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.     

Development and Application of the CGP-2 Catalyst in the MIP-CGP Process

The research and development of the CGP-2 catalyst, which was used in the MIP-CGP process for reducing the olefin and sulfur contents of FCC naphtha and enhancing the propylene yield, were introduced. A specific type of metal compound was added into the matrix to provide active centers for reactions including catalytic conversion and selective adsorption of sulfur containing compounds. The CGP-2 catalyst possessed excellent hydrothermal stability to meet the requirements of the 2rid reaction zone of the MIP-CGP process. The commercial test of the said catalyst at the SINOPEC Cangzhou refinery showed that in comparison with the base case （using the CGP-1Z catalyst） the CGP-2 catalyst could reduce the sulfur content of FCC naphtha by 30.32% and increase the propylene yield along with good coke selectivity. Thus, the naphtha produced by the MIP-CGP process at the Cangzhou refinery can meet the new gasoline standard enforced in July 2005.     

Commercial Tests on Continuous Production of lO-kt/a Polyether Polyol Passed Technical Appraisal

The commercial tests of the two-stage riser catalytic pyrolysis-maximizing propylene（TMP）technology independently developed by the State Key Heavy Oil Laboratory of China Petroleum University （East China） have revealed that atmospheric resid （AR） upon being subjected to TMP could achieve a propylene yield in excess of 18%, and the sum of LPG, gasoline and diesel yield could be close to 83%. Over the recent years such processes as FCC or DCC of heavy oil to maximize propylene yield have attracted special attention, because the conventional catalytic cracking technology can only contribute a propylene yield in the range of 3%-5%. If catalytic additive is added to the FCC catalyst, the propylene yield can only increased by 1%-2%. At relatively severe operating conditions the propylene yield can be increased with a significant increase in LPG yield at the expense of reduced diesel yield with obviously worse product quality.     

Successful Trial Production of Catalyst for Maximization of Propylene Yield Developed by Lanzhou Petrochemical Research Institute

The novel catalyst LCC-2 developed by PetroChina Lanzhou Petrochemical Research Institute (LPRI) to maximize the pro- pylene yield has been successfully manufactured in commer- cial scale at Lanzhou Petrochemical Company’s catalyst factory. Maximization of propylene yield from FCC units is the main goal of major refineries to increase their economic benefits. LPRI has developed the catalyst LCC-1 for maximization of propylene yield and the additive LCC-A. The additive LCC-A is be…     

Successful Trial Production of Additive for Propylene Catalytic Cracking by the Research Center of Lanzhou Chemical Company

The second-generation additive LOP-A for enhancing the propylene output and increasing the octane rating of gasoline developed by the Lanzhou Chemical Research Center under the PetroChina Petrochemical Research Institute has been successfully manufactured at the first attempt in the No. 1 microspheric catalyst unit of the catalyst factory at the Lanzhou Petrochemical Company.     

Effect of Olefins on Formation of Sulfur Compounds in FCC Gasoline

The effect of olefins on formation of sulfur compounds in FCC gasoline was studied in a small-scale fixed fluidized bed （FFB） unit at temperatures ranging from 400℃ to 500℃, a weight hourly space velocity （WHSV） of 10 h-1, and a catalyst/oil ratio of 6. The results showed that C4--C6 olefins contained in the FCC gasoline could react with HzS to form predominantly thiophenes, alkyl-thiophenes as well as a fractional amount of thiols, while large molecular olefins such as heptene could react with hydrogen sulfide to form benzothiophenes. The amount of sulfur compounds formed at different tem- peratures over different catalysts were in proportion to the mass fractions of olefins in the feedstock, with the amount of sulfur compounds formed over REUSY catalyst exceeding those formed over the shape selective zeolite catalyst owing to the effect of catalyst performance and the impact of catalyst on the degree of olefin conversion. The amount of sulfur compounds generated and their increase reached a maximum at 450℃ and a minimum at 400℃ because of the influence of temperature on the thermodynamic and kinetic constants for formation of sulfur compound as well as on the olefin conversion degree. Based on the above-mentioned study, a reaction network and a model for prediction of sulfur compounds generated upon reaction of olefins in FCC gasoline with HES were established.     

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%.     

Commercial Application of FCC Catalyst RSC-2006

SINOPEC Research Institute of Petroleum Processing has developed a FCC catalyst to crack heavy oil feedstock to improve high-value products yield, and its commercial application has been conducted successfully in RFCCU at SINOPEC Jingmen Branch Company. This catalyst has revealed its excellent bottoms crackability and coke selectivity. Commercial application tests showed that the slurry yield decreased by 2.84%, and the coke make dropped by 0.64%, with the total yield of LPG, gasoline and diesel increased by 3.99%.     

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.     

NEW REFORMING CATALYST DEVELOPED BY RIPP

To meet the demands for high-octane gasoline and aromatics,catalytic reforming process has been advancing quickly in China.The reforming catalysts developed by RIPP have been used in more than 80% capacity of domestic CCR and SR units.This paper introduces the properties of PSVI CCR catalyst developed by RIPP in recent years and also the result from commercial units.The PS-VI catalyst has high activity and good selectivity,under the same reaction conditions,the carbon on catalyst was lowered by 26% in mass as compared with that of the reference catalyst.Among the SR reforming catalysts,the new type of PRT series catalysts have excellent performance at low reaction pressure compared with the ref.Cat A.The aromatics and reformate mass yields of PRT catalyst were 2%-3% and 3%,respectively ,higher than those of Cat A,and the run length was 30%-40% longer as well,which exhibits good prospect of application.     

新型催化裂化催化剂的开发及工业应用

介绍了中国石油兰州化工研究中心研发的新型催化裂化催化剂制备技术及其系列催化剂的工业应用情况.结果表明,与国产同类型催化剂相比,LHO-1型重油降烯烃催化剂可使油浆收率降低0.97个百分点,汽油烯烃体积分数降低5.1个百分点;LCC-2型多产丙烯催化剂可使丙烯收率提高1.23个百分点;LIP-100型多产异构烷烃催化剂可使丙烯收率提高1.26个百分点,汽油研究法辛烷值提高1.7个单位.     

催化裂化汽油中芳烃含量随反应条件及催化剂的变化规律

首先将气相色谱法测定汽油馏分的芳烃含量和行业标准方法SH/T0693分析结果进行关联。在实验室小型固定流化床装置上，考察了裂化产物汽油馏分中芳烃含量随反应条件及催化剂的变化规律。结果表明，通过调节剂油比提高转化率时，苯含量增加较小；反应温度提高，汽油馏分中的苯含量显著提高；在催化剂中添加丙烯助剂时，在增产丙烯的同时，汽油中苯含量显著增加。     

CGP-1GQ催化剂在MIP装置上的工业应用

石油化工科学研究院研制的CGP-1GQ催化剂在中国石化上海高桥分公司1.40 Mt/a MIP装置上的工业应用结果表明，使用CGP-1GQ催化剂后，装置液化气产率达到18.71%，液化气中丙烯体积分数达到37.74％。液体收率、掺渣能力基本保持不变，装置汽油性质有所改善。表明CGP-1GQ催化剂用于MIP装置具有改善汽油性质和增产丙烯的效果。     

催化裂化催化剂及助剂的现状和发展

介绍了国内外催化裂化催化剂及助剂领域的最新动态.在全球范围内,许多催化剂企业进行了重组.在技术上,多种新的催化材料引入催化剂中.重油转化催化剂得到了越来越广泛的应用,降低汽油烯烃含量和硫含量催化剂的开发取得了实质进展.中国在特种催化裂化工艺专用催化剂技术方面明显处于国际领先水平,如CGP-1和CGP-2催化剂(MIP-CGP工艺专用催化剂)、MMC系列催化剂(DCC工艺专用催化剂),等等.受日益增长的丙烯市场需求影响,催化裂化催化剂对丙烯和液化石油气的选择性有了显著提高.今后,提高清洁汽油辛烷值的催化裂化催化剂以及减少催化裂化装置烟气污染排放的催化剂和助剂将成为研发的热点,催化剂低成本和清洁生产技术也将得到重视和发展.     

EFFECT OF ZSM-5 ADDITION ON PRODUCT DISTRIBUTION IN A HIGH SEVERITY FCC MODE

The high-severity fluid catalytic cracking (HS-FCC) process is a novel FCC process that enhances light olefins yield under high severity reaction conditions. The process has been investigated by using a small-scale FCC pilot plant (0.1 BPD) with a down-flow reactor. High severity reaction conditions are preferable for enhancing the production of light olefins by catalytic cracking of heavy oils. As another option for the light olefin production, adoption of ZSM-5 additive in conventional FCC units is well known. This presentation describes the effect of ZSM-5 additive on the catalytic cracking of vacuum gas oil under high severity reaction conditions, particularly focusing on the synergistic effect with the base catalyst. Three kinds of FCC catalysts with different activity were used as base catalysts. Although the employment of a ZSM-5 additive resulted in significant increase in the light olefins yield at the expense of gasoline in each catalyst system tested, the effectiveness was varied depending on the nature of the base catalysts. By choosing a suitable base cracking catalyst, more than 20 wt% of propylene yield was obtained at a one-pass conversion of fresh feed.     

EFFECT OF ZSM-5 ADDITION ON PRODUCT DISTRIBUTION IN A HIGH SEVERITY FCC MODE

The high-severity fluid catalytic cracking (HS-FCC) process is a novel FCC process that enhances light olefins yield under high severity reaction conditions. The process has been investigated by using a small-scale FCC pilot plant (0.1 BPD) with a down-flow reactor. High severity reaction conditions are preferable for enhancing the production of light olefins by catalytic cracking of heavy oils. As another option for the light olefin production, adoption of ZSM-5 additive in conventional FCC units is well known. This presentation describes the effect of ZSM-5 additive on the catalytic cracking of vacuum gas oil under high severity reaction conditions, particularly focusing on the synergistic effect with the base catalyst. Three kinds of FCC catalysts with different activity were used as base catalysts. Although the employment of a ZSM-5 additive resulted in significant increase in the light olefins yield at the expense of gasoline in each catalyst system tested, the effectiveness was varied depending on the nature of the base catalysts. By choosing a suitable base cracking catalyst, more than 20 wt% of propylene yield was obtained at a one-pass conversion of fresh feed.     

催化裂化汽油裂解制备低碳烯烃

在小型提升管催化裂化实验装置上研究了催化裂化(FCC)汽油催化裂解生产低碳烯烃的反应规律。实验结果表明,催化剂类型、反应温度、停留时间及水蒸气用量对乙烯、丙烯的产率均有显著的影响。高温、大剂油比、长停留时间及提高水蒸气用量都可促进汽油的裂解,增加低碳烯烃的产率。在实验室条件下,以ZC-7300为催化剂,多产低碳烯烃的最佳条件:反应温度580℃,停留时间1.6s左右,剂油质量比为11,水蒸气与汽油的质量比为0.20。对不同催化剂进行了对比实验得知,自制催化剂A的催化效果最好,汽油转化率达到40%以上,乙烯+丙烯的产率达到20%以上,焦炭和干气(不含乙烯)的产率不大于5%。     

两段提升管催化裂化生产丙烯工艺

采用小型提升管实验装置模拟两段提升管催化裂化(TSRFCC)工艺,在反应条件、操作方式和氢分配方面进行了研究。实验结果表明,停留时间对丙烯收率的影响最明显,提高剂油比是增产丙烯经济效益最好的措施。以大庆掺渣蜡油为原料,采用LCC-200型催化剂,二段提升管回炼一段“汽油+油浆”时,液化气和丙烯总收率分别为36.52%和16.30%,汽油和柴油总收率分别为26.11%和19.10%,表明TSRFCC工艺配合多产丙烯催化剂,可在生产丙烯的同时兼顾轻油收率和品质。第二段提升管回炼一段柴油不能显著提高丙烯收率,还会降低柴油总收率和品质。第一段提升管提供约70%的丙烯和第二段提升管的原料,因此TSRFCC工艺一段提升管需保持合适的转化深度。TSRFCC工艺的氢利用率可达89.82%,氢分配比较合理。     

多产汽油的催化裂化催化剂LPC-70的工业应用

多产汽油的催化裂化催化剂LPC-70含有富B酸多级孔基质材料APM-7,可有效提高重油转化能力,并提高汽油收率和液化气中的丙烯浓度。LPC-70催化剂在兰州石化3.0 Mt/a重油催化裂化装置应用结果表明,与空白标定相比,在原料劣质化和催化剂单耗降低0.2 kg/t的条件下,油浆产率下降0.71百分点,汽油收率增加2.53百分点,柴汽质量比由0.46下降至0.39,液化气中丙烯体积分数提高6.10百分点。