EP2650345A1 - Procédé d'élimination du soufre contenant des composés à partir de mélanges d'hydrocarbures - Google Patents

Procédé d'élimination du soufre contenant des composés à partir de mélanges d'hydrocarbures Download PDF

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Publication number
EP2650345A1
EP2650345A1 EP12164043.7A EP12164043A EP2650345A1 EP 2650345 A1 EP2650345 A1 EP 2650345A1 EP 12164043 A EP12164043 A EP 12164043A EP 2650345 A1 EP2650345 A1 EP 2650345A1
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Prior art keywords
compound
acid
deep eutectic
sulfur containing
eutectic solvent
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German (de)
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EP2650345B1 (fr
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Saeed Mohammed A-Zahrani
Inas Muen AlNashef
Sarwono Mulyono Mulyoprayitno
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King Saud University
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King Saud University
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G21/00—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents
    • C10G21/06—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents characterised by the solvent used
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G21/00—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents
    • C10G21/28—Recovery of used solvent

Definitions

  • the present invention relates to a method for removal of sulfur containing compounds from liquid hydrocarbons containing the sulfur containing compounds.
  • a deep eutectic solvent is a type of ionic solvent with special properties composed of a mixture of compounds which form an eutectic with a melting point much lower than either of the individual components.
  • DESs are useful as solvents, as electrolytes and as catalysts. Although DESs have many common characteristics with ionic liquids, they are considered as different type of solvents. Ionic liquids are composed entirely from ions while DESs have both ions and neutral molecules. In addition, ionic liquids are synthesized by chemical reactions while DESs are prepared by mixing and heating only. The first generation of eutectic solvents was based on mixtures of quaternary ammonium salts with hydrogen bond donors such as amines and carboxylic acids.
  • ionic liquids Compared to ionic liquids, they share many characteristics but are ionic compounds and not ionic mixtures, deep eutectic solvents are cheaper to make, much less toxic and sometimes biodegradable.
  • the major advantages of the approach used for the synthesis of DESs is that common, non-toxic components can be used and that they are easy to make by just mixing two compounds with gentle heating and subsequent cooling to room temperature.
  • WO 02/26701 relates to a method for the synthesis of DESs by the mixing of an amine salt, such as choline chloride, with an organic compound capable of forming hydrogen bond with the ion of the amine salt, such as urea.
  • WO 00/56700 relates to a method for the synthesis of deep eutectic solvents formed by mixing a quaternary ammonium compound or a mixture of two or more thereof with a halide of zinc, tin or iron or a mixture of two or more thereof.
  • US 7,763,768 discloses the use of a deep eutectic solvent comprising a quaternary ammonium salt and different hydrogen bond donors as a solvent for the preparation of hydrogen peroxide.
  • Sulfur compounds are the most notorious and undesirable petroleum contaminants and a large portion of these compounds is transferred to diesel oil during refining process.
  • sulfur occurs here in the form of hydrogen sulfide, organic sulfides and disulfides, benzothiophene, dibenzothiophene and their alkylated derivatives.
  • Sulfur compounds are usually present in almost all fractions of crude oil distillation. Higher boiling point fractions contain relatively more sulfur and the sulfur compounds are of higher molecular weight.
  • US 5,766,482 A relates to a process for capture, degradation and destruction of sulphur bearing compound by reacting a sulphur component containing mixture with a mixture of metals insoluble with a sulphur bearing compound, reduction agents and bases.
  • US 7,758,745 B2 relates to a diesel desulfurization method comprising mixing diesel fuel with room temperature ionic liquid, oxidant, phase transfer catalyst and acid catalyst in a tank in a mix, recycling the ionic liquid and recycling the acid catalyst in aqueous phase.
  • US 7,001,504 B2 discloses a method for extraction of organosulfur compounds from hydrocarbon using ionic liquids.
  • R 1 , R 2 , R 3 and R 4 are independently selected from substituted or unsubstituted, linear or branched C 1 -C 18 alkyl, C 1 -C 10 alkoxy, C 6 -C 10 cycloalkyl, C 6 -C 10 aryl or C 7 -C 12 alkaryl.
  • X is chlorine or bromine, preferably chlorine.
  • R 1 , R 2 , R 3 and R 4 can optionally be substituted with OH, SH, SR 5 , Cl, Br, F, I, NH 2 , CN, NO 2 CO 2 R 5 , CHO, COR 5 and/or OR 5 , wherein R 5 is selected from alkyl or cycloalkyl, more preferably, C 1 -C 10 alkyl or cycloalkyl.
  • the sulfur containing compound is selected from the group consisting of hydrogen sulfide, linear, branched or cyclic, aromatic or aliphatic thiols, thioethers and disulfides, preferably is thiophene and/or dibenzothiophene.
  • the invention further proposes that the sulfur containing compound does not contain any halogen atoms.
  • the at least one liquid hydrocarbon is crude oil and/or at least one fuel.
  • the molar ratio of compound (I) to compound (II) is 1:2.
  • the ratio of the at least one deep eutectic solvent to the at least one liquid hydrocarbon is in a range from 1:1 to 5:1.
  • step a), b) and/or c) is carried out within a temperature range from 25 to 100°C.
  • the pressure in step a), b) and/or c) is within a range from 1 to 10 bar.
  • the electrochemical generating takes place in a membrane electrochemical reactor.
  • the deep eutectic solvent has a freezing point of up to 100°C.
  • the hydrogen bond donor is selected from urea, acetamide, thiourea, glycoxic acid, malonic acid, oxalic acid dihydrate, trifluoro acetic acid, benzoic acid, benzyl alcohol, phenol, p-methylphenol, o-methylphenol, m-methylphenol, p-chlorophenol, D-fructase, vanillin, aniline or a substituted aniline, a C 1 -C 6 aliphatic acid, a C 1 -C 6 hydroxy aliphatic acid, a dicarboxylic acid of the formula HOOC (CH 2 ) n COOH, wherein n is 0 or 1, alkylene glycol, citric acid or ethylene glycol.
  • sulphur containing compounds can be removed from liquid hydrocarbons by the inventive method in an easy, cheap and efficient way.
  • inventive method allows an efficient extraction of sulphur containing compounds from liquid hydrocarbon mixtures as well as an easy subsequent decomposition of the extracted sulphur containing compounds in DESs by utilization of super oxide ions.
  • the at least one liquid hydrocarbon according to the inventive method can comprise one or more different liquid hydrocarbons.
  • other non-liquid hydrocarbon constituents can be contained, for example nitrogen or oxygen containing organic compounds like amines, alcohols, etc., as long as there is no interaction of this constituents which inhibits the extraction and/or the decomposition of the sulphur containing compound in a non-acceptable way.
  • the inventive method can be applied in the oil industry for the removal of sulphur containing compounds from the various hydrocarbon mixtures occuring in this field, for example for the removal from sulphur containing compound from crude oil, oil, petroleum, mineral oil, kerosine, petrol, gasoline, liquid paraffins, diesel etc..
  • Fig. 1 shows HPLC chromatograms of thiophene in a DES of choline chloride with ethylene glycol in a molar ratio of 1:3 after the extraction step with and without the addition of different amounts of KO 2 .
  • the used compounds were obtained from different sources. The stated purity of the used substrates was ⁇ 99%. All chemicals were used without further purification.
  • the extraction of the sulphur containing compound by means of the deep eutectic solvent was carried at a pressure of 100 kPa at a temperature of 25°C.
  • extraction at a temperature of up to 100°C and under increased pressure was obtained to be possible and advantageously in some cases.
  • a DES was synthesized by mixing choline chloride with ethylene glycol in a 1:3 mol ratio. The mixture was heated up to 70 °C under vigorous mixing for three hours. The freezing point of the resulting DES was less than room temperature. About 1 g of thiophene was added in decane as a model compound of diesel. A sample was drawn from the mixture of decane with thiophene, diluted with propanol and analyzed using HPLC. The extraction of thiophene from decane was performed by adding the DES to the decane phase in different mass ratios (0.75 - 3 mass units DES per 1 mass unit decane).
  • the mixtures were then agitated for at least 1 hour at about 200 rpm using an orbital shaker under ambient temperatures. After two hours of settling, the upper and bottom layers were separated using a saparatary funnel and samples from both phases were taken and analyzed using HPLC technique. HPLC analysis showed that about 40% of the thiophene was extracted by the DES for a mass ratio of DES:decane of 1:1.
  • Cyclic voltammetry was used as electrochemical analysis technique.
  • the DES to be used was dried overnight in a vacuum oven at 50 °C.
  • Electrochemical experiments were performed using EG&G 263A potentiostat/galvanostat controlled by computer and data acquisition software. CVs were conducted in a one compartment cell since the time of the experiment is relatively small to affect the DES.
  • the cell was a jacketed vessel (10 ml volume) with a Teflon cap including 4 holes for the three electrochemical electrodes and for gas sparging tube.
  • Glassy carbon (GC) macro-disc electrode was used as working electrode for cyclic voltammetry, while platinum mesh was used for the bulk electrolysis.
  • Platinum electrode was used as a counter electrode and Ag/AgCI electrode was used as a reference electrode. All experiments were performed in a dry glove box under either an argon or helium atmosphere. Prior to O 2 •- generation, a background voltammogram was obtained after removal of O 2 . The O 2 removal was achieved by purging the DES with dry N 2 . Oxygen was then bubbled into the tested DES for at least 30 min to ensure that the equilibrium was achieved. In addition, in order to confirm that the tested DES is saturated with O 2 , CVs at different time intervals were conducted and the final measurement was taken when the cathodic peak current of the CV was constant. Between consecutive CV runs, O 2 was bubbled briefly to refresh the system and to remove any concentration gradients.
  • the cathode and anode compartments were made of Plexiglas with appropriate openings to accommodate the electrodes and to load and unload solutions.
  • Proton transfer membranes of different thickness were used as a separator between the cathode and anode compartments.
  • the membranes were soaked in a boiling 5M NaOH solution for 2-3 h to get rid of H + and then in boiling distilled water for about 1 h. In some cases the membrane was soaked with DES for 24 h before being used.
  • the current density ranged from 1-2 mA/cm 2 depending on the type of electrode and reactor. The current efficiency was higher than 90% in all cases.
  • the sulfur containing compound decomposition was monitored as described in Example 3.
  • Potassium superoxide was added gradually into a vial containing the DES and the sulphur containing compound after extraction, the bottom layer in Example 1, under vigorous stirring.
  • Samples, before and after the addition of KO 2 were taken by dissolving 0.1 g of DES solution in 1 g of acetonitrile. The samples were then analyzed using HPLC.
  • Figure 1 shows that the peak representing thiophene decreased gradually with addition of KO 2 . The total destruction was about 98%. This procedure was repeated and more KO 2 was added until the peak of sulfur compound was not detected or did not change and then the sample was analyzed using GC/MS.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
EP20120164043 2012-04-13 2012-04-13 Procédé d'élimination du soufre contenant des composés à partir de mélanges d'hydrocarbures Not-in-force EP2650345B1 (fr)

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Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105294741A (zh) * 2015-12-03 2016-02-03 大连大学 以深共融溶剂为溶剂合成Cu-BTC材料的方法
CN105462607A (zh) * 2016-01-13 2016-04-06 山东联星能源集团有限公司 催化裂化汽油脱硫的组合工艺
CN107163977A (zh) * 2017-07-12 2017-09-15 青岛科技大学 一种邻卤芳香醇类低温共熔溶剂萃取脱硫的方法
CN107312565A (zh) * 2017-08-31 2017-11-03 青岛科技大学 一种三组分低共熔剂萃取脱硫的方法
CN107789376A (zh) * 2017-11-02 2018-03-13 南京林业大学 一种提取银杏叶活性成分的两相深共熔溶剂及其制备方法和提取方法
CN107987867A (zh) * 2017-11-14 2018-05-04 天津大学 用于重质油矿分离的微乳液萃取剂及用法
CN108840311A (zh) * 2018-06-22 2018-11-20 南京大学 一种以低共熔溶剂为介质的硫化氢液相氧化脱除法
CN109721145A (zh) * 2019-03-05 2019-05-07 河北科技大学 一种基于氨基酸类低共熔溶剂分离废水中酚类污染物的方法
CN112048334A (zh) * 2020-08-31 2020-12-08 上饶师范学院 一种芳香酸类低共熔溶剂萃取脱氮的方法
WO2022023986A1 (fr) * 2020-07-28 2022-02-03 Curve Energy Pte. Ltd. Procédé de désulfuration d'une composition d'huile
CN114887659A (zh) * 2022-03-21 2022-08-12 江苏大学 一种金属-磷酸配位型低共熔溶剂以及其在催化氧化燃油脱硫中的应用

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Publication number Priority date Publication date Assignee Title
US5766482A (en) 1996-05-21 1998-06-16 Paul B. Bertan's Living Trust Capture, degradation, and destruction of sulfur bearing compounds
WO2000056700A1 (fr) 1999-03-24 2000-09-28 University Of Leicester Liquides ioniques
WO2002026701A2 (fr) 2000-09-27 2002-04-04 Scionix Limited Liquides ioniques et leur utilisation comme solvants
US7001504B2 (en) 2001-11-06 2006-02-21 Extractica, Llc. Method for extraction of organosulfur compounds from hydrocarbons using ionic liquids
US7758745B2 (en) 2008-03-20 2010-07-20 Shun-Sheng Cheng Diesel desulfurization method
US7763768B2 (en) 2007-07-05 2010-07-27 King Saud University Method for the preparation of reactive hydrogen peroxide in deep eutectic solvents

Patent Citations (6)

* Cited by examiner, † Cited by third party
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US5766482A (en) 1996-05-21 1998-06-16 Paul B. Bertan's Living Trust Capture, degradation, and destruction of sulfur bearing compounds
WO2000056700A1 (fr) 1999-03-24 2000-09-28 University Of Leicester Liquides ioniques
WO2002026701A2 (fr) 2000-09-27 2002-04-04 Scionix Limited Liquides ioniques et leur utilisation comme solvants
US7001504B2 (en) 2001-11-06 2006-02-21 Extractica, Llc. Method for extraction of organosulfur compounds from hydrocarbons using ionic liquids
US7763768B2 (en) 2007-07-05 2010-07-27 King Saud University Method for the preparation of reactive hydrogen peroxide in deep eutectic solvents
US7758745B2 (en) 2008-03-20 2010-07-20 Shun-Sheng Cheng Diesel desulfurization method

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FA-TANG LI ET AL: "Desulfurization of dibenzothiophene by chemical oxidation and solvent extraction with Me3NCH2C6H5Cl.2ZnCl2 ionic liquid", GREEN CHEMISTRY, vol. 11, no. 6, 1 January 2009 (2009-01-01), pages 883, XP055033879, ISSN: 1463-9262, DOI: 10.1039/b815575e *
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Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105294741A (zh) * 2015-12-03 2016-02-03 大连大学 以深共融溶剂为溶剂合成Cu-BTC材料的方法
CN105462607A (zh) * 2016-01-13 2016-04-06 山东联星能源集团有限公司 催化裂化汽油脱硫的组合工艺
CN105462607B (zh) * 2016-01-13 2017-09-12 山东联星能源集团有限公司 催化裂化汽油脱硫的组合工艺
CN107163977B (zh) * 2017-07-12 2019-03-29 青岛科技大学 一种邻卤芳香醇类低温共熔溶剂萃取脱硫的方法
CN107163977A (zh) * 2017-07-12 2017-09-15 青岛科技大学 一种邻卤芳香醇类低温共熔溶剂萃取脱硫的方法
CN107312565A (zh) * 2017-08-31 2017-11-03 青岛科技大学 一种三组分低共熔剂萃取脱硫的方法
CN107312565B (zh) * 2017-08-31 2019-05-03 青岛科技大学 一种三组分低共熔剂萃取脱硫的方法
CN107789376A (zh) * 2017-11-02 2018-03-13 南京林业大学 一种提取银杏叶活性成分的两相深共熔溶剂及其制备方法和提取方法
CN107987867A (zh) * 2017-11-14 2018-05-04 天津大学 用于重质油矿分离的微乳液萃取剂及用法
CN107987867B (zh) * 2017-11-14 2020-05-22 天津大学 用于重质油矿分离的微乳液萃取剂及用法
CN108840311A (zh) * 2018-06-22 2018-11-20 南京大学 一种以低共熔溶剂为介质的硫化氢液相氧化脱除法
CN109721145A (zh) * 2019-03-05 2019-05-07 河北科技大学 一种基于氨基酸类低共熔溶剂分离废水中酚类污染物的方法
WO2022023986A1 (fr) * 2020-07-28 2022-02-03 Curve Energy Pte. Ltd. Procédé de désulfuration d'une composition d'huile
CN112048334A (zh) * 2020-08-31 2020-12-08 上饶师范学院 一种芳香酸类低共熔溶剂萃取脱氮的方法
CN112048334B (zh) * 2020-08-31 2022-06-17 上饶师范学院 一种芳香酸类低共熔溶剂萃取脱氮的方法
CN114887659A (zh) * 2022-03-21 2022-08-12 江苏大学 一种金属-磷酸配位型低共熔溶剂以及其在催化氧化燃油脱硫中的应用
CN114887659B (zh) * 2022-03-21 2023-08-04 江苏大学 一种金属-磷酸配位型低共熔溶剂以及其在催化氧化燃油脱硫中的应用

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