THE SOLVENT EXTRACTION APPROACH TO PETROLEUM DEMETALLATION

ABSTRACT

Metals are present in petroleum depending on age and conditions of diagenesis, and concentrate during refining in heavy fractions and residua. Nickel and vanadium show particularly deleterious effects on catalysts, such as poisoning, excessive gas and coke formation. Besides, removing vanadium from fuel oils reduces the environmental impact of “acid rain” due to the oxidation of sulphur dioxide in the atmosphere.

In this paper, research and industrial practice literature concerning the removal. of nickel and vanadium from petroleum and its fractions by solvent extraction and related techniques is reviewed and arranged into four groups as follows:

i) Processes employing hydrocarbon solvents, used to modify the oily matrix solubility parameter in such a way that asphalt/enes be separated. Because a fraction of total metals present are associated to asphalt/enes, deasphaltation implies partial demetallation.

ii) Processes using polar solvents, scarcely miscible with petroleum and able to selectively extract from it metallic complexes of heteroatomic ligands (e.g. metalloporphyri ns).

iii) Processes not based on molecular phase equilibria like i) and ii) but on the formation, by contact with aqueous solutions, of a separate, colloidally stabilized phase. Either surface active agents are added or the surface activity of substances naturally occurring in petroleum is promoted.

iv) Processes based on extraction with chemical reaction (oxidation, chelation) orion exchange between organometallic species in petroleum and ligandsin solution of non-miscibile media.     

胜利原油减一线油溶剂抽提分离石油酸

采用复合溶剂抽提分离胜利原油减一线油中的石油酸，经优选表明，复合溶剂的最佳配比为：活性组分A含量为1％—3％，60％乙醇含量为97％—99％；抽提的最佳剂油比为0.15。经复合溶剂抽提，可脱除减一线油中80％以上的石油酸，减一线精制油收率达99.3％，石油酸收率达0．62％，粗酸值为157mgKOH/g，复合溶剂可回收重复利用，回收率98.9％。采用该工艺每处理lt减一线油，可实现增值约10RMB￥。     

润滑油溶剂精制过程中助溶剂的应用

综述了在润滑油馏分溶剂精制过程中，加入助溶剂，以提高精制油收率，改善精制油质量的国内外研究应用情况。建议我国科研单位开展研究，尽快实现工业化应用     

溶剂抽提法处理油砂的研究

用溶剂抽提法对蒙古露头油砂进行处理,实验筛选出了最佳抽提试剂为120号溶剂油,综合考察了抽提温度、剂砂质量比、抽提时间等工艺操作条件对油砂处理的影响。结果表明,在抽提温度75℃、剂砂质量比3：1、抽提时间40min的条件下,120号溶剂油处理油砂可使油提取率达95%以上,回收溶剂油可循环重复利用。该方法经济可行,为油砂的开发利用提供了一条有效途径。     

一种提高润滑油溶剂精制过程效率的有效方法

通过快速准确的过程模拟方法,对润滑油的溶剂精制过程进行模拟,进而提高溶剂精罅过程的效率。采用的馈神经网络和反向传播算法,对精制油性能、操作条件和原料油性能进行了模拟,模拟结果与实验结果吻合较好。     

快速溶剂萃取法提取印尼油砂沥青的工艺研究

采用快速溶剂萃取技术提取油砂沥青,通过单因素试验和正交试验得出加压溶剂萃取技术的最佳工艺参数。研究结果表明,在高压条件下,混合适量硅藻土分散剂,快速溶剂萃取法提取油砂沥青比传统索氏抽提与费舍尔试验更有优势。利用正交试验获得快速溶剂萃取法提取油砂沥青的最佳工艺参数为：压力10 MPa,土砂比(硅藻土与油砂的体积比)2∶1,萃取温度160℃,循环次数5次,溶剂选择四氢呋喃,单次静态萃取时间12 min。     

溶剂萃取法生产变压器油的工艺研究

为解决兰州炼油化工总厂生产变压器油中产生的酸渣、碱渣对环境的污染问题,研究了用溶剂萃取精制来取代原有的电化学酸碱精制工艺,萃取剂为含水的Ｎ-甲基吡咯烷酮（ＮＭＰ）,含水量１％～３％,操作温度在３０～５０℃,剂油比为０．２５～０．５０,经多级革取和水洗,精制油的色号、酸值均达到与原工艺相同的半成品油的质量指标,再经低温白土精制,可生产出合格的变压器油。     

加拿大油砂溶剂提取分离的实验研究

采用半连续溶剂抽提法对加拿大油砂进行了提取分离试验,应用溶解度参数理论以及实验筛选出最佳抽提溶剂为重整汽油。综合考察了提取温度、溶剂流量、提取时间以及提取压力等工艺操作条件对油砂沥青提取的影响。结果表明,在提取温度80 ℃、溶剂流量60 mL/min、提取时间60 min、提取压力1.0 MPa的条件下,油砂沥青提取率达到92.74%。     

芳烃抽提溶剂再生新工艺在实际生产中的应用

介绍了JWF-Ⅱ型溶剂专用过滤器技术在中国石油辽阳石化分公司芳烃厂芳烃联合装置的应用情况，对其实际运行效果进行了评价。与原有工艺相比，装置运行平稳、经济效益明显。     

焦化蜡油溶剂萃取工艺的研究

焦化蜡油通常作为催化裂化的掺用原料，但焦化蜡油的碱氮和胶质含量高，容易使催化裂化催化剂中毒失活，且其催化裂化转化率低，生焦量大。溶剂抽提是解决这一问题的较好途径。用润滑油抽出液代替新鲜溶剂萃取焦化蜡油，不仅能达到降低焦化蜡油碱氮和胶质含量的目的，而且提余油收率又比新溶剂抽提高１０％左右，用很少的设备投资和操作费用即可实现润滑油抽出液萃取焦化蜡油工艺。     

改进和完善NMP生产工艺降低溶剂消耗

对NMP装置溶剂消耗进行分析，找出消耗大的原因，通过采取降低溶剂回收温度、改进氮气密封和溶剂国产化等措施，取得了显著效果，溶剂单耗由0．48k／t降至0．26k／t，达到国际同类装置先进水平，装置能耗由36．48kgEO／t降至32．17kgEO／t，取得较好的企业效益和社会效益。     

直馏柴油溶剂抽提精制

去除直馏柴油中的环烷酸，采用加氢精制法成本高，且氢源不足；采用碱洗法则损失大，污染严重。为此采用以助溶剂和溶剂组成的复合溶剂抽提方法脱除直馏柴油中的环烷酸，并对抽提的工艺条件进行了实验室研究。结果表明，采用单级抽提，剂油比为1～2：10，酸去除率达80％以上，柴油的回收率达99％以上，精制后柴油酸值合格，还可副产环烷酸。溶剂及助溶剂均可回收利用，不污染环境。     

脱蜡油与萃取溶剂临界溶解温度的研究

对脱蜡油与萃取溶剂临界溶解温度的影响因素进行了考察,对脱蜡油理化性能与临界溶解温度的关联性进行了研究,建立了脱蜡油饱和烃含量与临界溶解温度关联式,并对关联式进行了验证。     

催化裂化柴油溶剂抽提降芳烃工艺技术研究

针对中国石化长岭分公司催化裂化柴油芳烃含量高、十六烷值低的问题,采用溶剂抽提降芳烃技术改善柴油质量,同时对抽出的芳烃进行分离和利用。实验结果表明：在130～150 ℃、剂油体积比1.5～6.0的条件下进行溶剂抽提,抽余油的芳烃质量分数降至38.4%～63.3%,十六烷值大于45,较原料提高了20个单位以上;所抽出的芳烃混合组分中单环芳烃（烷基苯）含量高,可以作为芳烃溶剂油。     

SOLVENT EXTRACTION OF PAKISTAN COALS (III) EXTRACTION AND CHARACTERIZATION OF THE EXTRACTS BY SPECTROSCOPIC TECHNIQUES

Abstract

The Makerwal coal of Pakistan gives higher extractibi1ity with Tetrahydrofuran ( THF ) as compared to Sharigh, Sor-Range and Lakhra coals. The structural characterization of Pakistan coal extracts by FT-IR spectroscopy indicates that all the extracts contained less condensed aromatic rings in comparision to their original coal.     

SOLVENT EXTRACTION OF PAKISTAN COALS (III) EXTRACTION AND CHARACTERIZATION OF THE EXTRACTS BY SPECTROSCOPIC TECHNIQUES

The Makerwal coal of Pakistan gives higher extractibi1ity with Tetrahydrofuran ( THF ) as compared to Sharigh, Sor-Range and Lakhra coals. The structural characterization of Pakistan coal extracts by FT-IR spectroscopy indicates that all the extracts contained less condensed aromatic rings in comparision to their original coal.     

溶剂萃取法提高催化裂化柴油十六烷值的研究

用双溶剂萃取法提高催化裂化柴油的十六烷值，即用含有金属离子的糠醛作第一溶剂对催化裂化柴油中的双环以上芳烃进行萃取，再用石油醚对抽出油进行萃取以回收其中的高十六烷值组分。结果表明，经该方法处理所得到的合格柴油收率可达90％。糠醛中溶有金属离子可提高对双环以上芳烃及氮等杂原子化合物的选择性，从而提高催化裂化柴油的十六烷值和安定性。     

润滑油溶剂精制抽出油制取石油磺酸盐的研究

以减五线馏分油溶剂精制后的抽出油为原料，采用发烟硫酸为磺化剂进行磺化反应制取石油磺酸，进而制取石油磺酸钠。在磺化反应过程中主要考察了反应温度、反应时间和酸油体积比对石油磺酸收率的影响。在酸油体积比0.12、反应温度60℃、反应时间45min的条件下，石油磺酸收率为64.14%。在石油磺酸中加入10%的氢氧化钠，进行中和反应后，采用乙醇萃取出石油磺酸钠，所得石油磺酸钠的活性物含量为42.10%，可作为表面活性剂使用。     

AN INTRODUCTION TO THE PETROLEUM POTENTIAL OF NIGER

The Republic of Niger can be divided into two sedimentary and tectonic provinces: a Palaeozoic platform-type province in the north and west, and a series of Mesozoic grabens in the east.
Thick Palaeozoic successions are present in the NW (in the Tamesna-Talak area of the Iullemeden Basin), and the NE (in the Djado Basin). The petroleum potential of these areas is not yet proven. By analogy with the Algerian Illizi Basin and the Libyan Murzuk Basin, Silurian source rocks together with Ordovician, Devonian and Carboniferous sandstone reservoir units may occur here.
In East Niger, a complex rift system, whose sedimentary fill ranges in age from Late Jurassic to Early Tertiary, has proven petroleum potential. Reservoir rocks are mainly Cretaceous to Eocene sandstones, sourced by Cretaceous marine shales and Oligocene lacustrine shales.
This paper reviews the petroleum geology of Niger, and assesses potential exploration targets. Commercial developments can shortly be expected following the construction of an export pipeline from Chad to Cameroon, and the resumption of drilling activity in the Agadem and Djado Basins.     

降低酮苯脱蜡装置溶剂含水的有效途径

介绍了酮苯脱蜡装置溶剂含水原因及对生产过程的不利影响。通过对溶剂干燥系统的操作因素进行分析,找出了造成含水偏高的关键因素,主要是干燥塔进料温度受系统负荷影响较大,自身无调节手段,影响了干燥效果。通过分析探讨,指出干燥系统的操作重点是干燥塔进料温度、水分离罐界面及酮塔进料温度与汽提量,针对含水偏高问题提出了干燥塔底增设重沸器的解决对策。