In situ catalytic upgrading of heavy crude oil through low-temperature oxidation

The low-temperature catalytic oxidation of heavy crude oil (Xinjiang Oilfield, China) was studied using three types of catalysts including oil-soluble, watersoluble, and dispersed catalysts. According to primary screening, oil-soluble catalysts, copper naphthenate and manganese naphthenate, are more attractive, and were selected to further investigate their catalytic performance in in situ upgrading of heavy oil. The heavy oil compositions and molecular structures were characterized by column chromatography, elemental analysis, and Fourier transform infrared spectrometry before and after reaction. An Arrhenius kinetics model was introduced to calculate the rheological activation energy of heavy oil from the viscosity– temperature characteristics. Results show that the two oil-soluble catalysts can crack part of heavy components into light components, decrease the heteroatom content, and achieve the transition of reaction mode from oxygen addition to bond scission. The calculated rheological activation energy of heavy oil from the fitted Arrhenius model is consistent with physical properties of heavy oil (oil viscosity and contents of heavy fractions). It is found that the temperature, oil composition, and internal molecular structures are the main factors affecting its flow ability. Oil-soluble catalyst-assisted air injection or air huff-n-puff injection is a promising in situ catalytic upgrading method for improving heavy oil recovery.     

DEVELOPMENT OF DIRECT UPGRADING PROCESS FOR HEAVY CRUDE OIL

The direct upgrading process from heavy crude oil to sweet and light oil (IKC process) has been developed for about 10 years in Idemitsu Kosan. Compared with conventional refinery scheme consisting of YR-HDS, VGOHYC and so on, the new refinery scheme combined with IKC process and Topper was always economically feasible with lower cost and smaller energy consumption. In the existing refinery of no middle distillate HDS and residue HDS of HYC plants to supplement IKC process is expected to be one of the efficient methods to cope with the environmental regulations.     

Heating of heavy oil by circulating hot water in closed double casing in ultra-deep wells

In heavy oil production,the loss of energy to ambient surroundings decreases the temperature of the heavy oil flowing upwards in a vertical wellbore,which increases the oil viscosity and the oil may not flow normally in the wellbore.Therefore,it is necessary to lower the heavy oil viscosity by heating methods to allow it to be lifted easily.Heating of heavy oil in an oil well is achieved by circulating hot water in annuli in the well(tubing-casing annulus,casing-casing annulus).In this paper,based on heat transfer principles and fluid flow theory,a model is developed for produced fluids and hot water flowing in a vertical wellbore.The temperature and pressure of produced fluids and hot water in the wellbore are calculated and the effect of hot water on heavy oil temperature is analyzed.Calculated results show that the hot water circulating in the annuli may effectively heat the heavy oil in the tubing,so as to significantly reduce both oil viscosity and resistance to oil flow.     

Research on Optimized Utilization of Naphtha Resources Based on Adsorptive Separation with Zeolite

By means of molecular scale management, the technology of separating normal paraffins from naphtha through adsorption using 5A molecular sieves was studied with the purpose of optimizing the utilization of naphtha. The raw materials used in steam cracking and catalytic reforming processes could be allocated properly. During the adsorption process, the separation efficiency of the normal paraffins was above 99.9% with the purity of normal paraffins in the desorption oil exceeding 98.2%. With the use of the desorption oil as the feedstock of steam cracking, the ethylene yield increased from 29.7%--35.0% to 41.4%-49.2% compared to that of the naphtha in the existing plant under similar operation conditions. The potential aromatic content of the raffinate oil rose from 30.6% to 43.5% compared to that in naphtha. The research octane number of the raffinate oil reached more than 85 with an increase of 20 units compared to that of naphtha, so the raffinate oil is more suitable for use as a blending component for high-octane clean gasoline.     

PetroChina Faces Challenge from Domestie Petrochemical Sector

With China's entry into World Trade Organization,PetroChina is facing the unprecedented severe challenge fromits domestic counterparts in the chemicals sector, wherePetroChina is relatively weak in the production scale andfacilities. One of the key issues for PetroChina to solveurgently to reinforce its profit-makng capability rapidly isto boost the competitiveness of its ethylene facilities.Currently, PetroChina has seven sets of ethylene units witha total annual production capacity of 1.65 million tons. Theunits are usually small in the scale except for those at JilinPetrochemical Company and Daqing PetrochemicalCompany.Taking advantage of oil refining integration The enterprises with the ethylene units are usually ownedwith a certain scale of oil refining capacity. PetroChina hasa great potential to tap in the efforts to make use of the oilrefining and chemical integration for optimization of rawmaterials and reciprocation of their respective advantages.PetroChina should make comprehensive use of dry     

Calculating single layer production contribution of heavy oil commingled wells by analysis of aromatic parameters in whole-oil GC-MS

Traditional fluid production profile logging is not usually suitable for heavy-viscous crude oil wells.Biodegradation of heavy oil can lead to the loss of n-alkanes,and the use of chromatogram fingerprint techniques in studying the production contributions of single layers in heavy oil commingled wells has limitations.However,aromatic compounds are relatively well preserved.We took the heavy oil commingled wells of small layers NG55 and NG61 in the ninth area of the Gudong oil field as examples.Based on the principle of chromatography,the whole-oil GC-MS was used,and the aromatic parameters which have a strongly linear relationship with the ratio of mixed two end member oils were verified and selected in laboratory.Studies showed that the ratio of （1,4,6-＋ 2,3,6-trimethylnaphthalene） to 1,2,5-trimethylnaphthalene has a strongly linear relationship with the ratio of the mixed two end member oils （R2=0.992）.The oil contributions from single layers NG55 and NG61 in six commingled heavy oil wells were calculated using established charts and this relationship.The calculated results are consistent with the results of long period dynamic monitoring and logging interpretation in the study area and can provide a scientific basis for monitoring production performance and hierarchical management of reservoirs.The study provides a new geochemical method for calculation of the contributions of single layers in heavy oil commingled wells when conventional fluid production profile logging is not suitable.     

Study on Lumped Kinetic Model for FDFCC Ⅱ. Validation and Prediction of Model

On the basis of formulating the 9-lump kinetic model for gasoline catalytic upgrading and the 12- lump kinetic model for heavy oil FCC, this paper is aimed at development of a combined kinetic model for a typical FDFCC process after analyzing the coupled relationship and combination of these two models. The model is also verified by using commercial data, the results of which showed that the model can better predict the product yields and their quality, with the relative errors between the main products of the unit and commercial data being less than five percent. Furthermore, the combined model is used to predict and optimize the operating conditions for gasoline riser and heavy oil riser in FDFCC. So this paper can offer some guidance for the processing of FDFCC and is instructive to model research and development of such multi-reactor process and combined process.     

Kinetics and mechanisms of the catalytic thermal cracking of asphaltenes adsorbed on supported nanoparticles

The production of heavy and extra-heavy oil is challenging because of the rheological properties that crude oil presents due to its high asphaltene content. The upgrading and recovery processes of these unconventional oils are typically water and energy intensive, which makes such processes costly and environmentally unfriendly. Nanoparticle catalysts could be used to enhance the upgrading and recovery of heavy oil under both in situ and ex situ conditions. In this study, the effect of the Ni-Pd nanocatalysts supported on fumed silica nanoparticles on post-adsorption catalytic thermal cracking of n-C7 asphaltenes was investigated using a thermogravimetric analyzer coupled with FTIR. The performance of catalytic thermal cracking of n-C7 asphaltenes in the presence of NiO and PdO supported on fumed silica nanoparticles was better than on the fumed silica support alone. For a fixed amount of adsorbed n-C7 asphaltenes (0.2 mg/m2), bimetallic nanoparticles showed better catalytic behavior than monometallic nanoparticles, confirming their synergistic effects. The corrected Ozawa– Flynn–Wall equation (OFW) was used to estimate the effective activation energies of the catalytic process. The mechanism function, kinetic parameters, and transition state thermodynamic functions for the thermal cracking process of n-C7 asphaltenes in the presence and absence of nanoparticles are investigated.     

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.     

Study on Producing Heavy Paving Asphalt

The highly viscous crude oil from Shuguang No.1 zone of Liaohe oifield features high density,high viscosity and low wax content.It contains no gasoline fraction and its diesel oil fraction yiled is only 7.19%,which belongs to the low sulfur naphthenic stocks crude oil.Its heavy fraction is not suited for producing lubricating oil.Its heavy oil,whick contains more resins nd asphaltens and less wax,is not an ideal feedstock for catalytic cracking ,but is the ideal raw material for producing high-grade paving asphalt.Now this highy viscous crude oil is used as fuel oil after being emulsified in Liaohe oilfield,but its viscosity is so hight tha it cannot be atomized uniformly and burned completely,resuting not only in waste of oil resource but also in reduction of economical benefit.To make full use of this oil resource and alleviate the shortfall of high grade paving asphalt in China,various brands of asphal meeting Q/SHR003-1998 and ESSO specifications were developed by blending vaceuum residue of the said oil and a blending compo-net which are rich in aromatics and deficient in wax.The impct of blending component on proerties of blended ashalt has been investigated and road perfomances of these blended asphalts were studied.The labroatory test results show that the blended asphalts have good road performance and antiaging property.     

高硫含量原油加工

高硫含量原油加工路线的实质，主要是指常压渣油或减压渣油的加工方案。渣油加工有脱碳工艺、加氢工艺及沥青气化工艺。作者结合国内实际情况，重点介绍及推荐了沥青生产、减粘、延迟焦化、渣油加氢脱硫、溶剂脱沥青、沥青造气等渣油加工工艺，以及选择加氢裂化工艺的思路和原则。     

采用组合工艺提高辽河减压渣油轻油收率

以辽河减压渣油为原料,采用C5为溶剂,在压力4.0~7.0 MPa、剂油质量比4:1及温度160/180 ℃的条件下进行深度溶剂脱沥青试验,残炭降低率50%左右,90%以上的沥青质得到脱除,并富集到脱油沥青中。采用溶剂脱沥青-脱沥青油催化裂化-沥青残渣焦化组合工艺加工辽河减压渣油的研究结果表明：随溶剂脱沥青压力的提高,脱沥青油的收率增加,压力为7.0 MPa时,总脱沥青油收率达到74.22%,沥青残渣收率明显降低;轻、重脱沥青油催化裂化的平均液化气＋轻油收率分别为25.74%及12.72%,沥青残渣焦化的液化气＋轻油收率均值为7.17%。采用组合工艺技术,辽河减压渣油的液化气＋轻油收率较减压渣油直接焦化提高了4.06 百分点。     

溶剂脱沥青-焦化联合提高重质油综合液收实验研究

采用两种不同的减压渣油,对比分析了减压渣油直接焦化与溶剂脱沥青-焦化联合工艺实验,实验结果表明：采用溶剂脱沥青-焦化联合工艺,可以提高减压渣油的综合液收,减压渣油丙烷脱沥青-焦化联合工艺相对于直接焦化工艺液收提高9.61百分点;减压渣油丁烷脱沥青-焦化联合工艺相对于直接焦化工艺液收提高14.28百分点。     

Refining Tahe Heavy Crude Oil to Increase Light Product Yield

Traditional processing technology is not suitable for Tahe crude oil due to its low light distillate yield and poor quality. A new process, atmospheric flash evaporation-solvent deasphalting combined process, was put forward. The appropriate operating conditions of solvent deasphalting process were as follows: iso-pentane solvent, temperature of 175°C, pressure of 3.7MPa, solvent volume ratio of 5.0. Compared with atmospheric distillation-delayed coking process, total liquid product yield by new process could reach 78.77%, increasing by 9.47%. The quality of deasphalting oil met the feed requirements for catalytic cracking and de-oiled asphalt could be used as asphalt mixture additives.     

减压渣油掺炼催化裂化油浆丁烷脱沥青—糠醛精制组合工艺研究

摘要 以减压渣油、催化油浆为原料，在实验室开展了减压渣油掺炼催化裂化油浆溶剂脱沥青—糠醛精制组合工艺的研究工作。结果表明，新疆混合原油的减压渣油中掺入40％的催化裂化油浆，在适宜条件下经丁烷溶剂脱沥青可以得到合格的重交通道路沥青产品，脱沥青油在适宜条件下经糠醛精制后，其精制油具有更好的催化裂化性能，抽出油可以作为芳香烃型橡胶填充油的原料。此工艺为催化裂化装置外甩油浆的合理利用开辟了一条新的途径。     

应对高硫劣质原油的炼油总工艺流程设计

针对加工高硫劣质原油的发展模式,总结了延迟焦化＋循环流化床（CFB）锅炉、渣油加氢＋重油催化裂化以及溶剂脱沥青＋IGCC等三种成熟的炼油总工艺流程,分析了各流程的局限性。在炼油总工艺流程设计中,对炼油厂大型化和原油来源多样性的矛盾、加工非常规超重质原油、炼油厂多产汽油和提供化工轻油的矛盾、生产低硫产品以及油煤一体化的发展等问题提出了可行的思路和建议。     

渣油与废道路沥青共延迟焦化效果研究

利用由结构导向集总新方法构建的延迟焦化动力学模型计算了渣油掺炼废道路沥青的共焦化效果。结果表明,废道路沥青能够作为延迟焦化掺炼原料。小试试验表明,在470 ℃,0.15 MPa,零循环比条件下,80%渣油和20%废道路沥青共焦化比80%渣油焦化气体收率增加2.3百分点,液体收率提高2.91百分点,焦炭收率增加14.79百分点。通过焦化产物性质对比和经济性估算证实,废道路沥青作为延迟焦化掺炼原料是其再利用的一条新途径。     

渣油加工技术现状及发展趋势分析

目前,世界范围内增产的石油将主要是重质原油及重质合成油,炼油企业正面临着原料重质化和劣质化、产品轻质化和清洁化、炼制过程清洁化和低碳化的压力,需要尽快提升重油转化加工水平,提升重油轻质化的转化效率。以脱碳、加氢两种石油炼制技术路线为核心,分析了减黏裂化、溶剂脱沥青、延迟焦化、渣油催化裂化、渣油加氢等各种技术的现状及技术进展,并评价了影响渣油加工工艺选择的技术经济因素。延迟焦化技术将依然是渣油加工的主要技术手段之一,但是其经济性和环境表现略差;沸腾床、浆态床加氢技术将在渣油加工技术中承担越来越重要的角色,但在原料适应性和转化深度、催化剂寿命和消耗等方面还有待进一步提高;渣油加工组合工艺因能充分发挥各种渣油加工技术的组合优势,在实际生产中应优先加以考虑。     

掺炼丙脱沥青对焦化装置安全运行及产品的影响

中国石油天然气股份有限公司独山子石化分公司延迟焦化装置丙脱沥青掺炼比例的上升,使焦化原料的粘度和残炭升高,轻质油收率下降,焦炭收率上升。而更为严重的是：生产出的焦炭产品是弹丸焦,焦化蜡油残炭大幅超标。以上问题的出现,严重影响了焦化装置的安全运行,如严重影响冷焦和除焦操作的安全;关键机泵封油的密封效果差或可能中断;关键部位结焦;原料泵可能抽空等。针对存在的问题,分析了原因并提出了相应措施和建议。     

大型油厂零渣油加工方案的选择

加工高硫原油使炼油工业面临含硫渣油、沥青和焦炭产品最终不可避免的硫排放问题。国内大型炼油厂在加工进口原料时,所产生的残渣要进一步加工利用。论述了可选择的三个非加氯方案。气化（IGCC）方案是目前国外普遍采用的利用炼油厂废渣造气的渣油加工路线,延迟焦化加循环流化床锅炉和重交通道路沥青加硬沥青水浆两个方案对加工高硫原油的国内大型炼油厂具有现实的指导意义。可利用这些方案将销路不好的高硫渣油、沥青和焦碳转化为具有一定附加值的产品如电、蒸汽等。