特超稠油黏度的影响因素研究

为推动稠油降黏技术的发展,获得稠油黏度的控制因素,以塔河、轮古油田的15 个稠油样为研究对象,考察了稠油的黏温关系,进行了饱和分、芳香分、胶质、沥青质（SARA）四组分分离和元素组成分析并将其与黏度进行关联分析,研究了水热催化裂解法对稠油的降黏作用效果。研究结果表明,稠油中存在结构黏度,黏温关系较好地符合Arrhenius 方程。稠油黏度与组成有关,随稠油中饱和分、芳香分、胶质含量增加,稠油黏度降低;随沥青质含量增多,稠油黏度呈近似指数关系升高;随胶体稳定性参数（胶质/沥青质量比）增大,稠油黏度降低并呈近似指数关系;稠油黏度与N、Ni 含量正相关,与S、V含量关系不明显;氢碳原子比越小、芳碳率越高,稠油黏度越大。对LG-01 稠油进行水热裂解降黏实验结果表明,反应后油样的黏度变化与组成变化相对应,在80℃的黏度由反应前的34965 mPa·s 变为12165～295858 mPa·s,水热反应后对应的沥青质含量为21.50%～29.22%,胶体稳定性参数为1.19～0.63,氢碳原子比依次降低,杂原子S、N含量依次增加。图12 表3参16     

胜利稠油水热裂解过程中沥青质结构特征的变化分析

为了阐明在双亲性催化剂的条件下,在250 ℃和280 ℃下稠油水热裂解反应对稠油沥青质分子结构及稠 油黏度的影响,以胜利稠油为研究对象,使用C₁₂BSNi为催化剂,通过使用FT-IR 和1HNMR等手段分析水热裂解 反应前后沥青质分子结构的变化。研究结果表明,稠油在250 ℃下发生水热裂解反应后,黏度大幅降低,降黏率 可达到60.4%,但随着反应温度升高到280 ℃时,反应后的降黏率降至53.8%。随水热裂解反应温度从250 ℃升 高到280 ℃,稠油沥青质分子平均侧链长度逐渐减小,然而芳香度不断增加,芳环数量增多,说明沥青质分子发 生了自由基缩合反应,沥青质平均分子结构变大,导致降黏率相对减小;此外,沥青质分子在反应过程中发生一 系列的断键反应,导致其空间位阻减小,且沥青质分子单元片层越小越容易发生堆积。通过SEM观察到,随温 度升高,沥青质的孔道逐渐变大并且更加密集,但表面聚集颗粒变大。本文研究对稠油水热裂解反应操作条件 的优化有重要的指导意义。     

稠油地面催化改质降黏技术的研究进展

综述了稠油地面催化改质、催化水热裂解改质、离子液体改质和物理场辅助催化改质降黏技术的研究进展。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介绍,分析了稠油水热裂解涉及的催化裂解化学反应及其机理。     

磺化型有机金属催化剂在稠油降黏改质中的应用

制备了3种磺化型有机酸金属催化剂,用高温高压反应釜进行了稠油的催化降黏实验,筛选出了最佳催化剂和最佳降黏条件。结果表明,磺化型有机酸铁催化剂的降黏效果最佳,当稠油量为250g时,加入1g该催化剂,加入油层水量为m(油层水)∶m(稠油)=30%,在220℃反应24h,辽河稠油黏度从81 400mPa·s降至3 000mPa·s,降黏率达96.31%。检测了催化降黏前后稠油四组分及不凝气体产物:饱和分含量提高7.5%、芳香分含量提高3.2%,胶质含量降低8.2%,沥青质含量降低2.5%;检测出不凝气相产物含有甲烷、烯烃和二氧化碳等气体,符合稠油水热裂解降黏规律,证明由于催化改质降低了稠油的黏度。     

渤海稠油催化改质降黏实验*

为了探索海上稠油的热催化改质降黏技术的可行性,解决海上稠油的举升和集输问题,针对渤海西部某油田的稠油分析了稠油黏度与族组分关系,选择了PAS、FAS两种阴离子和Zn~(2+)、Cu~(2+)、Mn~(2+)、Fe~(3+)和Ni~(2+)5种阳离子组合共10种催化剂,进行催化改质降黏实验,对比了催化改质前后族组分的变化。研究结果表明:对于该渤海稠油来说,饱和烃和芳香烃含量越高黏度越低,饱和烃对稠油黏度影响明显大于芳香烃,胶质、沥青质含量越高,其黏度越大,沥青质对于该渤海稠油黏度影响略大于胶质,但由于稠油中胶质含量远大于沥青质含量,因此降低胶质含量是该渤海稠油催化改质的必然选择。PAS-Ni的催化降黏效果最好,可以使该渤海稠油黏度从2167 m Pa·s降至566 mPa·s,降黏率为73.88%,PAS-Fe的改质效果次之,稠油黏度降至716 mPa·s,降黏率为66.96%。改质后稠油四组分分析结果表明,催化改质反应主要降低了胶质含量,增加了饱和分和芳香分含量,沥青质含量有小幅度增加。图4表2参13     

单家寺稠油催化水热裂解实验研究

实验考察了一种商品水溶性钼盐催化剂(代号A)和一种自制油溶性钼盐催化剂(代号B)对胜利单家寺稠油水热裂解的催化效能。实验稠油50℃黏度111.469 Pa.s,含S 0.42%,含胶质46.5%,含沥青质16.5%,H/C=1.68。在加水量10%、水热裂解温度260℃、时间24小时条件下,催化剂B在加量0.05%~0.15%范围降黏率维持高值,加量0.08%时最高,催化剂A在加量0.2%时降黏率有明显的峰值;0.08%催化剂B的催化效能明显好于0.2%催化剂A,裂解后稠油的降黏率、含硫、含胶质、含沥青质和H/C值分别为71.2%和62.3%,0.23%和0.29%,26.3%和32.6%,10.3%和11.4%,1.70和1.69;当加水量增大时(≥5%),0.2%催化剂A的催化效能增大,加水量20%时达到最佳,此时水热裂解后稠油的降黏率、含胶质、含沥青质分别为65.8%,27.2%、10.6%;催化剂B在加水量5%时催化效能差,加水量在10%~50%范围时催化效能基本不变。根据不同温度下沥青质含量和降黏率随水热裂解时间变化,在0.08%催化剂B存在下水热裂解速率和程度均随温度升高而增大,最后均趋于平衡,280℃、12小时的降黏率为72%左右,240℃、24小时为64%左右,180℃、24小时为20%左右。用作稠油水热裂解催化剂的钼盐,油溶性的优于水溶性的。图3表2参5。     

自生热降黏剂的优化及原油降黏解堵性能

为了解决稠油黏度大而难开采问题,采用自生热降黏解堵工艺技术,利用化学生热剂和催化水热裂解的协同作用,开采近井地带富含沥青质的稠油.结果表明:优化开发的自生热降黏解堵体系,以浓度为5 mol/L的NaNO2和NH4 Cl为产热剂、质量浓度为10 g/L的硼氢化钠为产氢剂、质量浓度为15 g/L的水热裂解催化剂为添加剂,体...     

注蒸汽条件下稠油催化改质降黏实验研究

以自制的油溶性有机镍盐作为催化剂进行稠油水热裂解反应.考察了催化剂加量、反应温度、反应时间和加水量对催化水热裂解反应前后稠油黏度、族组成的影响.催化水热裂解反应的最佳条件为:反应温度240℃,反应时问24 h,加水量30％,催化剂质量分数0.1％.对反应前后稠油的元素分析结果表明,与水热裂解反应相比,加入催化剂后的稠油黏度由11000 mPa·s降至3414 mPa·s,沥青质、胶质含量分别降低1.7％、1.6％,芳香分、饱和分含量分别增加0.8％、2.5％,稠油中C含量降低,H含量增加,H、C原子数比提高,而杂原子与C的原子数比降低.图4表6参8     

稠油的甲酸供氢催化水热裂解改质实验研究

在0.3升高温高压反应釜中,以甲酸为供氢体、以油溶性有机镍盐为催化剂,研究了辽河稠油的水热裂解反应,考察了水热裂解前后稠油的黏度、族组成及硫含量变化.所用催化剂为绿色黏稠液体,nD(25℃)=1.4737,由环烷酸和硫酸镍制成,介绍了制备方法.所用稠油黏度的温敏性强,50℃、44.11/s黏度为3716 mPa·s.水热裂解反应条件如下:油水质量比4∶1,催化剂加量以稠油质量计为0.1%,反应温度280℃,时间24 h,初始充氮压力8.1MPa.催化水热裂解的降黏率为64.69%,使饱和烃、芳香烃由24.32%、36.89%增至26.12%、38.08%,使胶质、沥青质及硫含量由30.27%、8.52%及0.5650%减至28.27%、7.53%及0.3365%;加入1%～7%甲酸使降黏率增至69.16%～87.02%,使饱和烃、芳香烃增至27.73%～31.12%、39.68%～41.26%,使胶质、沥青质及硫含量减至26.29%～24.12%、6.66%～3.50%及0.3095%～0.0742%.红外光谱分析结果表明,稠油组分在供氢催化水热裂解中发生了脱羧反应且芳环数减少.讨论了甲酸作为供氢体在稠油催化水热裂解中的作用及其机理.图4表2参8.     

注蒸汽条件下稠油催化改质降黏实验

利用高温高压反应釜研究了自制油溶性有机镍盐作为催化剂的稠油水热裂解反应,考察了催化剂的加入量、反应温度、反应时间和加水量对催化水热裂解反应前后稠油黏度、族组成的影响,优选出最佳改质降黏反应条件,在此条件基础上,对改质降黏反应前后稠油元素进行分析。结果表明,与未添加催化剂的相比,在反应温度为240℃、加水量30%的体系中,添加0.1%的过渡金属有机酸镍催化剂,反应24 h 后稠油的黏度下降明显,沥青质含量下降1.4%,胶质含量下降5.0%,芳香分含量增加3.5%,饱和分含量增加2.9%.     

胜利含盐特超稠油水热改质降粘研究

针对胜利油田特超稠油因黏度过高而难以集输的问题,研究水热处理对其改质降黏效果,探讨水热处理在稠油集输过程中应用的可行性。通过水热反应工艺参数的调变及黏度、元素组成、四组分组成、馏分分布、盐含量等分析,发现水热处理能有效降低胜利油田特超稠油的黏度,水热处理后稠油的黏度主要由裂化转化率决定;通过添加催化剂,改变水热处理温度和水热处理时间,可以有效控制稠油的裂化转化率。加入合适的催化剂,提高水热反应温度,延长反应时间,皆利于提高稠油的裂化转化率。加入催化剂,可降低水热反应温度和缩短反应时间。多孔炭质催化剂A存在下,反应温度330 ℃,反应时间60 min时,胜利特超稠油的裂化转化率高达30.11%,黏度由水热反应前的52 410 mPa·s降低至水热反应后的1 536 mPa·s,降黏率高达97.07%。水热改质后油品的流动性较好,可作为普通原油进行集输,表明水热处理在稠油集输过程中具有良好的应用前景。     

低硫超稠油水热裂解反应的研究

研究了反应温度、反应时间、加水量对辽河曙一区超稠油水热裂解反应的影响。结果表明，随反应温度、反应时间和添加物料中水油比的增加，水热裂解反应后油样的饱和份、芳香份的含量逐渐增大，沥青质、胶质含量逐渐减小；在反应温度为240℃、反应时间24小时、添加的水油质量比为0.5时，超稠油水热裂解反应基本完成，50℃粘度由超稠油原样的147.5Pa·s降低到115.4Pa·s，平均相对分子量由超稠油原样的674降低到550。由此可知，含硫量仅为0.45m%的辽河曙一区超稠油能够通过水热裂解反应降低其粘度，实现降粘开采。     

Study of catalytic aquathermolysis of heavy oil in the presence of a hydrogen donor

We have studied the effect of catalytic aquathermolysis of heavy oil in the presence of a hydrogen donor (formic acid) on the viscosity of Liaohe extra-heavy oil. The paraffinic/naphthenic and aromatic hydrocarbon content of the oil as well as the H:C ratio of the oil increase after aquathermolysis in the presence of a hydrogen donor, while the sulfur, resin, and asphaltene content decreases dramatically. We use the thermogravimetric method to show that with aquathermolysis in the presence of formic acid, a substantial portion of the asphaltenes in the heavy oil is converted to paraffins. Accelerating the aquathermolysis reaction results in a synergistic effect between the catalyst and the hydrogen donor.     

Influences on the Aquathermolysis of Heavy Oil Catalyzed by Two Catalysts With Different Ligands

The dodecyl benzene sulfonic iron and p-toluenesulfonic iron were prepared and used in catalytic aquathermolysis of Xinjiang extra-heavy oil (8.5 × 10⁴ mPa·s at 50°C). The same and different influences on the aquathermolysis of heavy oil catalyzed by them were studied in depth and compared. The compositions and structure of oil sample before and after reaction were analyzed by element analysis instrument, ¹H nuclear magnetic resonance and gas chromatography-mass spectrometry. The results showed that the p-toluenesulfonic iron exhibit better viscosity reduction effect and more significant changes for the oil sample than the dodecyl benzene sulfonic iron.     

The use of a tartaric–Co(II) complex in the catalytic aquathermolysis of heavy oil

A tartaric–Co(II) complex was synthesized and then used in aquathermolysis of heavy oil as a catalyst at relatively low temperature, 180°C. The effects of water amount and catalyst concentration on aquathermolysis were investigated in this work. The crude oil before and after aquathermolysis was fully characterized, and the mechanism of viscosity reduction was discussed at last. The results show that heavy oil can undergo aquathermolysis in the present of water and the tartaric–Co(II) complex at low temperature. Besides, the catalytic aquathermolysis could not only decrease the viscosity of heavy oil, but also remove some heteroatoms, finally making the flow properties better and the quality upgraded.     

Catalytic Aquathermolysis of Heavy Oil With Oil-soluble Multicomponent Acrylic Copolymers Combined With Cu2+

A kind of oil-soluble multicomponent acrylic copolymer combined with Cu²⁺ was synthesized and used for catalytic aquathermolysis of heavy oil. This work showed this copper-bearing copolymer led to 84.52% viscosity reduction for the Lukeqin heavy oil at 513.15 K, and converted 10.01% of the resin fraction and 2.85% of the asphaltene fraction into light oil content. After aquathermolysis with this catalyst, some parts of the long-chain saturated hydrocarbons were broken into short-chain ones, and the aromaticity and aromaticity condensation of the resin and asphaltene decreased.     

Catalytic aquathermolysis of heavy oil by coordination complex at relatively low temperature

A series of Mannich base-transition metal coordination complex was synthesized and used for the catalytic aquathermolysis of heavy oil, among which we found that the Ni(II) complex is the most effective one. After reacted under a relative low temperature, 180°C, for 24 h, the viscosity of the heavy oil was decreased by 75.2% using 0.5 wt % Ni(II) complex. The results showed that the content of resin and asphaltenes was decreased, while the content of saturate and aromatic were increased after aquathermolysis reaction. Besides, the catalytic aquathermolysis could both decrease the viscosity of heavy oil, and reduce the content of heteroatoms, resulting in flow properties enhanced and the quality upgraded.     

塔河稠油催化降黏机理研究

通过对比分析催化降黏前后塔河稠油主要性质及组成变化,并结合以十二硫醇和辛硫醚为模型化合物的催化降黏反应,探讨塔河稠油催化降黏机理。结果表明：塔河稠油经催化降黏后,降黏率可达65.8%,比热降黏率高32百分点;且降黏后重质组分减少,轻质组分增加,表观相对分子质量降低,硫含量减少;模型化合物十二硫醇和辛硫醚在催化降黏条件下发生了C-S,S-H,C-C,S-S的断裂反应。塔河稠油经催化降黏处理后黏度降低的主要原因是克服了引起胶质、沥青质团聚的氢键、配位键等弱作用力,同时部分键能较弱的化学键如C-S,C-O,C-C等发生断裂,导致稠油分子聚集体变小,从而改变稠油缔合状态,实现不可逆降黏。     

Aquathermolysis of heavy crude oil with ferric oleate catalyst

Oil-soluble catalysts could be of special significance for reducing the viscosity of heavy crude oil, because of their good dispersion in crude oil and high catalytic efficiency toward aquathermolysis. Ferric oleate was synthesized and applied as catalyst in the aquathermolysis reaction of Shengli heavy oil. It was found that ferric oleate was more efficient for heavy oil cracking than Co and Ni oleates. Besides, it was superior to oleic acid and inorganic ferric nitrate and achieved the highest viscosity reduction rate of up to 86.1%. In addition, the changes in the components of Shengli heavy oil before and after aquathermolysis were investigated by elemental analysis, Fourier transform infrared spectrometry, and ¹H nuclear magnetic resonance spectroscopy. Results indicated that ferric oleate contributed to a significant increase in the content of light components and decrease in the content of resin, N and S. The as-prepared ferric oleate showed good activity for reducing the viscosity and improving the quality of the heavy crude oil, showing promising application potential in aquathermolysis of heavy crude oil.     

稠油水热裂解反应催化剂适应性研究

以辽河油田的稠油为原料,环烷酸钴、环烷酸镍、柠檬酸钴或柠檬酸镍为催化剂,研究了稠油水热裂解反应催化剂在地层中的适应性。结果表明,催化剂与地层水的配伍性良好,不会对地层造成伤害。以柠檬酸钴为催化剂,稠油催化改质的反应条件为:温度240℃,时间24 h,稠油100 g,地层水30 g,催化剂摩尔浓度9×10-3mol/L;在此条件下,稠油降黏率最高(达到66.82%)。外加催化剂与油藏矿物具有协同效应,催化剂的加入能够强化矿物催化的稠油水热裂解反应。