CN112391193B - Method for adsorbing and removing dibenzothiophene - Google Patents
Method for adsorbing and removing dibenzothiophene Download PDFInfo
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- CN112391193B CN112391193B CN202011260873.8A CN202011260873A CN112391193B CN 112391193 B CN112391193 B CN 112391193B CN 202011260873 A CN202011260873 A CN 202011260873A CN 112391193 B CN112391193 B CN 112391193B
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- dibenzothiophene
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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
- C10G25/00—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents
- C10G25/003—Specific sorbent material, not covered by C10G25/02 or C10G25/03
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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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
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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)
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- Silicates, Zeolites, And Molecular Sieves (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
A method for adsorbing and removing dibenzothiophene, belonging to the field of adsorption and separation. The method for solving the technical problem is to contact an adsorbent with the mixture, wherein the adsorbent is a composite adsorbent synthesized by polyethylene glycol and sodium montmorillonite; the mixture comprises dibenzothiophene and at least one solvent. The method provided by the invention has the advantages of low cost, mild operation condition, high extraction and removal efficiency and environmental friendliness.
Description
Technical Field
The invention relates to the field of adsorption separation, in particular to a method for adsorbing and removing dibenzothiophene.
Background
With the high-speed development of modern cities, the number of motor vehicles is growing at an exponential rate, and the level of all pollutants emitted by motor vehicles is closely related to the sulfur content in oil products. In order to protect the environment, increasingly strict standards for the sulfur content of light oils are promulgated successively by countries in the world. At present, the sulfur content in domestic gasoline is high due to the large amount of imported high-sulfur crude oil in China, so that the removal of sulfides in fuel oil is extremely important, and especially the deep removal of organic sulfides is the key point in the current desulfurization research field.
Although the traditional hydrodesulfurization method can effectively remove small molecular sulfur compounds such as mercaptan, thioether and the like, the thiophene organic sulfide is difficult to remove. Meanwhile, hydrodesulfurization needs high temperature and high pressure and high-efficiency catalyst, and side reaction can cause octane value reduction of oil products[1]. Therefore, more and more researchers shift the research focus to non-hydrodesulfurization, which mainly includes adsorption desulfurization, biological desulfurization, extraction desulfurization, alkylation desulfurization, oxidation desulfurization and the like[2]. Wherein the adsorption desulfurization has the advantages of low equipment investment, high desulfurization economy, no need of hydrogen and oxidant, simple process, easy operation, low investment and operation cost, and the like, and has larger development space and application potential[3]。
Montmorillonite (MMT) is the main component of the silicate natural mineral bentonite. The bentonite ore resources in China are rich and widely distributed, and 23 provinces (regions) in China all have bentonite ore output, and the reserves are the first in the world, so the montmorillonite has the advantages of nature, low price, large yield and the like. Meanwhile, the montmorillonite also has a series of characteristics of expansibility, ion exchange property, adsorptivity, dispersibility, stability, no toxicity and the like[4]However, the montmorillonite has small interlayer spacing and limited adsorption capacity because the active sites are occupied, thereby limiting the application range of the montmorillonite. The modification treatment is carried out on the modified MMT, so that the interlayer structure and the adsorption performance of the MMT are improved, and the application prospect of the MMT can be widened. Polyethylene glycol is nontoxic and nonirritatingNeutral high molecular polymer can improve interlaminar microenvironment of montmorillonite and enhance adsorption property of montmorillonite[5]. And the polyethylene glycol has good extraction and removal performance on organic sulfides in the fuel oil[6,7]. The polyethylene glycol and the montmorillonite are organically combined, the montmorillonite is modified by the polyethylene glycol, the synergistic effect of the polyethylene glycol and the montmorillonite is exerted, and the problem of low desulfurization efficiency of the montmorillonite is solved, so that the synergistic and efficient green deep desulfurization of the polyethylene glycol and the montmorillonite is realized.
Reference documents:
[1] sunzhijuan, Simouxin, Zhang Xinya, etc. the research on the removal technique of thiophene sulfides in oil products is advanced [ J ] the progress of chemical engineering, 2005,24, 1002-.
[2] Zhengkaiyuan, Qufengjiao, Chenying, etc. non-hydrodesulfurization technical research progress and application prospect in crude oil pre-desulfurization [ J ] chemical progress, 2013,32, 2859-supplement 2866.
[3] Miao Guang, Dong Lei, ren Xiao Ling, etc. research progress of fuel adsorption desulfurization [ J ] chemical progress 2020,39(6):2251-2261.
[4] Processing and application of ginger-Guilan, Zhang Peckweed and bentonite, Beijing, chemical industry Press, 2005.
[5] Lukeming, yulin beam, chenmin, et al preparation and structural characterization of polyethylene glycol/montmorillonite intercalated complexes [ J ], university of south china university of agriculture (natural science edition), 2004,25,112.
[6]E.Kianpour,S.Azizian,Polyethylene glycol as a green solvent for effective extractive desulfurization of liquid fuel at ambient conditions[J],Fuel,2014,137,36.
[7]Z.Li,Y.N.Cui,C.P.Li et al.Deep desulfurization of fuels based on deep eutectic theory[J],Separation and Purification Technology,2019,219,9.
Disclosure of Invention
Aiming at the defects, the invention provides a method for adsorbing and removing dibenzothiophene, and the method uses an adsorbent which is cheap and easy to obtain, is green and environment-friendly, has high desulfurization rate, and realizes the deep removal of dibenzothiophene in fuel oil.
The method for solving the technical problem is to contact an adsorbent with a mixture, wherein the adsorbent is a composite adsorbent synthesized by polyethylene glycol (PEG) and sodium montmorillonite; the mixture comprises dibenzothiophene and at least one solvent.
Further, the adsorbent is a composite adsorbing material synthesized by polyethylene glycol and sodium montmorillonite through an impregnation method, wherein the polyethylene glycol is one of PEG200, PEG400, PEG600, PEG1000, PEG2000, PEG4000, PEG6000, PEG10000 and PEG 20000.
Furthermore, the mixture consists of dibenzothiophene and n-octane, wherein the concentration of sulfur is 400-1600 ppm.
Further, the mass ratio of the adsorbent to the mixture is 0.1: 1-0.5: 1.
Further, the adsorption method comprises the steps of mixing the adsorbent with the mixture, and stirring for 5-60 min at the temperature of 20-50 ℃, wherein the stirring speed is 600-1000 rpm.
Further, mixing the polyethylene glycol-sodium montmorillonite composite adsorbent with a dibenzothiophene n-octane solution with the sulfur concentration of 400-1600 ppm according to the mass ratio of 0.1: 1-0.5: 1, stirring for 5-60 min at the temperature of 20-60 ℃, stirring at the speed of 600-1000 rpm, and standing for layering.
Has the advantages that: the method provided by the invention has the advantages of low cost, mild operation condition, high extraction and removal efficiency and environmental friendliness.
Detailed Description
The present invention is described by the following examples, but the present invention is not limited to the following examples, and variations and implementations are included in the technical scope of the present invention without departing from the spirit of the invention described above and below.
Example 1
0.2008g of PEG 200-sodium montmorillonite composite adsorbent and 1.0032g of dibenzothiophene n-octane solution with sulfur concentration of 1600ppm are weighed, stirred for 30min at 25 ℃, the stirring speed is 600rpm, and after standing and layering, the sulfur concentration in the n-octane layer is detected by using a gas chromatography, and the desulfurization rate is 73.44 percent.
Example 2
0.2010g of PEG 400-sodium montmorillonite composite adsorbent and 1.0039g of dibenzothiophene n-octane solution with sulfur concentration of 1600ppm are weighed, stirred for 30min at 25 ℃, the stirring speed is 600rpm, and after standing and layering, the sulfur concentration in the n-octane layer is detected by using a gas chromatography, and the desulfurization rate is calculated to be 75.90%.
Example 3
0.2009g of PEG 600-sodium montmorillonite composite adsorbent and 1.0038g of dibenzothiophene n-octane solution with sulfur concentration of 1600ppm are weighed, stirred for 30min at 25 ℃, the stirring speed is 600rpm, and after standing and layering, the sulfur concentration in the n-octane layer is detected by using a gas chromatography, and the desulfurization rate is calculated to be 77.84%.
Example 4
0.2001g of PEG 1000-sodium montmorillonite composite adsorbent and 1.0011g of dibenzothiophene n-octane solution with sulfur concentration of 1600ppm are weighed, stirred for 30min at 25 ℃, the stirring speed is 600rpm, and after standing and layering, the sulfur concentration in the n-octane layer is detected by using a gas chromatography, and the desulfurization rate is calculated to be 79.21%.
Example 5
0.2005g of PEG 2000-Na-montmorillonite composite adsorbent and 1.0028g of dibenzothiophene n-octane solution with sulfur concentration of 1600ppm are weighed, stirred for 30min at 25 ℃, the stirring speed is 600rpm, and after standing and layering, the sulfur concentration of the n-octane layer is detected by using a gas chromatography, and the desulfurization rate is 80.04 percent.
Example 6
0.2007g of PEG 4000-Na-montmorillonite composite adsorbent and 1.0027g of dibenzothiophene n-octane solution with sulfur concentration of 1600ppm are weighed, stirred for 30min at 25 ℃, the stirring speed is 600rpm, and after standing and layering, the sulfur concentration in the n-octane layer is detected by using a gas chromatography, and the desulfurization rate is calculated to be 81.54%.
Example 7
Weighing 0.2010g of PEG 6000-sodium montmorillonite composite adsorbent and 1.0044g of dibenzothiophene n-octane solution with sulfur concentration of 1600ppm, stirring for 30min at 25 ℃, wherein the stirring speed is 600rpm, standing for layering, detecting the sulfur concentration in the n-octane layer by using a gas chromatography, and calculating to obtain the desulfurization rate of 83.01%.
Example 8
0.2004g of PEG 10000-Na-montmorillonite composite adsorbent and 1.0018g of dibenzothiophene n-octane solution with sulfur concentration of 1600ppm are weighed, stirred for 30min at 25 ℃, the stirring speed is 600rpm, after standing and layering, the sulfur concentration in the n-octane layer is detected by using a gas chromatography, and the desulfurization rate is calculated to be 85.45%.
Example 9
Weighing 0.2009g of PEG 10000-Na-montmorillonite composite adsorbent and 1.0030g of dibenzothiophene n-octane solution with the sulfur concentration of 400ppm, stirring for 30min at 25 ℃, wherein the stirring speed is 600rpm, standing for layering, detecting the sulfur concentration in the n-octane layer by using a gas chromatography, and calculating to obtain the desulfurization rate of 85.83%.
Example 10
0.4012g of PEG 10000-Na-montmorillonite composite adsorbent and 1.0023g of dibenzothiophene n-octane solution with sulfur concentration of 1600ppm are weighed, stirred for 30min at 25 ℃, the stirring speed is 600rpm, and after standing and layering, the sulfur concentration in the n-octane layer is detected by using a gas chromatography, and the desulfurization rate is 88.45 percent.
Example 11
Weighing 0.2010g of PEG 10000-Na-montmorillonite composite adsorbent and 1.0028g of dibenzothiophene n-octane solution with sulfur concentration of 1600ppm, stirring for 60min at 25 ℃, wherein the stirring speed is 600rpm, standing for layering, detecting the sulfur concentration in the n-octane layer by using a gas chromatography, and calculating to obtain the desulfurization rate of 85.63%.
Example 12
Weighing 0.2014g of PEG 10000-Na-montmorillonite composite adsorbent and 1.0018g of dibenzothiophene n-octane solution with sulfur concentration of 1600ppm, stirring for 30min at 40 ℃, stirring at the speed of 600rpm, standing for layering, detecting the sulfur concentration in the n-octane layer by using a gas chromatography, and calculating to obtain the desulfurization rate of 82.09%.
Example 13
Weighing 1.0050g of PEG 10000-Na-montmorillonite composite adsorbent and 5.0054g of dibenzothiophene n-octane solution with sulfur concentration of 1600ppm, stirring at 25 ℃ for 30min at a stirring speed of 600rpm, standing for layering, and detecting the sulfur concentration in the n-octane layer by using a gas chromatography, wherein the sulfur concentration is 232.80 ppm; 4.0018g of the dibenzothiophene n-octane solution is taken, 0.8016g of PEG 10000-sodium montmorillonite composite adsorbent is added, the mixture is stirred for 30min at the temperature of 25 ℃, the stirring speed is 600rpm, the mixture is kept still for layering, and the sulfur concentration in the n-octane layer is detected by using a gas chromatography, wherein the sulfur concentration is 101.12 ppm; 3.0022g of the dibenzothiophene n-octane solution is taken, 0.6011g of PEG 10000-sodium montmorillonite composite adsorbent is added, the mixture is stirred for 30min at the temperature of 25 ℃, the stirring speed is 600rpm, the mixture is kept still for layering, and the sulfur concentration in the n-octane layer is detected by using gas chromatography, wherein the sulfur concentration is 44.71 ppm; 2.0017g of the dibenzothiophene n-octane solution is taken, 0.4009g of PEG 10000-sodium montmorillonite composite adsorbent is added, the mixture is stirred for 30min at the temperature of 25 ℃, the stirring speed is 600rpm, the mixture is kept still for layering, and the sulfur concentration in the n-octane layer is detected by using a gas chromatography, wherein the sulfur concentration is 17.91 ppm; taking 1.0008g of the dibenzothiophene n-octane solution, adding 0.2013g of PEG 10000/sodium montmorillonite composite adsorbent, stirring at the temperature of 25 ℃ for 30min at the stirring speed of 600rpm, standing for layering, and detecting the sulfur concentration in the n-octane layer by using a gas chromatography, wherein the sulfur concentration is 8.08 ppm.
While the invention has been described with reference to specific embodiments, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (3)
1. The method for adsorbing and removing dibenzothiophene is characterized in that an adsorbent is in contact with and mixed with a mixture, and the mixture is stirred for 5-60 min at the temperature of 20-50 ℃ and the stirring speed is 600-1000 rpm, wherein the adsorbent is a composite adsorbent synthesized from polyethylene glycol and sodium-based montmorillonite; the mixture comprises dibenzothiophene and at least one solvent; the adsorbent is a composite adsorption material synthesized by polyethylene glycol and sodium montmorillonite through an impregnation method, wherein the polyethylene glycol is one of PEG2000, PEG4000, PEG6000, PEG10000 and PEG 20000; the mass ratio of the adsorbent to the mixture is 0.1: 1-0.5: 1.
2. The method for adsorbing and removing dibenzothiophene according to claim 1, wherein the mixture is composed of dibenzothiophene and n-octane, and the concentration of sulfur is 400-1600 ppm.
3. The method for adsorbing and removing dibenzothiophene according to claim 2, wherein the composite adsorbent is mixed with a dibenzothiophene n-octane solution with sulfur concentration of 400-1600 ppm according to a mass ratio of 0.1: 1-0.5: 1, stirred at a stirring speed of 600-1000 rpm for 5-60 min at 20-50 ℃, and then allowed to stand for layering.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| GB823969A (en) * | 1955-07-28 | 1959-11-18 | Union Carbide Corp | Improvements in adsorbents and the separation of mixtures |
| CN1212375C (en) * | 2003-01-24 | 2005-07-27 | 中国石油化工股份有限公司 | Adsorbent for desulfurizing fuel oil and preparation method |
| CN1234808C (en) * | 2004-03-11 | 2006-01-04 | 天津大学 | Desulfate adsorbing agent for deep purifying sulfide in fuel oil and preparation process thereof |
| US20070138062A1 (en) * | 2005-12-15 | 2007-06-21 | The U. S. A. As Represented By The Administrator Of The U.S. Environ. Protection Agency | Sorbent compositions and desulfurization method using same |
| CN101372633B (en) * | 2007-08-22 | 2012-12-26 | 华东理工大学 | Fuel oil desulfurizer and preparation thereof |
| US20140374320A1 (en) * | 2010-07-20 | 2014-12-25 | Hsin Tung Lin | Method for Removing Sulfides from a Liquid Fossil Fuel |
| CN108192658A (en) * | 2017-12-20 | 2018-06-22 | 湖南大学 | The method of dibenzothiophenes in a kind of catalysis oxidation-filtering removal oil product |
| CN108579125A (en) * | 2018-05-11 | 2018-09-28 | 东莞理工学院 | A kind of adsorption method of dibenzothiophenes |
| CN109574119A (en) * | 2018-12-11 | 2019-04-05 | 嘉兴沃特泰科环保科技有限公司 | Modified alta-mud and its preparation process |
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