Selective separation of solvent from deasphalted oil using CO₂ for heavy oil upgrading process based on solvent deasphalting

Im, Soo Ik,Shin, Sangcheol,Park, Jun Woo,Yoon, Hyung Jin,Go, Kang Seok,Nho, Nam Sun,Lee, Ki Bong Elsevier 2018 Chemical Engineering Journal Vol.331 No.-

<P><B>Abstract</B></P> <P>The solvent deasphalting (SDA) process is a heavy oil upgrading process in which deasphalted oil (DAO) is extracted from heavy oil feedstock by precipitating asphaltene using an excess amount of alkane solvent (C3-C6). After the extraction, solvent recovery should be carried out for separating the solvent from the DAO in order to recycle the expensive solvent. In the conventional solvent recovery method, the mixture of solvent and DAO is heated to evaporate the solvent, which requires massive heat energy, resulting in reduced process efficiency. In this study, CO<SUB>2</SUB> is applied for the first time to selectively separate solvent from DAO at a relatively low temperature. The experimental results in a batch separator indicate that the temperature required for high solvent recovery of over 80% decreases from 200°C to 40°C when using CO<SUB>2</SUB> compared to the conventional method. The theoretical approach using Hansen distance calculation based on the Hansen solubility parameter (HSP) was used to verify the mechanism of solvent separation using CO<SUB>2</SUB>. The results suggest that the increase in the interaction between CO<SUB>2</SUB> and solvent causes the separation of solvent from DAO, leading to an increase in solvent recovery. Also, numerical simulation results show the possibility of continuous operation for solvent recovery using CO<SUB>2</SUB>.</P> <P><B>Highlights</B></P> <P> <UL> <LI> Solvent recovery using CO<SUB>2</SUB> was newly developed for solvent deasphalting process. </LI> <LI> High solvent recovery was achieved at relatively low temperature. </LI> <LI> CO<SUB>2</SUB> acts as an anti-solvent to separate the solvent from DAO. </LI> <LI> Numerical simulation confirmed the possibility of a new solvent recovery operation. </LI> </UL> </P> <P><B>Graphical abstract</B></P> <P>[DISPLAY OMISSION]</P>

Separation of solvent and deasphalted oil for solvent deasphalting process

Lee, J.M.,Shin, S.,Ahn, S.,Chun, J.H.,Lee, K.B.,Mun, S.,Jeon, S.G.,Na, J.G.,Nho, N.S. Elsevier Scientific Pub. Co 2014 Fuel processing technology Vol.119 No.-

Due to the depletion of conventional oil resources and increasing prices, various technologies for utilizing unconventional oil and low-value crude residues, which have not been fully exploited, are currently being explored. The exploitation of unconventional oil and low-value crude residues requires upgrading processes such as carbon rejection and hydrogen addition. Among many existing upgrading processes, solvent deasphalting (SDA), a technology for removing asphaltene-rich pitch and producing higher-value deasphalted oil (DAO) by using paraffinic solvents, is promising because it offers the advantages of low installation cost and flexibility in terms of the control of the quality of pitch and DAO. The SDA process requires a considerable amount of expensive solvent. Thus, solvent recovery, an energy-intensive process, is required for improved efficiency. In this paper, DAO/solvent separation experiments were carried out using two solvents, pentane and hexane, to investigate the effect of operating conditions such as temperature, pressure, and DAO/solvent ratio on the process. The DAO/pentane separation was superior to the DAO/hexane separation under similar conditions. Regardless of the solvent type, solvent recovery was increased as the DAO/solvent ratio in the feed was decreased. Solvent recovery was strongly influenced by variations in temperature but was relatively insensitive to changes in pressure.

Development of correlations between deasphalted oil yield and Hansen solubility parameters of heavy oil SARA fractions for solvent deasphalting extraction

박준우,Min Yong Kim,Soo Ik Im,고강석,Nam-Sun Nho,Ki Bong Lee 한국공업화학회 2022 Journal of Industrial and Engineering Chemistry Vol.107 No.-

Solvent deasphalting (SDA) is a heavy oil upgrading process that selectively extracts deasphalted oil(DAO) and rejects asphaltenes. In this study, a quantitative analysis was conducted to predict DAO yieldsin the SDA process using relative energy difference (RED); the RED was calculated from Hansen solubilityparameters (HSPs) of the feedstock and extraction solvent along with the extraction conditions, such astemperature and solvent-to-oil ratio (SOR). SDA extraction experiments were performed in a continuousbench-scale unit using vacuum residue (VR) and a mixture of bunker C fuel oil (BC) and VR as feedstocks. The HSPs of saturate, aromatic, resin, and asphaltene fractions derived from the VR and BC were measuredusing solubility tests, wherein the fractions were dissolved in 37 different solvents. Finally, simpleand accurate correlations between the DAO yield and corresponding modified RED were acquired andused to explain the effects of temperature and SOR on the DAO yield.

Solvent recovery in solvent deasphalting process for economical vacuum residue upgrading

안선주,신상철,임수익,이기봉,노남선 한국화학공학회 2016 Korean Journal of Chemical Engineering Vol.33 No.1

The solvent deasphalting (SDA) process is a heavy oil upgrading process and used to separate asphaltene, the heaviest and most polar fraction of vacuum residue (VR) of heavy oil, by using density differences, to obtain deasphalted oil (DAO). The SDA process consists of two main stages: asphaltene separation and solvent recovery. Solvent recovery is a key procedure for determining the operating cost of the SDA process, because it uses a considerable amount of costly solvent, the recovery of which consumes huge amounts of energy. In this study, the SDA process was numerically simulated by using three different solvents, propane, n-butane, and isobutane, to examine their effect on the DAO extraction and the effect of the operating temperature and pressure on solvent recovery. The process was designed to contain one extractor, two flash drums, and two steam strippers. The VR was characterized by identifying 15 pseudo-components based on the boiling point distribution, obtained by performing a SIMDIS analysis, and the API gravity of the components. When n-butane was used, the yield of DAO was higher than in the other cases, whereas isobutane showed a similar extraction performance as propane. Solvent recovery was found to increase with temperature and decrease with pressure for all the solvents that were tested and the best results were obtained for propane.

Removal of asphaltene with oxidized asphaltene in water-in-crude oil emulsion for solvent deasphalting process

최선웅,변도현,김종득 한국공업화학회 2014 한국공업화학회 연구논문 초록집 Vol.2014 No.0

Asphaltene precipitation with partially oxidized asphaltene from water/heavy crude oil emulsion

Choi, Seonung,Byun, Do Hyun,Lee, Kwangse,Kim, Jong-Duk,Nho, Nam Sun Elsevier 2016 Journal of petroleum science & engineering Vol.146 No.-

<P><B>Abstract</B></P> <P>A novel asphaltene precipitation method of using partially oxidized asphaltene was proposed to reduce the amounts of asphaltene in heavy crude oil. Partially oxidized asphaltene enhanced the aggregation of asphaltene in oil, and the precipitation of asphaltene from heavy crude oil. By adding a small amount of partially oxidized asphaltene in water/diluted-crude-oil emulsion, a half of asphaltene and a quarter of resin in the feed stream were separated by a single cycle of centrifugation. The degree of oxidation of partially oxidized asphaltene may determine the selective dissolution between the oil phase and the water phase. The partially oxidized asphaltene, which has amphiphilic functional groups, is adsorbed on the interface between asphaltene and water, and can therefore facilitate the aggregation of asphaltene dissolved in the oil. The interfacial adsorption may be controlled by the hydrophilicity and aromaticity of surfactants and may contribute to the aggregation and separation of asphaltene. Therefore, it is believed that the pretreatment of partially oxidized asphaltene could significantly reduce the asphaltene load in a solvent deasphalting process.</P> <P><B>Highlights</B></P> <P> <UL> <LI> Asphaltene was converted into an effective additive and characterized various analysis. </LI> <LI> Asphaltene was precipitated in water/crude oil emulsion with oxidized asphaltene. </LI> <LI> About a half of asphaltene and a quarter of resin were separated. </LI> </UL> </P>

고품위화 정제공정 부산물(SDAR) 활용을 위한 첨가제 개발 및 이를 이용한 아스팔트 혼합물의 실내 공용성능 평가

백철민,양성린,황성도 한국도로학회 2016 한국도로학회논문집 Vol.18 No.6

OBJECTIVES: The objective of this research is to develop additives for the modification of Solvent DeAsphalting Residue (SDAR) to be used as pavement materials, and evaluate the performance of asphalt mixture manufactured using the SDAR modified by developed additives. METHODS: The SDAR generally consists of more asphaltenes and less oil components compared to the conventional asphalt binder, and hence, the chemical/physical properties of SDAR are different from that of conventional asphalt binder. In this research, the additives are developed using the low molecular oil-based plasticizer to improve the properties of SDAR. First, the chemical property of two SDARs is analyzed using SARA (saturate, aromatic, resin, and asphaltene) method. The physical/rheological properties of SDARs and SDARs containing additives are also evaluated based on PG-grade method and dynamic shear-modulus master curve. Second, various laboratory tests are conducted for the asphalt mixture manufactured using the SDAR modified with additives. The laboratory tests conducted in this study include the mix design, compactibility analysis, indirect tensile test for moisture susceptibility, dynamic modulus test for rheological property, wheeltracking test for rutting performance, and direct tension fatigue test for cracking performance. RESULTS : The PG-grade of SDARs is higher than PG 76 in high temperature grades and immeasurable in low temperature grades. The dynamic shear modulus of SDARs is much higher than that of conventional asphalt, but the modified SDARs with additives show similar modulus compared to that of conventional asphalt. The moisture susceptibility of asphalt mixture with modified SDARs is good if, the antistripping agent is included. The performance (dynamic modulus, rutting resistance, and fatigue resistance) of asphalt mixture with modified SDARs is comparable to that of conventional asphalt mixture when appropriate amount of additives is added. CONCLUSIONS: The saturate component of SDARs is much less than that of conventional asphalt, and hence, it is too hard and brittle to be used as pavement materials. However, the modified SDARs with developed additives show comparable or better rheological/physical properties compared to that of conventional asphalt depending on the type of SDAR and the amount of additives used.

고도정제 부산물의 기존 아스팔트 대체재료로서의 가능성 평가

백철민,양성린,이문섭,황성도 한국도로학회 2013 한국도로학회 학술대회 발표논문 초록집 Vol.2013 No.09

최근 급격하게 상승하기 시작한 원유 가격으로 원유가 점점 중질화함에 따라 고도 정제 기술이 전세계 적으로 활발히 개발되고 있다. 도로 포장 재료로서 가장 많이 사용되는 아스팔트는 기존 경질유를 정제하고 남은 부산물로서 지금까지는 특별한 처리공정 없이 사용이 가능하였다. 하지만, 저가 중질유분의 고도 정제 과정(Solvent Deasphalting Process, SDA 공정)에서 발생하는 부산물(Pitch)은 기존의 아스팔트와 매우 다른 화학적 성분과 함께 고점도의 물리적 특성 등으로 인해 작업성 및 시공성이 제한적이므로 건설 재료로 활용하는데 어려움이 있다. 본 연구에서는 저가 중질유분의 고도 정제 과정의 부산물을 건설재료로서 활용하기 위한 연구를 수행하였다. 본 연구에 사용된 Pitch는 국내 정유회사에서 SDA 공정을 거쳐 발생한 경질화 부산물로서 일반 아스팔 트의 품질기준으로 규정된 기본물성과 더불어 유변학적 특성을 분석하였다. Pitch의 기본물성 실험결과, 모든 기본 시험에서 일반 아스팔트에 비해 유연성이 현저히 감소되고 매우 단단한 재료인 것으로 평가되 었다. Pitch의 유변학적 특성 평가를 위해 DSR 레오미터를 이용한 온도와 하중빈도에 따른 동전단계수를 평가하였으며, Time-Temperature Superposition 기법을 이용하여 동전단계수 마스터곡선을 결정하였다. 그림 1에서 보이듯이, Pitch의 동전단계수는 전범위에 걸쳐 AP5 아스팔트에 비해 매우 큰 것을 알 수 있다. 이러한 Pitch의 특성을 개선하기 위해 오일계열의 첨가제를 첨가한 후 동전단계수 평가를 수행하였으며, 그림에서 나타나듯이 개선된 Pitch의 유변학적 특성이 AP5와 거의 유사한 것으로 평가되었다. 이상과 같은 실험결과를 바탕으로, 중질유분의 고도정제 과정에서 발생하는 부산물에 적절한 첨가제를 사용하다면 기존 아스팔트와 유사한 특성을 가지는 좋은 대체재료가 될 것으로 판단된다. 향후 개선된 Pitch를 아스팔트 혼합물에 적용하여 다양한 공용성 평가 및 실제 현장적용을 통해 기존 아스팔트 대체재료로서의 활용가능성에 대한 지속적인 연구를 수행할 계획이다.

Investigation of asphaltene extraction in a solvent deasphalting process on a bench scale unit

김영두,최선아,권은희,김광호,임석현,( Hai Hung Pham ),노남선 한국공업화학회 2023 한국공업화학회 연구논문 초록집 Vol.2023 No.1

A Study on DAO Extraction Using Vacuum Residue in Bench scale SDA Process

김영두,최선아,권은희,김광호,임석현,( Hai Hung Pham ),노남선 한국공업화학회 2023 한국공업화학회 연구논문 초록집 Vol.2023 No.0