化剂具备良好的水热稳定性，可以适应MIP-CGP工艺的双反应区尤其是第二反应区对于降低汽油馏分烯烃和硫含量的需求，此外，该催化剂还有着很强的重油裂化和抗重金属污染能力。基质中添加的L酸碱对组分，可作为对硫化物有选择性吸附和催化转化作用的活性中心。中石化沧州分公司的工业试验结果表明：CGP-2催化剂除了兼有CGP-1Z催化剂良好的产品分布和汽油性质的特点，还增加了降硫功能，汽油硫含量降低30.32%，汽油诱导期增加；丙烯产率进一步提高，焦炭选择性良好。使得沧州MIP-CGP装置生产的汽油，可满足2005年7月全国实施的新汽油标准。     

MIP-CGP工艺专用催化剂CGP-1的开发与应用

阐述了生产汽油组分满足欧Ⅲ排放标准并多产丙烯的催化裂化工艺（简称MIP-CGP）专用催化剂（简称CGP-1）的研究开发与工业应用结果。CGP-1催化剂的基质具有良好的容炭性能，使活性组元受到良好保护，其优势作用在第二反应区得以充分发挥，具有更高的氢转移活性和强的汽油小分子烯烃裂化活性。中国石化九江分公司和镇海炼化公司的MIP-CGP工业试验标定结果表明，与常规FCC相比，采用CGP-1催化剂的MIP-CGP技术在生产烯烃体积分数小于18％的汽油组分的同时，丙烯产率达到8％以上。此外，汽油诱导期大幅提高，抗爆指数增加；总液体收率有所提高，干气产率下降，焦炭选择性良好。     

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%.     

Catalyst Innovation for Reducing Olefin Content in MGG Gasoline

In order to reduce the olefin content in gasoline manufactured by the MGG (Maximizing Liquefied Gas and Gasoline) process while retaining the LPG yield, RIPP has developed a novel catalyst consisting of a more pore-opened matrix and the modified Y-zeolite and the ZRP zeolite modified with metal oxides. Test results have revealed that compared with the commercial catalyst RAG under comparable reaction conditions the reaction conversion rate and product distribution provided by the novel catalyst were similar, but the olefin content in gasoline obtained thereof was decreased with the octane rating unchanged along with a slight reduction of olefin content in the LPG fraction. The hydrothermal stability of the novel catalyst was better than the commercial catalyst RAG.     

CGP-2催化剂的试生产及工业应用

CGP-2催化剂是针对中国石化沧州分公司MIP-CGP装置的特殊要求设计生产的。该催化剂在催化剂齐鲁分公司完成了工业试生产,并在中国石化沧州分公司MIP-CGP装置上成功进行了工业试验。结果表明:与前期使用的CGP-1Z催化剂相比,总液收率增加0.57个百分点,丙烯产率增加1.1个百分点,较低的汽油烯烃含量,MON增加2个单位,诱导期增加450 min,汽油硫含量下降30.32%。CGP-2催化剂除了兼具CGP-1Z良好的产品分布和汽油性质的特点,还增加了降硫功能,使得沧州MIP-CGP装置生产的汽油,可满足2005年7月1日全国实施的新汽油标准。     

降低汽油烯烃含量用RFG-NJ催化剂的工业试验

在 1.0Mt/a重油催化裂化装置上进行了降低汽油烯烃含量用RFG -NJ催化剂的工业试验 ,并进行了标定。标定结果和日常统计数据分析表明 ,RFG -NJ催化剂具有显著降低汽油烯烃含量的性能。在装置掺渣率为 2 5 %左右、反应温度下降 6℃的情况下 ,汽油烯烃含量由48.6%下降至 3 6.5 % ,下降了 12 .1个百分点 ,汽油的诱导期延长 ,安定性得到改善 ,但汽油辛烷值略有下降 ,装置的总轻烃收率变化不大 ,丙烯收率下降了 0 .13个百分点     

反应温度对汽油烯烃在酸性催化剂上反应的影响

以1-庚烯为模型化合物,在小型固定流化床上研究了反应温度对汽油烯烃在酸性催化剂上反应的影响。考察了产物烷烃和烯烃的选择性随反应温度变化的关系。实验结果表明,低温下烷烃的选择性甚至高于烯烃。在一定的反应温度范围内,提高反应温度有利于一些氢转移反应的进行。通过对反应产物的烷烯比分析发现,异丁烯的氢转移能力明显强于丙烯。结合烷烃的双重反应机理,对反应结果进行了分析,并给出了1-庚烯在酸性催化剂上反应生成烷烃和烯烃的反应途径。     

氢转移反应与催化裂化汽油质量

加工重质含硫原油以生产高辛烷值、低硫和低烯烃含量的汽油是催化裂化装置所面临的挑战。氢转移是催化裂化的特征反应之一。氢转移反应的进行程度可以在较大范围内改变裂化产品的分布。调控氢转移反应对氢的分配作用可直接降低催化裂化汽油中的硫和烯烃含量,这已引起研究者的关注。概述了氢转移反应及其对汽油产率和辛烷值的影响,介绍了利用氢转移反应对氢的分配作用降低催化裂化汽油硫和烯烃含量的研究进展,并分析和探讨操作条件和催化剂的影响。     

Commercial Application of X-62 Catalyst for Reducing Olefins in Gasoline

In order to reduce the coke yield and increase the economic benefits of FCC unit under the prerequisites of securing the olefin content of gasoline in compliance with the requirement, SINOPEC Luoyang Branch Company applied in the period from July through October 2004 the new generation X-62 catalyst （FlexTec-LOL1） developed by the Engelhard Corporation of USA to improve the heavy oil conversion and to reduce coke make. The result of tests has shown that indicators on reducing the unit catalyst consumption, amplitude on reduction of non-ideal products （coke＋oil slurry＋dry gas） yield, and amplitude on reduction of coke yield were comparatively satisfactory.     

降低催化裂化汽油硫含量的重油裂化催化剂DOS的工业应用试验

在九江分公司一套催化装置上进行了降低催化汽油硫含量和烯烃含量的催化裂化催化剂DOS的工业应用试验，试验结果表明，和GRV－C催化剂相比，液态烃、汽油和总液收产率有所增加，干气、焦炭的产率有所下降，反映出DOS催化剂具有裂化能力强、焦炭选择性好的特点。汽油烯烃含量降低7.8个体积百分点，汽油硫含量／原料油硫含量下降20.3ω%,说明DOS催化剂具有较好的降低汽油硫含量和烯烃含量的能力。     

氢转移反应与催化裂化汽油质量

从分析氢转移反应的机理及本质人手，论述了催化剂孔结构、硅铝比、稀土量、晶粒度、沸石与基质相互作用、沸石组成等对催化裂化氢转移反应活性的影响、指出通过改进催化剂制备技术，选择合适的工艺操作条件及氢转移活性适宜的催化剂可以降低催化裂化汽油烯烃含量，不降低其辛烷值，并抑制焦炭的生成。     

提高汽油质量的措施

针对汽油中硫及烯烃含量高、调和组分单一的现状，以欧洲Ⅲ汽油标准为指导原则，根据实际生产情况，优化催化裂化装置原料，使用降硫助剂和降烯烃催化剂，采用新技术新工艺，增加高标号调和组分．增建汽油加氢改质装置和吸附脱硫装置等一系列技术措施，使汽油产品质量指标满足GB17930—1999要求。     

MIP-CGP工艺对汽油硫含量的影响

考察了MIP-CGP工艺在降低汽油烯烃含量的同时所具有的降硫作用，阐明了MIP—CGP工艺降低汽油硫含量的基本原理和影响因素。结果表明，通过提高转化率和第二反应区催化剂的藏量，MIP—CGP工艺可以将催化裂化汽油中的硫含量降至所要求的水平。     

哈油FCC汽油硫及烯烃含量分布特征研究

我国每年要从哈萨克斯坦进口原油约10 Mt/a,进口哈油大部分是在中国石油天然气股份有限公司独山子石化分公司加工,其中二次加工生产的FCC汽油硫质量分数为600～1 000 μg/g.在生产国Ⅳ和国Ⅴ成品汽油时,需要对哈油FCC汽油进行选择性深度加氢精制,加氢精制时有部分烯烃被加氢饱和,降低了成品汽油的辛烷值.研究表明:将硫质量分数为686 μg/g、烯烃质量分数为47.60％的哈油FCC汽油切割成不同温度段的窄馏分,随着切割温度的提高,各窄馏分硫质量分数由170μg/g逐步增加到1 360 μg/g,而烯烃质量分数由75.51％逐步降低到30.93％.因此FCC汽油硫含量和芳烃含量主要集中在重汽油馏分中,烯烃含量主要集中在轻汽油馏分中,40℃以前轻汽油馏分中的硫有近50％的是硫醇硫.     

Selective Hydrogen Transfer Reaction in FCC Process：Characterization and Application

The product distribution and gasoline quality of FCC process, especially the olefin content,heavily depends on the catalyst performance in terms of selective/non-selective hydrogen transfer reaction selectivity. A reliable experimental protocol has been established by using n-dodecane as a probe molecule to characterize the selective hydrogen transfer ability of catalytic materials. The results obtained have been correlated with the performance of the practical catalysts.     

Investigation of the Operating Conditions on Decreasing FCC Gasoline Olefin Content by GOR-Q Catalyst

Abstract

Based on a fixed-fluid-bed reactor and a GOR-Q catalyst, the influence of process parameters on decreasing gasoline olefin content was studied. The results show that the catalyst had an obvious effect on the decreasing gasoline olefins. A higher catalyst-to-oil ratio, lower weighted hourly space velocity, and lower reactor temperature give rise to lower gasoline olefin content. The reduction of fluid catalytic cracking (FCC) gasoline olefin content is achieved by decreasing olefins of low carbon number. Reaction temperature under 520°C and catalyst-to-oil ratio = 7.0 for a GOR-Q catalyst are advantageous for decreasing olefin content of FCC gasoline.     

工艺条件对降低催化汽油烯烃过程中汽油烯烃分布的影响

着重考察了在使用降烯烃催化剂GOR-Q和常规催化剂MLC-500时工艺条件对催化汽油烯烃分布的影响。结果表明：GOR-Q催化剂具有明显降低催化汽油各类烯烃的效果。从碳数分布看,催化汽油中的烯烃主要集中在C5～C7之间。从类型看,单烯烃是催化汽油烯烃的主要存在形式,其中又以正构烯烃和单支链烯烃为主。降低催化汽油烯烃主要是通过小分子烯烃或单烯烃、正构烯烃、单支链烯烃的降低来实现。低温、低空速、高剂油比有利于降低催化汽油中单烯烃、正构烯烃、单支链烯烃和二烯烃含量,但为了减少辛烷值的损失,在降低催化汽油烯烃时首先应采用提高剂油比的方式。     

催化剂,多环芳烃及硫对1—甲基萘以及二（1—萘）甲烷氢转移？…

探讨了在温和反应条件下,催化剂、多环芳烃及硫对金属催化剂催化的１－甲基萘（１－ＭＮ）以及二（１－萘）甲烷（ＤＮＭ）加氢反应的影响。结果表明,铁和镍对促进１＿ＭＮ和ＤＮＭ的加氢非常有效,而多环芳烃却显降低了１－ＭＮ和ＤＮＭ的加氢转化率;加入硫显阻碍了加氢反应,却大大促进了加氢裂解反应。初步探讨了有关的反应机理。     

RFCC汽油降烯烃前后氢平衡计算与分析

通过对中国石油化工股份有限公司北京燕山分公司三催化装置使用GOR－DQ降烯烃催化剂前后氢平衡及氢分布的计算与分析，验证了该装置物料平衡的准确性，并发现使用该催化剂在明显降低汽油烯烃的同时，使氢分布趋于合理。     

Commercial Test of HGY-2000R FCC Catalyst for Maximizing Gasoline Yield

HGY-2000R catalyst developed by Research Institute of Petroleum Processing, SINOPEC was tested in the RFCC unit, Ulsan complex, SK Corporation, Korea from July to August 2002. The primary results of commercial test show that it has good performance of higher activity, good hydrotherrnal stability,higher residue cracking ability, good coke selectivity and good fluidization properties as well as maximizing gasoline yield with a lower olefin content.