阅读说明：本技术 一种吸附脱除噻吩的方法 (Method for adsorbing and removing thiophene ) 是由 李慎敏 崔颖娜 贾颖萍 刘璇 于 2020-11-12 设计创作，主要内容包括：一种吸附脱除噻吩的方法,属于吸附分离领域。本发明解决技术问题问题采用的方法是使吸附剂与混合物接触,其中,吸附剂为由聚乙二醇与钠基蒙脱石合成的复合吸附剂；所述混合物包含噻吩和至少一种溶剂。本发明提供的方法成本低、操作条件温和、萃取脱除效率高和环境友好。(A method for adsorbing and removing thiophene, belonging to the field of adsorption 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 thiophene 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.)

1. The method for adsorbing and removing thiophene is characterized in that an adsorbent is contacted with a mixture, wherein the adsorbent is a composite adsorbent synthesized by polyethylene glycol and sodium montmorillonite; the mixture comprises thiophene and at least one solvent.

2. The method for adsorbing and removing thiophene according to claim 1, wherein the adsorbent is a composite adsorbing material synthesized by polyethylene glycol and sodium-based montmorillonite through an impregnation method, wherein the polyethylene glycol is one of PEG200, PEG400, PEG600, PEG1000, PEG2000, PEG4000, PEG6000, PEG10000 and PEG 20000.

3. The method for adsorbing and removing thiophene according to claim 1, wherein the mixture is composed of thiophene and n-octane, and the concentration of sulfur is 400-1600 ppm.

4. The method for adsorbing and removing thiophene according to claim 1, wherein the mass ratio of the adsorbent to the mixture is 0.1:1 to 0.5: 1.

5. The method for adsorbing and removing thiophene according to claim 1, wherein the adsorbing method comprises mixing an adsorbent with the mixture, and stirring at a temperature of 20-50 ℃ for 5-60 min at a stirring speed of 600-1000 rpm.

6. The method for adsorbing and removing thiophene according to claim 1, wherein the polyethylene glycol-sodium montmorillonite composite adsorbent is mixed with a thiophene n-octane solution with the sulfur concentration of 400-1600 ppm according to the mass ratio of 0.1: 1-0.5: 1, stirred at the stirring speed of 600-1000 rpm for 5-60 min at 20-60 ℃, and then kept standing for layering.

Technical Field

The invention relates to the field of adsorption separation, in particular to a method for adsorbing and removing thiophene.

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 oil product octaneReduction of the cetane number^[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 of the montmorillonite 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 as a nontoxic and nonirritating neutral high molecular polymer can improve the microenvironment between montmorillonite layers and enhance the 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 thiophene, 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 thiophene in fuel oil.

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 (PEG) and sodium montmorillonite; the mixture comprises thiophene 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 thiophene 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 thiophene 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 conditions, high extraction and removal efficiency and environmental friendliness, and the sulfur concentration can be reduced to below 10 ppm.

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

0.2001g of PEG 200-sodium montmorillonite composite adsorbent and 1.0003g of thiophene 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 56.45 percent.

Example 2

0.2011g of PEG 400-sodium montmorillonite composite adsorbent and 1.0039g of thiophene 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 60.36%.

Example 3

Weighing 0.2009g of PEG 600-sodium montmorillonite composite adsorbent and 1.0033g of thiophene 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 67.80%.

Example 4

0.2012g of PEG 1000-sodium montmorillonite composite adsorbent and 1.0034g of thiophene 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 73.18 percent.

Example 5

0.2002g of PEG 2000-sodium montmorillonite composite adsorbent and 1.0006g of thiophene 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 74.64 percent.

Example 6

0.2005g of PEG 4000-Na-montmorillonite composite adsorbent and 1.0016g of thiophene 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 79.38%.

Example 7

Weighing 0.2006g of PEG 6000-sodium montmorillonite composite adsorbent and 1.0019g of thiophene 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 81.00%.

Example 8

Weighing 0.2006g of PEG 10000-Na-montmorillonite composite adsorbent and 1.0022g of thiophene 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 85.30%.

Example 9

Weighing 0.2006g of PEG 10000-Na-montmorillonite composite adsorbent and 1.0020g of thiophene 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 89.48%.

Example 10

0.4012g of PEG 10000-Na-montmorillonite composite adsorbent and 1.0009g of thiophene 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 90.91%.

Example 11

Weighing 0.2011g of PEG 10000-Na-montmorillonite composite adsorbent and 1.0032g of thiophene 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 85.68%.

Example 12

0.2004g of PEG 10000-Na-montmorillonite composite adsorbent and 1.0018g of thiophene n-octane solution with sulfur concentration of 1600ppm are weighed, stirred for 30min at 40 ℃, 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 80.78%.

Example 13

Weighing 1.0016g of PEG 10000-sodium montmorillonite composite adsorbent and 5.0062g of thiophene n-octane solution with sulfur concentration of 1600ppm, stirring for 30min at 25 ℃, wherein the stirring speed is 600rpm, standing for layering, and detecting the sulfur concentration in the n-octane layer by using a gas chromatography, wherein the sulfur concentration is 231.33 ppm; 4.0012g of thiophene n-octane solution is taken, 0.8011g 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 120.62 ppm; 3.0021g of thiophene n-octane solution is taken, 0.6004g 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 40.80 ppm; 2.0021g of thiophene n-octane solution is taken, 0.4006g 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 gas chromatography, wherein the sulfur concentration is 16.05 ppm; taking 1.0002g of thiophene n-octane solution, adding 0.2011g of PEG 10000-Na 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 2.19 ppm.

The above description is only for the purpose of creating a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can substitute or change the technical solution and the inventive concept of the present invention within the technical scope of the present invention.