轻质原油低温氧化动力学研究

为研究轻质油藏空气驱的可行性,建立低温氧化动力学模型。将空气注入油藏,原油与氧气会发生低温氧化反应,反应的难易程度由相应的动力学参数来描述。通过低温氧化实验,获得了不同条件下的氧化速率等数据,运用Arrhenius定律来计算反应中的活化能、预幂率指数等动力学参数。结果表明：压力越高,活化能越小,预幂率指数越大,越有利于反应的进行;不同油样的动力学参数也不同。     

稠油注空气低温催化氧化动力学实验

摘要：为提高埕北稠油油藏注空气采油过程的安全性,进行了注空气低温氧化实验,研究了温度和催化剂对稠油低温氧化过程的影响。基于Ａｒｒｈｅｎｉｕｓ 方程,确定出了稠油在催化和非催化条件下的反应动力学参数-反应级数、频率因子和反应活化能。实验结果表明,３ 种催化剂的催化活性由强到弱依次为ＺｎＬ、ＭｎＬ、ＦｅＬ,反应温度越高,稠油的耗氧速率越高。同非催化氧化相比,ＺｎＬ 催化氧化反应的反应级数由０ 级变为１ 级,反应活化能由９２􀆰 ３８５ ｋＪ／ ｍｏｌ 降至７７􀆰 ５７６ ｋＪ／ ｍｏｌ。ＺｎＬ 可显著提高稠油的耗氧速率,对保障注空气采油全过程的安全性具有重要意义。     

几种过渡金属化合物对沥青的催化氧化

以铁、钴、锰等过渡佥属的化合物作为催化剂，对沥青催化氧化。根据沥青的延度、针入度和软化点的变化．研究催化剂的种类和催化剂的加入量对沥青氧化的影响。     

轻质原油低温氧化动力学模型——以中原油田胡12块为例

针对中原油田胡12块油样,在组分分析的基础上,利用物质平衡定律确定了反应方程式,通过原油静态氧化实验,研究了油样在油藏温度和压力下的氧化过程,基于简化的Arrhenius方程,确定了氧化反应的活化能和反应速率常数,并用键能法确定了反应焓,从而建立了低温氧化动力学模型,为注空气油藏数值模拟提供了理论基础。低温氧化实验结果还表明,实验温度越高,生成的二氧化碳量越大,氧气消耗速率也越大,110℃时氧气的消耗速率为80％时的4倍,说明温度是影响低温氧化反应的重要因素。     

稠油注空气低温催化氧化技术适应性研究

稠油注空气低温催化氧化采油技术是集热采、Ｎ２ 驱、表面活性剂驱及稠油井下改质技术 于一体的稠油开采新技术,该技术成本低廉,可促进稠油改质和有效提高原油采收率。研究分 析了该技术的原油及油藏的适应性。结果表明,该技术对于普通稠油、特稠油、超稠油及海上 稠油样均具有较好的低温催化氧化性能,可应用于注蒸汽热采后的稠油老区、海上及难动用稠 油油藏。该技术在辽河油田的现场试验也取得了较好的效果。     

担载催化注空气低温氧化实验研究

以新杜1块储层为研究对象,筛选了8种担载催化材料,经过石英砂表面处理制成低温氧化实验岩心。通过常规岩心和担载催化岩心的空气与原油低温氧化实验,比较了反应前后空气组成和原油组分的变化。实验说明:有效的担载催化岩心可大大提高空气与原油的低温氧化反应速度,与常规岩心相比氧化反应速度可提高7倍多;低温氧化反应使长链的碳氢化合物部分氧化形成短链的碳氢化合物,加入催化剂后使发生断裂的碳链范围增大,生成的短碳链更加集中;通过担载催化材料的方法,可以大幅度提高注空气低温氧化的安全范围,为现场试验提供安全保障。     

注空气低温氧化工艺：轻质油藏提高采收率技术

本文描述了开采轻质油藏残余油的注空气提高采收率（IOR）工艺。与应用于重质油藏的注空气技术不同，轻质油藏主要关心的是通过原油和氧气之间的某种自然反应从注入空气中消除氧。重质油藏的火烧油层工艺是达到完全氧消耗和生成提高采收率热量的十分有效的反应途径。对于较深的轻质油藏，火烧油层是不必要的且不容易维持。更可能的是，所谓的低温氧化（LTO）将取得成功。本文调研了消耗氧的LTO反应的潜力、反应速度和反应途径。根据间歇（批量）反应器试验获得的试验数据建成了一个简化LTO反应模型。该模型对氧化管中的高压流动驱替试验是有效的。油藏规模的一系列模拟研究业已能够对工艺的灵敏度进行和采油的油层温度和热效应。与常规注空气（火烧油层）的一般了解相比，注空气LTO工艺在注入速度方面是灵活的，因是自发反应而很稳定（如果油层温度足够高），而且还是烃类、氮或二氧化碳的一种经济的替代品。它还能用于不适宜注水油层的二次采油。     

轻质油油藏注空气催化氧化技术效果评价

对ZJ油田轻质原油开展注空气氧化实验,考察了添加催化剂HS对氧化反应速率、总耗氧量及原油组分与黏度的影响。结果表明,加入催化剂后氧化反应速率及总耗氧量均增加5.75倍;ZJ轻质原油经过氧化后,C9~C13组分含量有所增加,C14~C36组分含量略有下降;饱和烃含量基本不变,芳烃含量下降近4个百分点,非烃和沥青质含量均增加近2个百分点,氧化后脱气原油的黏度略有增加。研究认为,可以将注空气催化氧化技术作为油田开发的储备技术。     

注空气轻质原油低温氧化油气组分变化研究

运用气相色谱、红外光谱等测试分析手段,对大庆油田油样低温氧化后气体组成和油样族组分组成变化规律的研究结果表明,反应后气体中氧气含量降低,同时生成一氧化碳、二氧化碳等气体,反应后油样中增加了羟基、羧基、醚键等官能团.油样族组分的变化与温度有关:150℃之前,主要是饱和烃、芳香烃与氧气发生低温氧化反应转化成胶质、沥青质;150℃之后,将有部分胶质、沥青质发生裂解反应,饱和烃、芳香烃含量又随着温度的升高而增大,胶质、沥青质含量则降低.     

Low-temperature isothermal oxidation of crude oil

In this work, the low-temperature oxidation (LTO) characteristics of different API gravity crude oils, involving one light, one medium, and one heavy, are studied comprehensively from the aspects of effluent gas, oxidized oil, and pressure drop. The results reveal that heavy oil exhibits faster LTO reaction rate and stronger O₂ consumption capability compared with lighter ones. There are a certain amount of carbonaceous deposits in oxidized oils and the carbonation progress of heavy oil is brought to a deeper degree. The pressure drop rule of oil samples is speculated to be the consequence of “skin effect” and crude oil with more heavy species shows higher oxidation activity, which contributes to an improved understanding about the LTO mechanism from the molecular perspective and needs further research.     

The mechanism of the oxidation of light oil

High pressure air injection (HPAI) has been proven as an enhanced oil recovery process in many fields. The reactions associated with crude oil and oxygen are the main difference between HPAI and other gas injection processes. In order to study the reaction schemes, different experiments, such as the combustion tube, kinetic cell, accelerating rate calorimeter, and thermogravimetry analysis, are conducted. In this paper, a reaction scheme is build that includes three classes of reactions: low-temperature oxidation, cracking, and combustion. We then use simulation models with the proposed reaction scheme included to history match the data from a combustion tube experiment and a kinetic cell experiment. It is demonstrated that the reaction scheme is valid. Based on this study, lumping the crude oil into four pseudocomponents brings a good matching result, and the kinetic parameters are obtained through matching the experimental results.     

The influence factors analysis of the light crude oil oxidation reaction process

During the high pressure air injection process, there are different types of oxidation reactions, which do not exist, and the predominant reaction type of is dependent on the specific conditions. In this study the influences of formation temperature, pressure, and oxidation time on light crude oxidation have been studied via oxidation experiments. And it is shown that the reaction types could be effectively improved by the temperature increment, which decreases the oil viscosity. As well, the pressure and oxidation time have obvious effects that were mainly present in oxygen addition reactions and the viscosity increase.     

压力对轻质原油氧化动力学参数的影响

利用高压差示扫描量热仪(PDSC)研究了不同压力下轻质原油的氧化放热特性,并结合Friedman方法计算了反应体系的活化能,分析了不同反应阶段压力对氧化动力学参数的影响。结果表明:随着压力升高,放热起始温度、峰值温度和反应结束温度均趋向低温,放热量也随之增大,尤其低温氧化放热速度大幅提高,氧化反应明显加强,说明压力增大导致原油在低温下更容易发生氧化反应;活化能在低温氧化前期迅速上升再下降,进入低温氧化后期趋于稳定,到高温氧化阶段再次上升,活化能随反应进程的波动,说明原油反应行为或反应速度发生了变化;对比不同压力下各反应阶段的活化能发现,活化能均随压力升高而降低,说明压力对氧化反应有促进作用,压力越大,反应越容易进行。     

Thermal investigation on crude oil oxidation kinetics through TG/DTG and DTA tests

In this nonisothermal research, the thermal behavior and oxidation kinetics of crude oils were investigated through TG/DTG and DTA tests at three heating rates. The resulting curves exhibit three integrated reactions of distinct oxidation mechanisms (LTO, FD, and HTO) sequentially in overlapped temperature intervals as reaction progresses, the behaviors of that are affected greatly by heating rate. Because of the larger amounts of heavy components and higher availability of deposited fuel, heavy oil exhibits more excellent heat release capability but higher kinetic parameters than light oil, especially in HTO region. Due to the insufficient parameters calculation based on a single kinetic method, other formulated models would be introduced for comparative analysis in the next work to upgrade kinetic research.     

原油脱氯技术的研究进展

综述了原油中氯化物的来源及分布,氯化物对原油加工过程中所造成的设备腐蚀、管线堵塞、催化剂中毒等危害的原因,脱氯剂、脱氯技术、防护工艺及防腐技术的应用等防护措施。总结了国内外现行的氯化物标准检测方法,简述了原油脱氯研究领域中相转移催化脱氯技术的最新研究动态并提出了该技术在当前发展中可能面临的应用推广难题。     

Thermal kinetics investigation on light oil oxidation during high-pressure hypoxic air injection process

In this work, the effects of oxygen concentration and reservoir cutting on thermokinetic characteristics of light oil were analyzed using thermogravimetry (TG/DTG). Results show that three consecutive oxidation reactions of distinct chemical mechanism (low-temperature oxidation [LTO], fuel deposition [FD], and high-temperature oxidation) are detected for all tested samples. Hypoxic air weakens the LTO and FD process and causes a poor FD performance, while reservoir cutting positively influences the thermal characteristics of oil. Kinetic parameters comparison exhibits that the positive effect of reservoir cutting on oil oxidation is significantly stronger than the negative impact caused by hypoxic air. The existence of reservoir cutting greatly reduces the activation energy of oil oxidation in hypoxic air environment, which is a positive signal for the implementation of high-pressure hypoxic air injection process.     

Low-temperature oxidation and thermal kinetics analysis of light and medium crude oils

In this research, low-temperature oxidation (LTO) and thermal kinetics analysis of light and medium crude oils were analyzed by static isothermal experiments and thermogravimetry (TG). The results elucidated that, during LTO process, medium oil possessed stronger oxygen consumption capability than light oil and oxygen addition was the dominating reaction path for both light and medium oils; more heavy components contained in medium oil were oxidized to form higher molecular-weight material with lower H/C. In TG experiments, three main reaction zones were identified known as LTO, fuel deposition (FD) and high-temperature oxidation (HTO). Compared with light oil, LTO range and corresponding mass loss were lowered for medium oil with more oxygenated compounds left behind to be converted into coke materials. The activation energy for medium oil were higher than that for light oil in LTO stage while less in HTO stage owing to the difference of oil components.     

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.     

轻油绝热催化预转化工艺探讨

综述了轻油制富甲烷气的预转化工艺，讨论了该工艺所涉及的反应条件与各种参数对运转结果的影响，并相应开发与该新工艺相配套的新型转化催化剂。