催化裂解降粘技术在孤东油田的应用

稠油蒸汽吞吐开采过程中,普遍存在热利用率低、采收率不高等问题,大量研究结果表明,在注蒸汽开采稠油过程中,稠油与水蒸气之间可以发生开环、脱硫等一系列化学反应即水热裂解反应,在催化剂的化学辅助作用下,可以加大稠油的水热裂解反应的程度,从而大大降低稠油水热裂解反应后的粘度,改善稠油的品质,可以解决稠油常规注蒸汽热采所无法解决的问题.     

蒸汽吞吐渗流规律与催化裂解降粘机理的研究

稠油通常是指粘度高,相对密度大,胶质和沥青质含量高的原油。稠油在油层中粘度高,流动阻力大,用常规技术难以经济有效地开发。最近十几年,国内外通常采用以热采技术为主的稠油开采技术,使稠油产量不断增加。蒸汽吞吐是一种相对简单和成熟的注蒸汽开采稠油的技术。蒸汽吞吐的机理主要是加热近井地带原油,使之粘度降低,当生产压力下降时,为地层束缚水和蒸汽的闪蒸提供气体驱动力。催化剂在稠油水热裂解反应中起着极其重要的作用,也是水热裂解开采稠油技术的关键技术之一。目前主要的学术观点认为,在稠油水热裂解反应中催化剂的主要作用在于降低稠油中有机硫化物等组分的裂解反应的活化能,使之易于发生,同时为水热裂解反应提供氢离子并促进产生的氢或阻聚剂中的氢向稠油中的某些结构转移,进而起到加速稠油水热裂解反应的作用。本文主要对蒸汽吞吐稠油的渗流规律、催化裂解的降粘机理以及改质稠油的有杆泵举升进行了初步研究。     

超声波协同催化剂低温裂解超稠油实验研究

以超声波协同催化剂裂解超稠油,研究了催化剂浓度、反应温度、时间和加水量对超稠油裂解效果的影响,分析了超稠油处理前后的族组成及平均分子量变化。结果表明,超声协同催化剂裂解超稠油最佳反应条件为:催化剂浓度0.3%,反应温度150℃,时间10 h和加水量50%。与催化水热裂解相比,超声辅助催化水热裂解使稠油分子质量进一步减小,轻烃含量增加,重质组分含量减少;超声波与催化剂间具有协同效应,超声波作用可促进稠油催化水热裂解反应,提高稠油裂解效果,降低反应条件。     

蒸汽和金属盐作用下稠油粘度变化研究

探讨了在注蒸汽条件下,稠油的粘度随蒸汽温度、时间的变化规律。研究结果表明,在注蒸汽开采条件下,辽河稠油可以发生水热裂解反应。金属盐的存在,可以加速稠油的水热裂解反应,从而导致粘度降低,这为实现井下催化降粘开采稠油、就地提高稠油质量提供了理论依据。     

注蒸汽条件下供氢催化改质稠油及其沥青质热分解性质

利用CWYF-Ⅰ型高压反应釜模拟热采条件下,以甲酸作为供氢体.以自制的油溶性有机镍盐为催化剂进行的稠油水热裂解反应.考察了供氢体的加入对催化水热裂解反应前后稠油黏度、族组成及硫含量的影响,并采用TG-DTA分析法对供氢催化改质反应前后稠油中沥青质的热转化行为进行了分析.结果表明,随着加入供氢体质量分数增加,供氢催化水热裂解后稠油降黏率增大,饱和烃、芳香烃含量增加,胶质,沥青质含量降低,同时硫含量下降.供氢催化水热裂解反应后的稠油中沥青质TG-DTA曲线分析表明,供氢催化水热裂解反应后稠油中沥青质失重量高于催化水热裂解反应前稠油中含有的沥青质的失重量.经过供氢催化水热裂解反应,稠油中沥青质的稳定性下降.     

蒸汽驱热波耦合辅助催化裂解降粘技术及先导试验

针对水热催化裂解反应发生效率低,有效反应范围有限等问题,以WN采油厂稠油为例,利用具有多活性点的水热裂解催化剂,在低频谐振波的协同作用下,优化了振动降粘参数,并在动态模拟条件下研究了蒸汽驱热波耦合催化裂解的效果,并进行了矿场先导试验。结果表明:蒸汽驱热波耦合催化裂解技术降低了反应的最低反应温度,提高了稠油的降粘效果。先导试验3口井,累计增油1644t,油汽比提高0.28,油井峰值产油量明显提高,稳产时期明显延长,该技术在稠油的热采过程中具有较强的推广价值。     

稠油水热催化裂解机理的研究进展

在论述了催化裂解开采稠油对能源保证的重要性意义上,从催化水热裂解的理论机理研究方面对水热裂解催化降黏方法进行了全面介绍。对稠油水热裂解发生涉及的催化裂解化学反应及其机理作了分析讨论。同时对近年来的主要研究使用的三类催化剂做了重点介绍,着重分析了其催化降黏机理。     

油溶性纳米Fe_3O_4催化稠油水热裂解降黏

通过低温双相法合成了油溶性纳米Fe_3O_4粒子,并将其应用于催化新疆克拉玛依稠油的水热裂解降黏实验。结果表明,该催化剂能有效降低稠油黏度。在240℃水热条件下,使用油溶性纳米Fe_3O_4催化剂,当催化剂加入量为稠油质量的0.3%,水加入量为稠油质量的25%时,反应24 h后稠油降黏率达到60.3%。对处理前后稠油的各组分进行了四组分分析、红外、元素分析等,发现稠油胶质含量下降10.32%,沥青质含量下降23.43%。     

稠油催化改质技术研究

综述了注空气催化氧化和注水蒸汽水热裂解两种技术的降粘机理及国内外研究进展,通过对稠油催化改质、改变稠油的组分、降低沥青质和胶质总的相对分子量以实现降粘。其中空气催化氧化技术包括低温氧化和高温氧化两个主要过程:实现芳环破裂,大分子断裂。从水溶性催化剂、油溶性催化剂到微乳催化剂研究;水热裂解中水蒸汽和供氢剂的协同可使稠油中C-S、C-O、C-N键断裂更为充分,同时综述了水热裂解的现场应用和催化剂的进展。     

稠油水热裂解中固体催化剂的研究进展

综述了稠油固体催化降粘催化剂开发所取得的进展和基本问题。稠油水热裂解反应中,最合适的催化剂是那些含有强活性位点的催化剂,它们可以有效地破坏胶质和沥青质中的C—C、C—S、C—O和其他相关化学键,使得饱和烃和轻质芳香烃的浓度增加,从而达到稠油降粘的目的。天然沸石,杂多酸,改性氧化锆,Mo、W、Co和Ni的合金,Cu和Fe的纳米氧化物,纳米Fe颗粒,疏水性沸石,W和Mo的碳化物等物质作为催化剂用于水热裂解反应也被大量报道。同时论述了这些固体催化剂的水热稳定性,说明了固体催化剂在水热裂解反应中的优越性。但是这些所有提到的催化剂,都需要进一步研究探索最佳的催化剂合成方式、操作条件和实际反应机理,才能真正投入到油田的使用推广中。     

Kinetic study of crude oil-to-chemicals via steam-enhanced catalytic cracking in a fixed-bed reactor

This study presents new experimental results on the direct conversion of crude oil to chemicals via steam-enhanced catalytic cracking. We have organized the experimental results with a kinetics model using crude oil and steam co-feed in a fixed-bed flow reactor at reaction temperatures of 625, 650, and 675°C over the Ce-Fe/ZSM-5 catalyst. The model let us find optimum conditions for crude oil conversion, and the order of the steam cracking reaction was 2.0 for heavy oil fractions and 1.0 for light oil fractions. The estimated activation energies for the steam cracking reactions ranged between 20 and 200 kJ/mol. Interestingly, the results from kinetic modelling helped in identifying a maximum yield of light olefins at an optimized residence time in the reactor at each temperature level. An equal propylene and ethylene yield was observed between 650 and 670°C, indicating a transition from dominating catalytic cracking at a lower temperature to a dominating thermal cracking at a higher temperature. The results illustrate that steam-enhanced catalytic cracking can be utilized to effectively convert crude oil into basic chemicals (52.1% C2-C4 light olefins and naphtha) at a moderate severity (650°C) as compared to the conventional high-temperature steam cracking process.     

催化裂解制低碳烯烃技术研究进展

综述了目前国内外以轻烃到重油范围内为原料的催化裂解工艺技术,着重介绍了我国有代表性的研究成果DCC、CPP及HCC工艺。而重油催化裂解更适合于我国国情,并指出在研制与工艺技术相匹配的高效新型催化剂方面,找到催化剂酸强度、孔道分布、金属含量和活性组分含量与催化裂解活性之间的关系,为催化裂解制低碳烯烃工艺技术能够全面实行工业化奠定更坚实的基础。     

稠油注空气催化氧化采油催化剂的制备与评价

注空气催化氧化采油技术是一项提高稠油采收率的创新技术,因其气源丰富、成本低,越来越受到人们关注。该文针对SZ36-1稠油,制备了5种油溶性催化氧化催化剂——过渡金属环烷酸盐,并加以筛选,得到环烷酸铜催化效果最佳。对稠油注空气催化氧化条件进行了初步评价。在催化剂用量为原油质量的0.2%,反应温度100℃,反应时间3 d的条件下,稠油酸值从3.96 mg KOH/g上升至13.50 mg KOH/g,黏度由2.004 Pa.s上升到11.48 Pa.s,尾气中φ(O2)由21.0%降至10.0%。向氧化油中分别加入氧化油质量1.2%的助剂SW-1和质量分数40%的水,保温50℃搅拌,生成大量表面活性剂,形成O/W乳化油,黏度最终降至0.067 Pa.s,总降黏率达到96.66%。     

Kinetic studies on extra heavy crude oil upgrading using nanocatalysts by applying CFD techniques

Regarding the growth of global energy consumption and the paucity of light crude oil,extracting and using heavy and extra heavy crude oil has received much more attention,but the application of this kind ofoil is complicated due to its very high molecular weight.High viscosity and low flowability complicate the transportation of heavy and extra heavy crude oil.Accordingly,it is essential to reduce the viscosity of heavy and extra heavy crude oil through in-situ operations or immediate actions after extraction to reduce costs.Numerical simulations are influential methods,because they reduce calculation time and costs.In this study,the cracking of extra heavy crude oil using computational fluid dynamics is simulated,and a unique kinetic model is proposed based on experimental procedures to predict the behavior of extra heavy crude oil cracking reaction.Moreover,the hydrodynamics and heat transfer of the system and influence of nanocatalysts and temperature on the upgrading of crude oil are studied.The geometry of a reactor is produced using commercial software,and some experiments are performed to examine the validity and accuracy of the numerical results.The findings reveal that there is a good agreement between the numerical and experimental results.Furthermore,to investigate the main factors affecting the process,sensitivity analysis is adopted.Results show that type of catalyst and concentration of catalyst are the parameters that influence the viscosity reduction of extra heavy crude oil the most.The findings further revealed that when using a 25 nm SiO2 nanocatalyst,a maximum viscosity reduction of 98.67％ is observed at 623 K.Also,a catalyst concentration of 2.28wt％ is best for upgrading extra heavy crude oil.The results obtained through sensitivity analysis,simulation model,and experiments represent effectual information for the design and development of high performance upgrading processes for energy applications.     

Investigating the process of heavy crude oil steam cracking in the presence of dispersed catalysts. II: Investigating the effect of Ni-containing catalyst concentration on the yield and properties of products

The process of heavy crude oil (HCO) steam cracking under a batch regime at 425°C in the presence of Ni-containing nanodispersed catalyst (0.3–2.0 wt % with respect to Ni) is investigated. It is established that using this catalyst facilitates the upgrading of semi-synthetic oil produced from HCO: the Н: С ratio rises (in comparison to steam cracking with no catalyst), and the sulfur content and viscosity are reduced. The Н: С ratio in the liquid products grows slightly along with the catalyst content, but the yield of liquid products falls from 81 to 76% during the process with a simultaneous increase in the yield of coke and gaseous products (from 8 to 13 and from 2 to 4 wt %, respectively). Catalyst with coke residue is investigated by means of XRD and TEM. It is shown that nanosized particles of the Ni9S8 phase with sizes of 15–40 nm form from the catalyst precursor (Ni(NO₃)₂ · 6H₂O) under the process conditions. The selection and investigation of catalytic systems for heavy crude oil cracking in the presence of superheated steam, along with optimization of the process conditions, are required to further enhance the efficiency of the upgrading process.     

稠油降粘输送室内研究

应用注蒸汽开采稠油中的水热裂解反应及稠油的降粘机理,将它应用到稠油集输过程中,通过实验找出较好的催化剂,从当中得出一些结论,可能被油田使用。