Additional Feedstock for Fluid Catalytic Cracking Unit

Fuel refineries are configured with Fluid Catalytic Cracking Unit (FCCU) to convert Vacuum Gas Oils (VGO) into higher value gasoline and middle distillates. But such refineries also generate 8-12% of heavy oils known either as decant oil or clarified oil (CLO), which has to be downgraded as furnace oil. The recycling of the decant oil into FCCU along with VGO feed is restricted to maintain the coke formation within design limits so that there is no decrease either in conversion or yield of liquid products from FCC operations. The condensed aromatic ring compounds present in CLO makes it undesirable feedstock for cracking, as it promotes heavy coke formation on the catalyst. Hence, CLO is disposed by absorbing in the residual fuel oils.

Of late, FCC units are being operated with higher severity to maximize gasoline, and this has resulted in much higher concentration of condensed aromatics in CLO. Hence, better utilization of CLO depends on separating its saturated hydrocarbon components as a good feedstock for recycling into FCCU with the simultaneous production of extract with enriched poly condensed aromatics as a value added product, namely Carbon Black Feed Stock (CBFS). This article describes several extraction studies carried out on CLO to obtain raffinate for which cracking studies were carried out in automated Micro Activity Test (MAT) unit. The quality of extract phase from each of the above studies was evaluated for its suitability as feedstock for carbon black.     

Additional Feedstock for Fluid Catalytic Cracking Unit

Abstract

Fuel refineries are configured with Fluid Catalytic Cracking Unit (FCCU) to convert Vacuum Gas Oils (VGO) into higher value gasoline and middle distillates. But such refineries also generate 8–12% of heavy oils known either as decant oil or clarified oil (CLO), which has to be downgraded as furnace oil. The recycling of the decant oil into FCCU along with VGO feed is restricted to maintain the coke formation within design limits so that there is no decrease either in conversion or yield of liquid products from FCC operations. The condensed aromatic ring compounds present in CLO makes it undesirable feedstock for cracking, as it promotes heavy coke formation on the catalyst. Hence, CLO is disposed by absorbing in the residual fuel oils.

Of late, FCC units are being operated with higher severity to maximize gasoline, and this has resulted in much higher concentration of condensed aromatics in CLO. Hence, better utilization of CLO depends on separating its saturated hydrocarbon components as a good feedstock for recycling into FCCU with the simultaneous production of extract with enriched poly condensed aromatics as a value added product, namely Carbon Black Feed Stock (CBFS). This article describes several extraction studies carried out on CLO to obtain raffinate for which cracking studies were carried out in automated Micro Activity Test (MAT) unit. The quality of extract phase from each of the above studies was evaluated for its suitability as feedstock for carbon black.     

Clarified Oil from Fluid Catalytic Cracking as an Additional Source of Group II Base Oil Components

Abstract

Clarified oil (CLO) from a commercial fluid catalytic cracking unit was subjected to solvent extraction followed by solvent dewaxing and adsorption chromatography to analyze its various components for different end-use applications. The clarified oil was first solvent extracted using N-methyl pyrrolidone (NMP) to produce paraffinic rich raffinate (68.9 wt% yield). The raffinate thus obtained was dewaxed using methyl isobutyl ketone (MIBK) to get an oil of pour point 0°C. This dewaxed oil was then subjected to adsorption chromatography to determine group II base oil potential through yield v/s viscosity index (VI) curve. The results revealed that clarified oil has an actual potential of around 27.1 wt% of group II base oil components, suggesting that clarified oil can be used as an additional source of feed for production of group II base oil. This article also describes the potential of other components in clarified oil such as slack wax (24.2 wt%), aromatics (31.1 wt%), and low VI oil (17.6 wt%).     

溶剂萃取法分离沙特中质原油VGO及其硫分布规律

以不同水含量的糠醛和N-甲基吡咯烷酮作萃取溶剂,沙中原油减压馏分油经3段萃取被分离为重芳烃相、中芳烃相、轻芳烃相和饱和烃相4个亚组分,采用气相色谱-质谱联用、傅里叶变换离子回旋共振质谱等方法分析了亚组分中烃类组成和硫化物的分布,考察了萃取分离过程各烃类的分离效率和芳烃萃取选择性。结果表明,3段萃取分离出的重芳烃相、中芳烃相和轻芳烃相中芳烃质量分数分别在89.6%~95.6%、80.8%~91.0%和63.9%~77.7%,表明糠醛和NMP是适于分离减压馏分油中芳烃的溶剂;芳烃环数增加,分子极性提高,溶剂对其溶解能力增强,极性较强的三环及以上芳烃主要存在于重芳烃相和中芳烃相;不同水含量的糠醛和NMP对芳烃,尤其是对三环及以上芳烃的分离效率高于饱和烃;水含量增加,溶剂的萃取分离效率降低,但对芳烃的萃取选择性β值提高;NMP对芳烃的萃取选择性高于糠醛。三环及以上噻吩类硫化物主要存在于重芳烃相和中芳烃相中,单、双环噻吩类硫化物基本均匀分布于各亚组分中。     

STRUCTURAL CHARACTERIZATION OF PETROLEUM BASED FEEDSTOCKS FOR CARBON BLACK PRODUCTION

Some selected petroleum based feedstocks have been characterized by ¹H and ¹³C NMR spectroscopy for their possible use as carbon black feedstock (CBFS). Feedstocks studied are pyrolysis tars, clarified oils, aromatic extracts and vacuum residue. Analysis of average structural NMR parameters show that pyrolysis tars because of their being highly aromatic in character (high BMCI) are the most suitable feedstock for carbon black. Aromatic extracts rank the next. Clarified oils of Indian refinery origin needs further processing due to middle distillate mode refining severity.     

溶剂抽提改质减压瓦斯油作蒸汽裂解原料

对溶同提改质大庆减压瓦斯油（VGO）作蒸汽裂解原料的工艺进行了研究,结果表明,N－甲基吡烷酮（NMP）具有优异的脱芳烃和脱胶质性能,在200t/a中试抽装置上,温度75℃,相比（原料油与溶剂体积比）为2的条件下,试验所得抽余油的收率和脱芳烃率无大于70％,BMCI值小于16,经785℃模拟蒸汽裂解试验,提抽改质油乙烯收率和乙烯,丙烯及丁二烯总收率分别大于27％和50％,表明NMP溶剂提提改质减压瓦斯油的工艺是一条生产蒸汽裂解原料的可行途径。     

Extraction of aromatic from lube oil using a surfactant as an additive

Solvent extraction is a practical method for the reduction of lube oil aromatic content. Common solvents are phenol, furfural, and N-methyl pyrrolidone (NMP). The extractive power and the selectivity parameters can be increased by the addition of surfactants, which facilitates phase separation and consequently increases the refinery yield. The operatory extraction temperatures and surfactant concentrations ranged, respectively, from 333.15 to 343.15 K and from 0.01 to 0.1%wt. Optimal extraction conditions were systematically determined by measuring the temperatures and surfactant concentrations. The amounts of aromatic, paraffinic, and naphthenic compounds were compared to ASTM standards, namely refractive index (RI), viscosity, molecular weight, and sulfur content. The experimental results show that the best results were realized with 0.01%wt of surfactant and at 343.15 K.     

浅析炼油厂重质芳烃油的利用

炼油企业副产大量的重质芳烃油,开发利用重芳烃资源,实现炼油企业经济效益最大化,具有现实意义,炼油厂重质芳烃油有多种化工用途,可作为蒸馏工艺强化剂,优化溶剂脱沥青工艺添加剂,橡胶工业的橡胶填充油和工艺软化油,工业导热油,黑色油墨溶剂油等。     

润滑油溶剂精制装置抽出油综合利用的应用研究

抽出油是润滑油溶剂精制装置生产过程中的一种副产物,因富含大量芳烃、部分饱和烷烃和少量胶质、沥青质,使其直接加工利用受到限制,常作为燃料油的调和组分,经济效益低。为提高抽出油的利用价值,对其进行处理后进一步加工利用,包括:炼油装置掺炼,调和道路沥青,制备表面活性剂,生产橡胶填充油、溶剂油、导热油、绝缘油和缩合多环芳烃树脂,对抽出油的综合利用前景进行了展望。     

多级错流萃取分离糠醛抽出油中烃类组分

针对烃类组成复杂多样的糠醛抽出油(FEO),分别选取糠醛、二甲基亚砜(DMSO)、N-甲基吡咯烷酮(NMP)为溶剂,研究三级错流萃取分离FEO中不同烃组分的分离规律。采用气相色谱-质谱联用、傅里叶变换离子回旋共振质谱等手段分析了萃取抽出油、抽余油的组成信息,并计算萃取平衡分配系数、萃取选择性与抽余油收率。结果表明：DMSO萃取后抽余油中多环芳烃含量显著降低,糠醛与烃组分形成的“连续体”被破坏,促使糠醛对芳烃的萃取选择性显著增大;多种溶剂组合的三级错流萃取能有效分离FEO中的烃类组分,可将不同环数的芳烃分别富集在不同萃取级;相同的芳核结构,短侧链的芳烃更易溶解于极性溶剂中;三级萃取对杂环化合物的选择性明显高于纯碳氢芳烃化合物。     

润滑油N-甲基吡咯烷酮精制工艺条件的优化

以兰州炼油化工总厂减二线馏分油为原料 ,研究了溶剂比、温度以及溶剂中的乙醇胺含量和水含量对N 甲基吡咯烷酮 (NMP)精制效果的影响 ,以期寻找润滑油NMP精制的优化工艺条件。实验结果表明 :NMP对于改善润滑油基础油的质量和去除原料油中的有机酸有很大的作用。增加溶剂比和升高温度可以降低润滑油的折光率 ,但是升高温度不利于对原料油中酸性物质的抽提。为了降低产品的酸值 ,向溶剂中加入适量的乙醇胺是一个好方法 ,但是会使产品的折光率略有上升。另外 ,NMP中的水也会对产品折光率和馏分油中酸性物质的抽提产生不利影响。     

溶剂抽提精制催化裂化油浆的研究

以中国石油大连石化分公司第七生产厂的催化裂化油浆为原料,分别以糠醛、复配A作为萃取溶剂,对溶剂抽提精制催化裂化油浆进行研究,考察抽提温度、剂油比对单级抽提的精制效果,优选最佳的抽提条件进行多级逆流抽提试验。结果表明：分别以糠醛和复配A作为萃取溶剂,在抽提温度60 ℃、剂油质量比2～3的条件下,均可以有效地将油浆中的烷烃与芳烃分离,分离效果较好。抽余油（精制油）可作为RME(F)180系列船用残渣燃料油的调合组分,抽出油可作为KA8520橡胶填充油的调合组分。     

润滑油精制中NMP对石油酸抽提规律的研究

NMP(N-甲基吡咯烷酮)润滑油精制是国外近年发展起来的一种性能较优的精制工艺。以减三线油为原料,系统地研究了NMP作为溶剂对石油酸的抽提能力,包括温度、乙醇胺和水的加入对抽提能力的影响。实验结果表明,NMP对石油酸具有相当高的抽提能力;但随着原料油酸值的升高,现有的工艺条件下抽提能力仍嫌不足;在溶剂中加入适量的乙醇胺和水对于石油酸的抽提有较大的改进。     

催化裂化回炼油溶剂精制新工艺的研究

以炼厂催化裂化回炼油为原料,选取一种胺类复合溶剂作萃取剂,可有效分离重质油中的芳烃组分和可裂化组分.考察了抽提温度、剂油比和萃取时间对产品收率的影响.结果表明:在抽提温度为60℃,剂油比为2∶1,萃取时间30 min时,原料油的分离效果较好.在此条件下,抽提油收率达到79.03％,其中芳香烃组分的质量分数达87.58％...     

炼厂干气中乙烯回收和利用技术进展

炼厂干气中乙烯回收和利用对石化企业提高经济效益和资源再利用有重要意义。综述了炼厂干气中乙烯回收和利用的技术进展,重点介绍了深冷分离法、冷油吸收法、溶剂抽提法、化学吸收法、变压吸附法和膜分离法等在干气回收乙烯过程中的应用;对干气中乙烯的直接利用,介绍了干气制乙苯、干气制环氧乙烷、干气制丙醛等技术的进展;建议干气的回收和利用需要根据炼化企业的自身特点,选择合适的工艺,以取得最佳的经济效益。     

催化裂化油浆溶剂萃取生产环保橡胶油和裂化原料研究

以糠醛为萃取溶剂、石油醚为助溶剂,采用错流和逆流两种萃取方式,研究了催化裂化油浆生产环保型橡胶填充油或催化裂化原料的方法,考察了萃取温度、剂油比和萃取级数的影响。结果表明：单级萃取的最优条件为萃取温度50 ℃、剂油比2.5:1,在此最优条件下,萃取级数越高,萃取效果越好,当萃取级数达到三级时,两种工艺所得精制油多环芳烃质量分数（PCA）3%以下,8种致癌性多环芳烃PAHs<10 μg/g,芳碳率10%以上,均满足欧盟环保型橡胶油要求;同时精制油密度降到0.9 g/cm3以下,饱和烃含量达到80%以上,也是优质催化裂化原料。多级逆流萃取精制油收率可达到30%以上,明显高于多级错流萃取。     

基于分子管理的萃取分离工艺优化利用石脑油资源

In this paper, the separation of aromatics from light naphtha by using extraction process was investigated for improving the utilization efficiency of naphtha. It is indicated that, using a mixture of propylene carbonate-diethylene glycol as the solvent, the optimal extraction conditions cover: a volume fraction of propylene carbonate in the mixed solvent of 0.3, a solvent to feed ratio of 8, and an extraction temperature of 308 K. Through the extraction process, the aromatics mass fraction increases from 10.05% in naphtha to 27.74% in extract oil. It is found that the aromatics yield of extract oil, R_A, reaches 92.11%. As a result, in comparison with naphtha, the potential aromatics content of extract oil increases impressively by 18.03%. Meanwhile, the aromatics content of raffinate oil decreases to 1.33%, and the normal paraffin yield of raffinate oil, Rp, is 76.61%. Accordingly, higher total olefins yields can be obtained when using raffinate oil as the raw material for steam cracking. The present results show that the utilization efficiency of naphtha is improved through extraction process.     

催化裂化芳烃萃取油用作煤液化起始溶剂的研究

 选用一种催化裂化（FCC）芳烃抽提装置生产的芳烃萃取油作为煤液化开车起始溶剂的原料，在0.1t/d连续装置上进行的煤液化实验。利用色质联用仪解析其组成和结构，应用常温常压黏度仪考察了其成浆性。结果表明,芳烃萃取油具有多环芳烃含量高的特点, 3次加氢后的芳烃萃取油与煤液化加氢循环溶剂的结构组成十分接近。采用三次加氢萃取油制备的煤浆具有良好的成浆性、输送性和反应性，与煤液化加氢循环油参与煤液化的效果相当, 是理想的煤液化起始溶剂。     

A PROCEDURE FOR THE PRODUCTION OF ULTRA-PURE PRECURSORS FROM COAL FOR THE MANUFACTURE OF VALUE-ADDED CARBON PRODUCTS - PREPARATION OF AN EXTRACT

Solvent extraction is a potential technique for the production of coal-derived extracts which may be suitable as precursors for value-added carbon products. At present. the development of new and non-conventional markets for coal has resulted in the exploration of new applications such as slurry fuels, coal-based graphites, carbon-carbon composites and carbon anodes. However, for carbon products to perform acceptably in such applications, the ash content of the precursor must be less than 0.1%. Although, work to produce a low-ash (ca. 0.2%), low-sulfur coal-derivcd material had begun about a decade ago through solvent extraction using the solvent NMP (N-methyl-2-pyrrolidone), it was practically impossible to produce a coal-dcrivcd extract containing less than 0.2% ash. This is due to the presence of ultra-fine mineral matter particles and solvent soluble inorganic species. The principal objective of the present work was to investigate techniques for the separation of the coal-derived extract from the NMP-coal suspension after solvent extraction and to produce a ultra low-ash precursor. The significant     

A PROCEDURE FOR THE PRODUCTION OF ULTRA-PURE PRECURSORS FROM COAL FOR THE MANUFACTURE OF VALUE-ADDED CARBON PRODUCTS - PREPARATION OF AN EXTRACT

ABSTRACT

Solvent extraction is a potential technique for the production of coal-derived extracts which may be suitable as precursors for value-added carbon products. At present. the development of new and non-conventional markets for coal has resulted in the exploration of new applications such as slurry fuels, coal-based graphites, carbon-carbon composites and carbon anodes. However, for carbon products to perform acceptably in such applications, the ash content of the precursor must be less than 0.1%. Although, work to produce a low-ash (ca. 0.2%), low-sulfur coal-derivcd material had begun about a decade ago through solvent extraction using the solvent NMP (N-methyl-2-pyrrolidone), it was practically impossible to produce a coal-dcrivcd extract containing less than 0.2% ash. This is due to the presence of ultra-fine mineral matter particles and solvent soluble inorganic species. The principal objective of the present work was to investigate techniques for the separation of the coal-derived extract from the NMP-coal suspension after solvent extraction and to produce a ultra low-ash precursor. The significant