阅读说明：本技术 一种酰胺基iv型低共熔溶剂及其制备方法和在燃油脱硫中的用途 (Amide IV type eutectic solvent, preparation method thereof and application thereof in fuel oil desulfurization ) 是由 蒋伟 罗亚平 朱坤 徐丽仙 李宏平 朱文帅 李华明 于 2020-11-23 设计创作，主要内容包括：本发明属于燃油萃取脱硫技术领域,公开了一种酰胺基IV型低共熔溶剂及其制备方法和在燃油脱硫中的用途。本发明以含酰胺基的有机配体和金属卤化物为原料在一定条件下混合得到；萃取脱硫的步骤如下将所述新型酰胺基IV型低共熔溶剂加入到油品中,搅拌反应一段时间后,停止搅拌。本发明所述的方法中,反应结束后,由于低共熔溶剂和油品呈现两相,通过简单的倾倒即可分离油品所制备的低共熔溶剂可直接循环使用,也可以通过再生后使用。(The invention belongs to the technical field of fuel oil extraction desulfurization, and discloses an amide IV type eutectic solvent, a preparation method thereof and application thereof in fuel oil desulfurization. The preparation method is obtained by mixing an organic ligand containing an amido group and a metal halide serving as raw materials under a certain condition; the step of extraction desulfurization is that the novel acylamino IV type eutectic solvent is added into oil products, and stirring is stopped after stirring reaction is carried out for a period of time. In the method, after the reaction is finished, because the eutectic solvent and the oil product are in two phases, the eutectic solvent prepared by separating the oil product through simple pouring can be directly recycled and can also be used after regeneration.)

1. An amido group-IV eutectic solvent, which is a mixture of an amido group-containing organic ligand and a metal halide, wherein the amido group-containing organic ligand has a structure shown in formula 1:

in the formula 1, R₁Can be H, alkyl or benzene ring; r₂Is H or alkyl, R₃Is H or alkyl;

the metal halide is ZnCl₂、FeCl₃、CuCl₂、MgCl₂、NaCl、CoCl₂、NiCl₂、ZnBr₂One kind of (1).

2. The preparation method of the amido IV type eutectic solvent is characterized in that an amido-containing organic ligand and a metal halide are heated and mixed for 0.5-8 hours at the temperature of 30-100 ℃ in an oil bath according to a proportion, and then the mixture is stood and cooled to room temperature to obtain a uniform liquid, namely the amido IV type eutectic solvent.

3. The method of claim 2, wherein the molar ratio of the organic amide group-containing ligand to the metal halide is 1 to 3.

4. Use of the amido type IV eutectic solvent according to claim 1 for the desulfurization of fuel oils.

5. Use according to claim 4, wherein the fuel oil is crude oil, fuel oil or semi-finished oil in a crude oil refining process.

6. The use according to claim 4, wherein the amide group IV eutectic solvent is added to fuel oil and stirring is stopped after a period of stirring reaction.

7. The use as claimed in claim 6, wherein the mass ratio of the fuel oil to the amide group IV type eutectic solvent is 1: 2-20: 1.

8. The use according to claim 6, wherein the temperature of the stirring reaction is 0-80 ℃ and the stirring reaction time is 1min-3 h.

Technical Field

The invention belongs to the field of fuel oil desulfurization, and relates to an amide IV type eutectic solvent, a preparation method thereof and application thereof in fuel oil desulfurization.

Background

The sulfides in the fuel oil are converted into sulfur oxides (SOx) by combustion, which has adverse effects on the environment and human health. In order to protect the environment, strict legislation has been passed worldwide to limit the maximum allowable sulphur content in fuel oils to 10 ppm. Hydrogenation ofDesulfurization (HDS) and non-hydrogen desulfurization are two methods to obtain ultra low sulfur fuel oils. Under the conditions of high pressure (3.5-7.0MPa) and temperature (300-₂S, HDS technology for removing sulfides has been applied to industrial production, resulting in high production costs. In addition, aromatic sulfur compounds such as Benzothiophene (BT), Dibenzothiophene (DBT), and 4, 6-dimethyldibenzothiophene (4,6-DMDBT) are difficult to remove by HDS. Thus, non-HDS techniques such as: adsorption, oxidation, extraction and coupling techniques thereof are widely studied. Among other things, Extractive Desulfurization (EDS) has milder conditions and lower octane number loss and therefore may be a potential alternative or coupling to HDS. However, it is challenging to find an efficient extractant.

For EDS, conventional polar solvents, such as dimethyl sulfoxide (DMSO), N-methylpyrrolidone (NMP), and N, N-Dimethylformamide (DMF), can remove the S compounds in the oil to some extent, however, molecular solvents experience higher volatility and greater solubility in the oil. This causes environmental problems, namely VOCs and secondary pollution of the oil. Compared to these solvents, Ionic Liquids (ILs) and eutectic solvents (DESs) have lower vapor pressures and less solvency in oil. Therefore, over the past few years, many ILs and DES have been extensively studied for fuel desulfurization applications. Compared with ILs, DESs are simple to synthesize, low in raw material cost, low in toxicity and easy to degrade. The eutectic solvent is obtained by mixing 2 or more raw materials, and is widely applied to the fields of catalysis, organic synthesis and the like. In 2003, the eutectic solvent is used for extraction desulfurization for the first time and shows a good extraction desulfurization effect, so that the eutectic solvent has a certain application prospect when being used for oil product extraction desulfurization.

Disclosure of Invention

Based on the current situation, the invention synthesizes the novel acylamino IV type eutectic solvent, the preparation process is simple, the reaction raw materials are cheap, the obtained eutectic solvent has higher desulfurization performance, the separation is simple and convenient after the extraction is finished, and the eutectic solvent can be regenerated or recycled.

The invention relates to a novel method for extracting and desulfurizing an amide IV type eutectic solvent, which has mild reaction conditions and simple and convenient operation and can effectively remove sulfides in oil products.

The invention is realized by the following technical scheme:

an amido group IV eutectic solvent, which is a mixture of an amido group-containing organic ligand and a metal halide, wherein the amido group-containing organic ligand has a structure shown in formula 1:

in the formula 1, R₁Can be H, alkyl or benzene ring; r₂Is H or alkyl, R₃Is H or alkyl;

the metal halide is ZnCl₂、FeCl₃、CuCl₂、MgCl₂、NaCl、CoCl₂、NiCl₂、ZnBr₂One kind of (1).

A preparation method of an amido IV type eutectic solvent comprises the steps of heating an amido-containing organic ligand and a metal halide for 0.5-8 hours in an oil bath at the temperature of 30-100 ℃ according to a proportion, mixing, standing and cooling to room temperature to obtain a uniform liquid, namely the amido IV type eutectic solvent.

Wherein the molar ratio of the organic ligand containing amide groups to the metal halide is 1-3.

The amide IV type eutectic solvent is used for desulfurizing fuel oil, wherein the fuel oil is crude oil, fuel oil or semi-finished oil in the crude oil refining process, and the method comprises the following specific steps: and adding the amide IV type eutectic solvent into fuel oil, stirring and reacting for a period of time, and stopping stirring.

Further, the mass ratio of the fuel oil to the amide IV type eutectic solvent is 1: 2-20: 1.

Further, the temperature of the stirring reaction is 0-80 ℃, and the stirring reaction time is 1min-3 h.

The invention has the following advantages:

(1) the invention synthesizes the novel acylamino IV type eutectic solvent for the first time, has simple synthesis and high utilization rate of reactants, the acylamino used for synthesizing the eutectic solvent is a choline-like compound, and the metal chloride has no heavy metal, is not easy to volatilize, has strong heat stability and has no toxicity.

(2) The novel acylamino IV type eutectic solvent prepared by the invention has high extraction efficiency, and after the reaction is finished, the oil product can be separated by simple pouring because the eutectic solvent and the oil product are in two phases.

(3) The eutectic solvent prepared by the invention can be directly recycled and can also be used after regeneration.

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.

Preparing a laboratory simulation oil product: benzothiophene (BT), 3-methylbenzothiophene (3-MBT), Dibenzothiophene (DBT), 4-methylbenzothiophene (4-MDBT) or 4, 6-dimethylbenzothiophene (4,6-DMDBT) are respectively dissolved in n-dodecane solution to prepare the simulated oil with the sulfur content of 200 ppm.

The N-methylformanilide is MFA for short, the N-methylformamide is FA for short, and the acetamide is EA for short;

example 1

8.1096g MFA and 2.726g ZnCl₂Adding into a 100mL round-bottom flask, magnetically stirring for 4h under the condition of 80 ℃ constant-temperature water bath, and naturally cooling to room temperature after the reaction is finished to obtain the deep red eutectic solvent (DES 1).

0.1g of eutectic solvent DES1[ MFA/ZnCl₂]Adding into 0.2g (0.29mL, DBT) simulation oil with sulfur content of 10ppm, stirring at 0 deg.C for 1min, stopping, detecting DBT content in oil by GC-FID, and calculating oil removal rate to be 48%.

Example 2

The preparation process of DES1 is carried out in the same manner as in example 1.

1g of eutectic solvent DES1[ MFA/ZnCl₂]Adding to 2g(2.9mL, DBT) in the simulated oil with 200ppm of sulfur content, stirring for 30min at 25 ℃ and stopping, wherein the eutectic solvent is at the lower layer and the oil product is at the upper layer, detecting the DBT content in the oil by adopting GC-FID, and calculating the removal rate of the oil product to be 38.5%.

Example 3

The preparation process of DES1 is carried out in the same manner as in example 1.

4g of a eutectic solvent DES1[ MFA/ZnCl₂]Adding into 2g (2.9mL, DBT) simulation oil with sulfur content of 50ppm, stirring at 80 deg.C for 3h, stopping, detecting DBT content in oil by GC-FID, and calculating oil removal rate to be 60.3%.

Example 4

The preparation process of DES1 is carried out in the same manner as in example 1.

1g of eutectic solvent DES1[ MFA/ZnCl₂]Adding into 2g (2.9mL, BT) simulation oil with 500ppm sulfur content, stirring at 25 deg.C for 1h, stopping, with eutectic solvent at lower layer and oil at upper layer, detecting BT content in oil by GC-FID, and calculating oil removal rate to be 40.1%.

Example 5

The preparation process of DES1 is carried out in the same manner as in example 1.

1g of eutectic solvent DES1[ MFA/ZnCl₂]Adding the mixture into 2g (2.9mL,4,6-DMDBT) of simulated oil with 200ppm of sulfur content, stirring for 1h at 25 ℃, stopping stirring, detecting the content of 4,6-DMDBT in the oil by adopting GC-FID (gas chromatography-flame ionization Detector), wherein the eutectic solvent is at the lower layer and the oil is at the upper layer, and calculating the removal rate of the oil to be 29.7%.

Example 6

The preparation process of DES1 is carried out in the same manner as in example 1.

1g of eutectic solvent DES1[ MFA/ZnCl₂]Adding into 2g (2.9mL,4-MDBT) simulation oil with 200ppm sulfur content, stirring at 25 deg.C for 1h, stopping, detecting the 4-MDBT content in the oil by GC-FID, and calculating the oil removal rate to be 32.4%.

Example 7

The preparation process of DES1 is carried out in the same manner as in example 1.

1g of eutectic solvent DES1[ MFA/ZnCl₂]Adding into 2g (2.9mL,3-MBT) simulation oil with sulfur content of 200ppm, stirring at 25 deg.C for 30min, stopping, detecting 3-MBT content in oil by GC-FID, and calculating oil removal rate to be 36.9%.

Example 8

3.544g of FA and 2.726g of ZnCl₂Adding into a 100mL round-bottom flask, magnetically stirring for 4h under the condition of 80 ℃ constant-temperature water bath, and naturally cooling to room temperature after the reaction is finished to obtain the transparent eutectic solvent (DES 2).

1g of eutectic solvent DES2[ FA/ZnCl ]₂](FA: N-methylformamide) is added into 2g (2.9mL, DBT) of simulated oil with 200ppm of sulfur content, the stirring is stopped after 10min at 25 ℃, the eutectic solvent is at the lower layer and the oil product is at the upper layer, the content of DBT in the oil is detected by adopting GC-FID, and the removal rate of the oil product is 33.9 percent by calculation.

Example 9

3.544g EA and 2.726g ZnCl₂Adding into a 100mL round-bottom flask, magnetically stirring for 4h under the condition of 80 ℃ constant-temperature water bath, and naturally cooling to room temperature after the reaction is finished to obtain a light yellow eutectic solvent (DES 3).

1g of eutectic solvent DES3[ EA/ZnCl ]₂](EA: acetamide) was added to 2g (2.9mL, DBT) of a simulated oil with 200ppm of sulfur content, and the mixture was stirred at 25 ℃ for 30min and then stopped, with the eutectic solvent in the lower layer and the oil in the upper layer, and the content of DBT in the oil was measured by GC-FID, and the removal rate of the oil was calculated to be 35.2%.

Example 10

8.1096g of MFA and 2.689g of CuCl₂Adding into a 100mL round-bottom flask, magnetically stirring for 4h under the condition of 80 ℃ constant-temperature water bath, and naturally cooling to room temperature after the reaction is finished to obtain the eutectic solvent (DES 4).

1g of eutectic solvent DES4[ MFA/CuCl₂]Adding into 2g (2.9mL, DBT) simulation oil with sulfur content of 200ppm, stirring at 25 deg.C for 10min, stopping, detecting DBT content in oil by GC-FID, and countingThe removal rate of the oil product is calculated to be 28.9 percent.

Example 11

8.1096g MFA and 2.592g NiCl₂Adding into a 100mL round-bottom flask, magnetically stirring for 4h under the condition of 80 ℃ constant-temperature water bath, and naturally cooling to room temperature after the reaction is finished to obtain the eutectic solvent (DES 5).

1g of eutectic solvent DES5[ MFA/NiCl ]₂]Adding into 2g (2.9mL, DBT) simulation oil with sulfur content of 200ppm, stirring at 25 deg.C for 10min, stopping, detecting DBT content in oil by GC-FID, and calculating oil removal rate to be 33.9%.

Example 12

8.1096g MFA and 3.244g FeCl₃Adding into a 100mL round-bottom flask, magnetically stirring for 4h under the condition of 80 ℃ constant-temperature water bath, and naturally cooling to room temperature after the reaction is finished to obtain the eutectic solvent (DES 6).

1g of eutectic solvent DES6[ MFA/FeCl₃]Adding into 2g (2.9mL, DBT) simulation oil with sulfur content of 200ppm, stirring at 25 deg.C for 10min, stopping, detecting DBT content in oil by GC-FID, and calculating oil removal rate to be 42.7%.

Example 13

8.1096g of MFA and 1.904g of MgCl₂Adding into a 100mL round-bottom flask, magnetically stirring for 4h under the condition of 80 ℃ constant-temperature water bath, and naturally cooling to room temperature after the reaction is finished to obtain the eutectic solvent (DES 7).

1g of eutectic solvent DES7[ MFA/MgCl ]₂]Adding into 1g (2.9mL, DBT) simulation oil with 200ppm sulfur content, stirring at 25 deg.C for 10min, stopping, detecting DBT content in oil by GC-FID, and calculating oil removal rate to be 28.6%.

Example 14

8.1096g of MFA and 1.169g of NaCl are added into a 100mL round-bottom flask, magnetic stirring is carried out for 4 hours under the condition of 80 ℃ constant-temperature water bath, and after the reaction is finished, the mixture is naturally cooled to room temperature, so that the eutectic solvent (DES8) is obtained.

Adding 1g of eutectic solvent DES8[ MFA/NaCl ] into 2g (2.9mL, DBT) of simulated oil with 200ppm of sulfur content, stirring for 10min at 25 ℃, stopping, detecting the DBT content in the oil by GC-FID, wherein the eutectic solvent is at the lower layer and the oil is at the upper layer, and the removal rate of the oil is 21.6% by calculation.

Example 15

8.1096gMFA and 4.504g ZnBr₂Adding into a 100mL round-bottom flask, magnetically stirring for 4h under the condition of 80 ℃ constant-temperature water bath, and naturally cooling to room temperature after the reaction is finished to obtain the eutectic solvent (DES 9).

1g of eutectic solvent DES9[ MFA/ZnBr ]₂]Adding into 1g (2.9mL, DBT) simulation oil with 200ppm sulfur content, stirring at 25 deg.C for 10min, stopping, detecting DBT content in oil by GC-FID, and calculating oil removal rate to be 31.0%.

The novel acylamino IV type eutectic solvent prepared by the invention can be used for crude oil, fuel oil or semi-finished oil in the crude oil refining process, and has good extraction effect.