萃取法脱除南海原油中环烷酸的工艺研究

在LES萃取脱酸试验装置上,用LES-1萃取剂对南海原油进行了脱酸工艺研究。结果表明,在典型的工艺条件下,可以将南海高酸原油的酸值从2．80 mgKOH/g降到0．5 mgKOH/g以下。萃取后溶剂经过蒸馏回收可以循环使用,并获得了副产品粗环烷酸。     

原油中环烷酸腐蚀预测方法综述

对国内外有关环烷酸腐蚀预测方法的文献报道进行分析得出 :原油的总酸值和硫含量无法准确预测环烷酸腐蚀 ;以环烷酸腐蚀介质中的高压釜失重实验为基础的金属挂片法可提供与环烷酸腐蚀最为直接的参考数据 ,其中腐蚀速率与金属挂片单位面积上失重量的比值 (环烷酸腐蚀指数法 )是目前最好的预测方法 ;其次是与流体流速有关的壁剪切应力比较法     

实沸点蒸馏前后高酸重质原油的石油酸分布表征

The molecular transformations of carboxylic acids in heavy acidic SL crude before and after true boiling point distillation were examined by ultra-high resolution negative-ion electrospray ionization （ESI） Fourier transform ion cyclotron resonance mass spectrometry （FT-ICR MS）. The acid class （heteroatom number）, type （z numbers） and carbon number distributions were positively characterized. It was found out that the total acid number （TAN） of SL crude decreased after true boiling point distillation, and the abundance of O2 class in mass spectra was also found to be reduced from 67.6% to 34.5% in SL TBP mixed crude as measured by MS spectra, indicating to a potential carboxylic acid decomposition. However, it was interesting that the carboxylic acids type distribution in both oils was almost the same although their relative abundance in SL TBP mixed crude turned to be much lower, suggesting that various petroleum carboxylic acid types have the similar thermal decomposition reaction behavior. Furthermore, for each O2 type of acids in SL TBP mixed crude, the abundance of carboxylic acids with carbon number higher than 35 was reduced greatly, especially for those with carbon number higher than 60, the mass peaks of which were nearly totally removed, indicating that the large carboxylic acid molecules in heavy fractions decomposedmore significantly because of longer heating time during the true boiling point distillation process. As a result, the reduction ofTAN may be caused by the thermal decomposition of carboxylic acids especially those with high carbon number, suggesting that quick distillation or much lower pressure is required to avoid the thermal decomposition.     

复合溶剂氨法萃取高酸值原油中环烷酸的实验室研究

对复合溶剂氨法抽提高酸值原油环烷酸抽提工艺条件进行了实验室研究。结果表明，在温度55℃，溶剂配比(体积分数)为乙醇50％、异丙醇15％、氨2％，剂油体积比为1．0，搅拌速率250r／min，反应时间30min，沉降时间80min的条件下，使用复合溶剂氨法脱除苏丹高酸值原油中的环烷酸具有良好的脱酸效果，二次脱除率在92％以上。分离所得的环烷酸品质较高，其酸值在190mgKOH／(100mL)左右，纯度达90％左右，达到85号环烷酸行业标准。     

流速和硫含量对原油中环烷酸腐蚀性的影响

 设计了一种现场腐蚀旁路试验方法,该方法不仅可以直接研究实际生产原油中环烷酸对材质的腐蚀性,还可以实现变流速试验。采用该装置研究了原油流速和硫含量对其中环烷酸腐蚀性的影响规律。结果表明,在试验条件下,随原油流速的增加,10#碳钢和Cr5Mo的腐蚀速率均成线性增大,321不锈钢的腐蚀速率基本不变;在各个流速情况下321不锈钢的耐腐蚀性最优,Cr5Mo其次,10#碳钢最差。在硫质量分数不大于0.86％时,硫含量对原油中环烷酸腐蚀性的影响较小;当原油中硫质量分数大于0.86％时,随着硫含量的增加,10#碳钢和Cr5Mo的腐蚀速率显著减小, 321不锈钢的腐蚀速率均很小;在各个硫含量情况下321不锈钢的耐腐蚀性最优,Cr5Mo其次, 10#碳钢最差。     

重质高酸原油酯化脱酸催化剂的研究

 高酸原油的加工是炼油厂面临的一大难题。笔者开发了一种用于高酸原油酯化脱酸的固定床酯化催化剂，使高酸原油中的环烷酸与甲醇反应生成环烷酸甲酯来降低原油的酸值和腐蚀性。结果表明，SnO是催化酯化脱酸催化剂的有效活性组分，适当增大催化剂的孔径可提高原油的酯化脱酸率。该催化剂应用于中海绥中36-1高酸原油，可有效降低原油的酸值，在反应温度300℃、醇/油质量比0.02，体积空速1.0h-1时，可使原油的酸值由2.8mgKOH/g降低到0.34mgKOH/g, 能够满足炼油厂加工的需要。     

酯化高酸原油的腐蚀性研究

研究了石油酸酯和酯化高酸原油的热稳定性及腐蚀性规律。结果表明,石油酸酯在高温下会发生一定的分解,但石油酸经酯化后可有效抑制腐蚀,缓蚀率达95%以上;酯化降酸抑制腐蚀的程度与酯化高酸原油中金属羧酸盐含量有关,通过脱除原油中的金属羧酸盐及采用稳定的非均相催化剂,可降低石油酸酯分解反应速率,达到抑制腐蚀的目的。     

ZnMgAl-HTlc催化酯化高酸原油脱酸

 加工高酸原油是炼油厂面临的一大难题。在ZnMgAl类水滑石为催化剂作用下,原油中的环烷酸与乙醇反应生成环烷酸乙酯,可有效降低原油的酸值并降低其对设备的腐蚀性。实验结果表明,ZnMgAl-HTlc是一种有效的酯化脱酸催化剂,反应后其结构基本未变。在醇酸摩尔比3:1,反应温度220℃,反应时间40min,原油和催化剂质量比200时,可使辽河高酸原油的酸值由3.61 mgKOH/g降至0.22 mgKOH/g,能够满足炼油厂在不进行材质升级条件下加工高酸原油的需要。     

高酸原油酯化法脱酸研究进展

国外在上世纪末就对原油酯化法脱酸进行了研究,Guido等人在专利中提出向含酸的原油加入一定量的醇,在室温～450℃、0.1～0.3 MPa的条件下可以将原油中的酸转化为酯。酯化法脱酸投资少,操作费用低,脱酸效率高,具有可观的工业化前景。对于高酸原油酯化法的研究还可从研究新型高效的酯化脱酸催化剂或对处理工艺进行改进方面着手,如采用超声波等辅助方法,来提高酯化法脱酸的效果。     

阿尔巴克拉高酸原油的石油酸结构分析

以阿尔巴克拉原油为模型,对高酸原油中石油酸分子的结构进行了研究。对其进行实沸点蒸馏分析,表明间歇蒸馏过程中部分石油酸类化合物在受热过程中会发生脱羧反应,不利于分子结构特性的研究。借助高分辨质谱、红外光谱对常减压装置中馏分油的酸性氧化物进行了组成及结构分析,认为相对丰度均为:O2>O1>N1O2>N1O1>N2O1;各馏分油中O2类石油酸化合物分子的等价双键数(DBE)值范围在1~19,碳数范围在C10~C54;丰度较高的化合物分子碳数集中在C25~C30之间,DBE值为2~4附近;采用碱醇液萃取的方法对环烷酸进行了富集和红外光谱分析,推断原油及馏分油中存在的石油酸分子以环烷酸类为主,羧基连接在环烷酸的侧链上且侧链的碳数一般不超过5。     

Reduction of naphthenic acids in high TAN crude oil using a fluid catalytic cracking catalyst

A commercial Fluid Catalytic Cracking (FCC) catalyst is used to reduce naphthenic acids (NAs) in a high Total Acid Number (TAN) crude oil sample. The influence of temperature, oil/catalyst ratio is investigated using non-treated and thermally treated FCC catalyst. It is shown that the FCC catalyst is capable of reducing NAs with a reduction in TAN of 15.9% and 13.22% at an oil/catalyst ratio of 3:1 and 4:1 respectively. Thermal pre-treatment of the FCC catalyst, in combination with an increase in the temperature of the Crude Oil to 190°C, resulted in an overall TAN reduction of 22.34%.     

The transformation of basic nitrogen compounds in coker gas oil during catalytic cracking

Two narrow fractions distilled from Liaohe coker gas oil were used for the research. The distribution of basic nitrogen compounds in feedstocks and their liquid products were characterized by ESI FT-ICR MS. The results showed that N1 class species were the most predominant in both feedstocks and products. The catalytic cracking progress reduced the relative abundance of all class species, except for the N1 and N1S1 class species. Although the N1 class species had longer side chains and higher condensation in the heavier feedstock, the distribution of N1 class species became similar in the two liquid products.     

Molecular Characterization of Hydrotreated Atmospheric Residue Derived from Arabian Heavy Crude by GC FI/FD TOF MS and APPI FT-ICR MS

High resolution mass spectrometry in combination with distillation and SARA fractionation provides us an opportunity for in-depth understanding about the hydrotreating process at the molecular level. In this study, the atmospheric residue derived from Arabian heavy crude and its hydrotreated products were initially subjected to distillation and SARA fractionation. The saturates were characterized by GC FI/FD TOF MS. The aromatics and resins were characterized by APPI FT-ICR MS. Compositional changes of different compounds (paraffins, naphthenes, aromatic hydrocarbons, and heteroatomic compounds) contained in different distillates (vacuum gas oil, vacuum residue) were obtained. More detailed knowledge about the hydrotreating process was achieved.     

Tracking Catalytic Esterification of Naphthenic Acids in Crude Oil by ESI FT-ICR MS

The catalytic esterification reaction was used to decrease total acid number(TAN) of crude oil by converting naphthenic acids to naphthenic acid esters in the presence of Zn-Al hydrotalcite used as the catalyst and glycol used as the reactant. The crude oil and its corresponding esterified oil were characterized by the negative-ion electrospray ionization(ESI) Fourier transform ion cyclotron resonance mass spectrometry(FT-ICR MS). Six acidic class species, O_2, O_1, N_1, N_2, N_1O_1 and N_1O_2 were assigned in the negative-ion spectrum both in the crude oil and its esterified oil. Among the identified acidic compounds, the O2 class was dominant. The relative abundance of O_2 class species was much higher than other acidic class species in crude oil, while it was significantly decreased after esterification. The most abundant O_2 class species had a carbon number of 30-34 and a double-bond equivalence(DBE) value of 5 before and after esterification. It could be concluded that the naphthenic acids in crude oil can be esterified to lower its TAN value, and each of them seems to exhibit identical esterification efficiency approximately due to the similar DBE versus the-carbon number distribution before and after esterification.     

车用废润滑油中酸性组分的高分辨质谱分析

车用新鲜及废润滑油样品的傅里叶变换红外光谱(FT-IR)表明,两者中均存在羧基及羟基官能团,即存在酸性组分。利用具有超高分辨率的负离子电喷雾-傅里叶变换离子回旋共振质谱仪(negative-ion ESI FT-ICR MS)分析了车用新鲜及废润滑油中酸性化合物的组成及分布。结果表明,从新鲜润滑油中鉴定出的酸性化合物主要为O3、O1及O2类,而从废润滑油中鉴定出的酸性化合物则主要为O3、O2、O4及O1类。经对比分析可知,新鲜润滑油中的酸性化合物在废润滑油中均存在,其种类及所占比例基本未发生变化,但绝对含量不同;废润滑油中新产生的O3、O2及O1类酸性化合物种类较多,但其所占比例较小;车用新鲜与废润滑油中酸性组分的显著差异在于后者中产生了前者所没有的O4类化合物,且所占比例较大。     

加拿大油砂沥青中极性化合物的电喷雾——高分辨质谱研究

目前,生物降解作用对饱和烃生物标志物、芳香烃生物标志物参数以及小分子含氮化合物参数影响的研究较多,而对大分子极性化合物组成影响的研究较少。采用负离子电喷雾—傅立叶变换离子回旋共振质谱（ESI FT-ICR MS）分析不同降解级别的加拿大油砂沥青中酸性及非碱性氮化合物分子组成,结果表明,加拿大油砂沥青中杂原子化合物组成非常复杂,共鉴定出10种不同杂原子类型（N₁、N₁O₁、N₁O₂、N₁S₁、O₁、O₁S₁、O₂、O₂S₁、O₃、O₄）的化合物,其中以O₂类化合物为主。随着生物降解程度的加深,N₁、N₁O₁及O₁类化合物的相对丰度逐渐降低,而O₂及O₂S₁类化合物的相对丰度显现出逐渐增加的趋势;高分辨质谱分析在石油大分子杂原子化合物研究方面所独有的优势,为石油地球化学研究提供了新的思路。     

The distribution of corrosive acidic compounds in petroleum fractions

Because the acidic compounds of the feedstock of T refinery (FTAC) have special high corrosivity, the composition and class distribution of the acidic compounds were analyzed by electrospray ionization Fourier transform ion cyclotron resonance mass spectroscopy, and compared with the acidic compounds of the lubrication distillation fraction from D refinery and commercial naphthenic acids. This study indicates that the feature of FTAC is exceptionally high proportion of acyclic carboxylic acids, aromatic acids, and alkylphenol-like compounds, which are some of the reasons for the high corrosivity of the feedstock of T refinery.