Method for extracting and desulfurizing quaternary ammonium salt composite eutectic solvent
阅读说明：本技术 一种季铵盐类复合低共熔溶剂萃取脱硫的方法 (Method for extracting and desulfurizing quaternary ammonium salt composite eutectic solvent ) 是由 徐航 吴峰敏 郭亚菲 魏学锋 牛安琪 于 2021-11-25 设计创作，主要内容包括：一种季铵盐类复合低共熔溶剂萃取脱硫的方法,包括以下步骤：取含羟基、阴离子为氯的季铵盐与金属氯化物通过金属离子与氯离子配位反应制得氢键受体A,取氢键受体A与氢键供体混合制备得到共熔溶剂A；取含羟基、阴离子为氢氧根的季铵盐与过硫酸铵反应制备得到氢键受体B,取氢键受体B与氢键供体混合制备得到共熔溶剂B；取共熔溶剂A和共熔溶剂B混合制备得到复合共熔溶剂；取复合共熔溶剂与含硫油品混合搅拌进行萃取脱硫。本发明的萃取脱硫方法利用自身含催化剂金属离子和氧化剂过硫酸根离子的共熔溶剂,无须外加氧化剂,能够实现燃料油的快速、安全、高效脱硫。(A method for extracting and desulfurizing a quaternary ammonium salt composite eutectic solvent comprises the following steps: taking quaternary ammonium salt containing hydroxyl and chlorine as anions and metal chloride to perform coordination reaction of metal ions and chlorine ions to prepare a hydrogen bond acceptor A, and taking the hydrogen bond acceptor A and a hydrogen bond donor to mix to prepare a eutectic solvent A; reacting quaternary ammonium salt containing hydroxyl and taking anions as hydroxyl with ammonium persulfate to obtain a hydrogen bond receptor B, and mixing the hydrogen bond receptor B with a hydrogen bond donor to obtain a eutectic solvent B; mixing the eutectic solvent A and the eutectic solvent B to prepare a composite eutectic solvent; and mixing and stirring the composite eutectic solvent and the sulfur-containing oil product for extraction and desulfurization. The extraction desulfurization method of the invention utilizes the eutectic solvent which contains the catalyst metal ions and the oxidant persulfate ions, does not need to add the oxidant, and can realize the quick, safe and high-efficiency desulfurization of the fuel oil.)
1. A method for extracting and desulfurizing a quaternary ammonium salt composite eutectic solvent is characterized by comprising the following steps:
taking quaternary ammonium salt containing hydroxyl and chlorine as anions and metal chloride to perform coordination reaction of metal ions and chlorine ions to prepare a hydrogen bond acceptor A, and taking the hydrogen bond acceptor A and a hydrogen bond donor to mix to prepare a eutectic solvent A;
reacting quaternary ammonium salt containing hydroxyl and taking anions as hydroxyl with ammonium persulfate to obtain a hydrogen bond receptor B, and mixing the hydrogen bond receptor B with a hydrogen bond donor to obtain a eutectic solvent B;
mixing the eutectic solvent A and the eutectic solvent B to prepare a composite eutectic solvent;
and mixing and stirring the composite eutectic solvent and the sulfur-containing oil product for extraction and desulfurization.
2. The method for extraction desulfurization of the quaternary ammonium salt composite eutectic solvent according to claim 1, wherein in the preparation of the hydrogen bond acceptor A, the molar ratio of the quaternary ammonium salt containing hydroxyl and chlorine as anions to the metal chloride is 1:1, the reaction temperature is 100-130 ℃, and the reaction time is 12-48 h.
3. The method for extraction desulfurization of the quaternary ammonium salt composite eutectic solvent according to claim 2, wherein the molar ratio of the hydrogen bond acceptor A to the hydrogen bond donor is 1: 1-1: 10, and mixing.
4. The method for extraction desulfurization of the quaternary ammonium salt composite eutectic solvent according to claim 1, wherein in the preparation of the hydrogen bond acceptor B, the molar ratio of the quaternary ammonium salt containing hydroxyl and taking hydroxide anion to ammonium persulfate is 2:1, the reaction temperature is 0-30 ℃, and the reaction time is 12-48 h.
5. The method for extraction desulfurization of quaternary ammonium salt composite eutectic solvent according to claim 4, wherein the molar ratio of the hydrogen bond acceptor B to the hydrogen bond donor is 1: 2-1: 10, and mixing.
6. The method for extraction desulfurization of the quaternary ammonium salt composite eutectic solvent according to claim 1, wherein the quaternary ammonium salt containing hydroxyl and chlorine as an anion isWherein n is 1-6, R1、R2、R3Is a hydrocarbon group having 1 to 4 carbon atoms.
7. The method for the extraction desulfurization of the quaternary ammonium salt composite eutectic solvent according to claim 1, wherein the quaternary ammonium salt containing hydroxyl and having hydroxide as an anion isWherein n is 1-6, R1、R2、R3Is a hydrocarbon group having 1 to 4 carbon atoms.
8. The method for the extraction desulfurization of the quaternary ammonium salt composite eutectic solvent according to claim 1, wherein the metal chloride is: CoCl2、ZnCl2Or FeCl3。
9. The method for the extraction desulfurization of the quaternary ammonium salt composite eutectic solvent according to claim 1, wherein in the preparation of the composite eutectic solvent, the molar ratio of the eutectic solvent A to the eutectic solvent B is 1: 1-1: 20, the reaction temperature is 10-50 ℃, and the reaction time is 20-120 min.
10. The method for extraction desulfurization of the quaternary ammonium salt composite eutectic solvent according to claim 1, wherein the hydrogen bond donor is one or more of polyethylene glycol, ethylene glycol, glycerol, ethylene glycol, malonic acid, benzoic acid, urea and acetamide.
Technical Field
The invention relates to the technical field of fuel oil desulfurization, in particular to a method for extracting and desulfurizing a quaternary ammonium salt composite eutectic solvent.
Background
With the improvement of the sulfur-containing standard of motor vehicle fuel oil for many times in recent years in China, the requirement on the desulfurization of petroleum fuel is higher and higher, the traditional petroleum desulfurization method utilizes hydrodesulfurization, which requires high temperature and high pressure, harsh reaction conditions, high investment cost, large consumption of unsafe hydrogen and the like, so that the desulfurization cost is huge. In recent years, the ionic liquid extraction catalytic oxidation room temperature desulfurization technology is concerned with due to the reasons of mild reaction conditions, high reaction speed, high desulfurization efficiency and the like, and the ionic liquid extraction catalytic oxidation is specifically to prepare iron-containing ionic liquid, firstly extract sulfur-containing substances in raw oil, then couple the iron-containing ionic liquid with dilute hydrogen peroxide, and perform catalytic oxidation desulfurization at room temperature, wherein the desulfurization rate is up to more than 99%.
However, hydrogen peroxide as an oxidant in the process of ionic liquid extraction catalytic oxidation desulfurization has the disadvantages of instability, easy decomposition, easy explosion, strong corrosivity and the like, in recent years, eutectic solvents have the characteristics of simple preparation, low cost, low toxicity, good solubility, difficult volatilization, environmental friendliness, biodegradability and the like, and are gradually applied to the field of oil product desulfurization, the chinese patent of CN106753514B describes a method for extraction desulfurization of choline eutectic solvents, which prepares metal-containing choline eutectic solvents for extraction desulfurization, but the desulfurization rate is not high, the amount of eutectic solvents is large, the chinese patent of CN110194965A describes a method for catalytic oxidation fuel oil desulfurization of three-component eutectic solvents, which introduces hydrogen peroxide into choline eutectic solvents to realize high-efficiency desulfurization, however, hydrogen peroxide still needs to be adopted in the desulfurization process and is unstable, easy decomposition, easy explosion, strong corrosivity and the like, so that how to realize safe and efficient desulfurization of oil products is still a problem to be solved by researchers in the field.
Disclosure of Invention
The invention aims to provide a method for extracting and desulfurizing a quaternary ammonium salt composite eutectic solvent, which utilizes the eutectic solvent containing catalyst metal ions and oxidant persulfate ions, does not need to add an oxidant, and can realize quick, safe and efficient desulfurization of fuel oil.
The technical scheme adopted by the invention is as follows:
a method for extracting and desulfurizing a quaternary ammonium salt composite eutectic solvent comprises the following steps:
taking quaternary ammonium salt containing hydroxyl and chlorine as anions and metal chloride to perform coordination reaction of metal ions and chlorine ions to prepare a hydrogen bond acceptor A, and taking the hydrogen bond acceptor A and a hydrogen bond donor to mix to prepare a eutectic solvent A;
reacting quaternary ammonium salt containing hydroxyl and taking anions as hydroxyl with ammonium persulfate to obtain a hydrogen bond receptor B, and mixing the hydrogen bond receptor B with a hydrogen bond donor to obtain a eutectic solvent B;
mixing the eutectic solvent A and the eutectic solvent B to prepare a composite eutectic solvent;
and mixing and stirring the composite eutectic solvent and the sulfur-containing oil product for extraction and desulfurization.
Further, in the preparation of the hydrogen bond acceptor A, the molar ratio of the quaternary ammonium salt containing hydroxyl and chlorine as anions to the metal chloride is 1:1, the reaction temperature is 100-130 ℃, and the reaction time is 12-48 h.
Further, the molar ratio of the hydrogen bond acceptor A to the hydrogen bond donor is 1: 1-1: 10, and mixing.
Further, in the preparation of the hydrogen bond receptor B, the molar ratio of the quaternary ammonium salt containing hydroxyl and taking hydroxide ions as anions to the ammonium persulfate is 2:1, the reaction temperature is 0-30 ℃, and the reaction time is 12-48 h.
Further, the hydrogen bond acceptor B and the hydrogen bond donor are mixed according to a molar ratio of 1: 2-1: 10, and mixing.
Further, the quaternary ammonium salt containing hydroxyl and chlorine as anion isWherein n is 1-6, R1、R2、R3Is a hydrocarbon group having 1 to 4 carbon atoms.
The quaternary ammonium salt containing hydroxyl and taking hydroxide radical as anion isWherein n is 1-6, R1、R2、R3Is a hydrocarbon group having 1 to 4 carbon atoms.
Further, the metal chloride is: CoCl2、ZnCl2Or FeCl3。
Further, in the preparation of the composite eutectic solvent, the molar ratio of the eutectic solvent A to the eutectic solvent B is 1: 1-1: 20, the reaction temperature is 10-50 ℃, and the reaction time is 20-120 min.
Further, the hydrogen bond donor is one or more of polyethylene glycol, ethylene glycol, glycerol, ethylene glycol, malonic acid, benzoic acid, urea and acetamide.
The invention has the beneficial effects that:
1. the quaternary ammonium salt eutectic solvent extraction desulfurization method provided by the invention is used for preparing quaternary ammonium salt containing metal ions and persulfate ions, forming a coupling hydrogen bond acceptor and combining with a hydrogen bond donor containing hydroxyl or amino to form a three-component eutectic solvent, wherein the eutectic solvent contains catalyst metal ions and oxidant persulfate ions, and the quick, safe and efficient desulfurization of fuel oil can be realized without an additional oxidant.
2. In the method for extraction desulfurization of the quaternary ammonium salt eutectic solvent, the oxidant persulfate ions are carried by the eutectic solvent, so that the problems of instability, easy decomposition, easy explosion, strong corrosivity and the like of the oxidant caused by adding additional hydrogen peroxide in the conventional oil product desulfurization are effectively solved, in addition, when persulfate ions are adopted, the sulfate ions formed by failure can recover the oxidation capacity of the persulfate ions in an electrolytic regeneration mode after the sulfate ions are oxidized, and compared with the conventional hydrogen peroxide, the method can push the eutectic solvent to be recycled by means of electric energy.
3. The eutectic solvent provides a stable extraction catalytic oxidation environment, the purified fuel oil and the eutectic solvent are immiscible, the separation can be realized by a simple pouring method, the reaction condition is mild, the operation is simple, and the environment is friendly.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The invention provides a method for extracting and desulfurizing a quaternary ammonium salt composite eutectic solvent, which comprises the following steps:
taking quaternary ammonium salt containing hydroxyl and chlorine as anions and metal chloride to perform coordination reaction of metal ions and chlorine ions to prepare a hydrogen bond acceptor A, and taking the hydrogen bond acceptor A and a hydrogen bond donor to mix to prepare a eutectic solvent A;
reacting quaternary ammonium salt containing hydroxyl and taking anions as hydroxyl with ammonium persulfate to obtain a hydrogen bond receptor B, and mixing the hydrogen bond receptor B with a hydrogen bond donor to obtain a eutectic solvent B;
mixing the eutectic solvent A and the eutectic solvent B to prepare a composite eutectic solvent;
and mixing and stirring the composite eutectic solvent and the sulfur-containing oil product for extraction and desulfurization.
In the preparation of the hydrogen bond acceptor A, the molar ratio of the quaternary ammonium salt containing hydroxyl and chlorine as anions to the metal chloride is 1:1, the reaction temperature is 100-130 ℃, and the reaction time is 12-48 h.
Wherein, the molar ratio of the hydrogen bond acceptor A to the hydrogen bond donor is 1: 1-1: 10, and mixing.
In the preparation of the hydrogen bond receptor B, the molar ratio of the quaternary ammonium salt containing hydroxyl and taking hydroxide ions as anions to ammonium persulfate is 2:1, the reaction temperature is 0-30 ℃, and the reaction time is 12-48 h.
Wherein, the hydrogen bond acceptor B and the hydrogen bond donor are mixed according to the molar ratio of 1: 2-1: 10, and mixing.
Wherein the quaternary ammonium salt containing hydroxyl and chlorine as anion isWherein n is 1-6, R1、R2、R3Is a hydrocarbon group having 1 to 4 carbon atoms.
Wherein the quaternary ammonium salt containing hydroxyl and taking hydroxide radical as anion isWherein n is 1-6, R1、R2、R3Is a hydrocarbon group having 1 to 4 carbon atoms.
Wherein the metal chloride is: CoCl2, ZnCl2Or FeCl3。
Wherein, in the preparation of the composite eutectic solvent, the molar ratio of the eutectic solvent A to the eutectic solvent B is 1: 1-1: 20, the reaction temperature is 10-50 ℃, and the reaction time is 20-120 min.
Wherein, the hydrogen bond donor is one or more of polyethylene glycol, ethylene glycol, glycerol, ethylene glycol, malonic acid, benzoic acid, urea and acetamide.
Example one
(1) 0.1mol of 2-hydroxyethyl trimethylamine chloride (b) is taken) With 0.1mol of zinc chloride (ZnCl)2) Performing coordination reaction for 24 hours at 120 ℃, completely dissolving the two to prepare zinc chloride 2-hydroxyethyl trimethylamine as a hydrogen bond acceptor A, and reacting the hydrogen bond acceptor A with hydrogen bond donor ethylene glycol according to a molar ratio of 1: 1. mixing and reacting for 24h at room temperature to prepare the eutectic solvent A.
(2) 0.1mol of 2-hydroxyethyl trimethylamine hydroxide reacts with 0.05mol of ammonium persulfate at the temperature of 30 ℃ for 12h to obtain milk white solid, and the white solid is dried in vacuum to remove impurity ammonia water to obtain 2-hydroxyethyl trimethylamine persulfate salt (used as a hydrogen bond acceptor B)) Taking hydrogen bond acceptor B and hydrogen bond donor ethylene glycol according to a molar ratio of 1:1, mixing and slowly dissolving to prepare a eutectic solvent B.
(3) Taking the eutectic solvent A and the eutectic solvent B according to a molar ratio of 1:1, mixing to prepare the quaternary ammonium salt composite eutectic solvent containing zinc and persulfate.
(4) The method comprises the following steps of taking 6g of simulated fuel oil containing 500ppm of sulfur, dissolving 0.2875g of dibenzothiophene in 100g of normal octane to prepare the simulated fuel oil, adding 2g of prepared composite eutectic solvent into the obtained simulated fuel oil, reacting for 90min at the temperature of 30 ℃, enabling the purified fuel oil and the composite eutectic solvent to be immiscible, separating the purified fuel oil and the composite eutectic solvent by pouring, obtaining supernatant oil product liquid, and detecting the content of sulfur-containing substances in the oil product by using an ultraviolet visible spectrophotometry method to be 4.5ppm, wherein the desulfurization rate is 99.1%.
Example two
(1) 0.1mol of 2-hydroxybutyl triethylamine chloride (b) is taken) With 0.1mol of ferric chloride (FeCl)3) Performing coordination reaction for 48 hours at the temperature of 100 ℃, completely dissolving the two to prepare ferric chloride 2-hydroxyethyl triethylamine serving as a hydrogen bond acceptor A, and reacting the hydrogen bond acceptor A with hydrogen bond donor glycerol according to the molar ratio of 1: 5. mixing and reacting for 24h at room temperature to prepare the eutectic solvent A.
(2) 0.1mol of 2-hydroxybutyl triethylamine hydroxide and 0.05mol of ammonium persulfate are taken to react for 24h at the temperature of 15 ℃ to obtain milk white solid, and the white solid is dried in vacuum to remove impurity ammonia water to obtain the persulfuric acid 2-hydroxybutyl triethylamine salt (ammonium salt) as a hydrogen bond acceptor B) Taking hydrogen bond acceptor B and hydrogen bond donor ethylene glycol according to a molar ratio of 1: 5, mixing and slowly dissolving to prepare a eutectic solvent B.
(3) Taking the eutectic solvent A and the eutectic solvent B according to a molar ratio of 1: 2.5, preparing the quaternary ammonium salt composite eutectic solvent containing iron and persulfate radicals.
(4) Taking 6g of simulated fuel oil containing 500ppm of sulfur, adding 1g of the prepared composite eutectic solvent, reacting for 90min at the temperature of 30 ℃, wherein the desulfurization rate reaches 99%, the purified fuel oil and the composite eutectic solvent are immiscible, separating the two by pouring, obtaining supernatant oil product clear liquid, and detecting the content of sulfur-containing substances in the oil product by using an ultraviolet-visible spectrophotometry, wherein the desulfurization rate reaches 99%.
EXAMPLE III
(1) 0.1mol of chlorinated 2-hydroxybutyltrimethylamine (b) is taken) With 0.1mol of cobalt chloride (CoCl)2) Performing coordination reaction for 12h at 130 ℃, completely dissolving the two to prepare cobalt chloride 2-hydroxybutyl tributylamine containing cobalt ions as a hydrogen bond acceptor A, and reacting the hydrogen bond acceptor A with hydrogen bond donor glycerol according to a molar ratio of 1: 10. mixing and reacting for 12h at room temperature to prepare the eutectic solvent A.
(2) 0.1mol of 2-hydroxybutyltributylamine hydroxide reacts with 0.05mol of ammonium persulfate at 0 ℃ for 48 hours to obtain a milky white solid, and the white solid is dried in vacuum to remove impurity ammonia water to obtain 2-hydroxybutylttributylamine persulfate serving as a hydrogen bond acceptor B (ammonium persulfate)) Taking hydrogen bond acceptor B and hydrogen bond donor ethylene glycol according to a molar ratio of 1: 10, and slowly dissolving to prepare a eutectic solvent B.
(3) Taking the eutectic solvent A and the eutectic solvent B according to a molar ratio of 1: 5, mixing to prepare the quaternary ammonium salt composite eutectic solvent containing cobalt and persulfate.
(4) Taking 6g of simulated fuel oil containing 500ppm of sulfur, adding 0.5g of the prepared composite eutectic solvent, reacting for 120min at the temperature of 20 ℃, ensuring that the purified fuel oil and the composite eutectic solvent are immiscible, separating the purified fuel oil and the composite eutectic solvent by pouring, obtaining upper oil product clear liquid, and detecting the content of sulfur-containing substances in the oil product to be 15ppm by using an ultraviolet-visible spectrophotometry, wherein the desulfurization rate reaches 97%.
Example four
The method is the same as the first embodiment, and is different from the first embodiment in that the hydrogen bond donor is glycerol, purified fuel oil and the composite eutectic solvent are immiscible, the purified fuel oil and the composite eutectic solvent are separated by pouring, a supernatant oil product clear liquid can be obtained, the content of sulfur-containing substances in the oil product is detected to be 20ppm by an ultraviolet-visible spectrophotometry, and the desulfurization rate is 96%.
EXAMPLE five
The method is the same as the first embodiment, and is different from the first embodiment in that the sulfur content of the simulated fuel oil is increased to 1000ppm, other conditions are unchanged, the purified fuel oil and the composite eutectic solvent are immiscible, the purified fuel oil and the composite eutectic solvent are separated by pouring, an upper oil clear liquid can be obtained, the content of sulfur-containing substances in the oil is detected to be 110ppm by an ultraviolet-visible spectrophotometry, and the desulfurization rate is 89%.
It should be noted that the above embodiments are only for illustrating the present invention, but the present invention is not limited to the above embodiments, and any simple modification, equivalent change and modification made to the above embodiments according to the technical essence of the present invention fall within the protection scope of the present invention.