CN113897217A - Method for extracting and desulfurizing quaternary ammonium salt composite eutectic solvent - Google Patents
Method for extracting and desulfurizing quaternary ammonium salt composite eutectic solvent Download PDFInfo
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- CN113897217A CN113897217A CN202111413760.1A CN202111413760A CN113897217A CN 113897217 A CN113897217 A CN 113897217A CN 202111413760 A CN202111413760 A CN 202111413760A CN 113897217 A CN113897217 A CN 113897217A
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- eutectic solvent
- hydrogen bond
- quaternary ammonium
- ammonium salt
- desulfurization
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- 230000005496 eutectics Effects 0.000 title claims abstract description 93
- 239000002904 solvent Substances 0.000 title claims abstract description 92
- 239000002131 composite material Substances 0.000 title claims abstract description 43
- 150000003242 quaternary ammonium salts Chemical class 0.000 title claims abstract description 43
- 238000000034 method Methods 0.000 title claims abstract description 20
- 230000003009 desulfurizing effect Effects 0.000 title claims abstract description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 67
- 239000001257 hydrogen Substances 0.000 claims abstract description 67
- 238000006477 desulfuration reaction Methods 0.000 claims abstract description 43
- 230000023556 desulfurization Effects 0.000 claims abstract description 43
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 25
- 238000002156 mixing Methods 0.000 claims abstract description 25
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000000605 extraction Methods 0.000 claims abstract description 21
- -1 chlorine ions Chemical class 0.000 claims abstract description 20
- 150000001450 anions Chemical class 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 15
- 239000011593 sulfur Substances 0.000 claims abstract description 15
- 239000000460 chlorine Substances 0.000 claims abstract description 14
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 14
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims abstract description 11
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910001510 metal chloride Inorganic materials 0.000 claims abstract description 10
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 8
- 238000003756 stirring Methods 0.000 claims abstract description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 30
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 18
- 238000002360 preparation method Methods 0.000 claims description 10
- 230000035484 reaction time Effects 0.000 claims description 9
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 6
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 6
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 5
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 5
- 239000011592 zinc chloride Substances 0.000 claims description 4
- 239000005711 Benzoic acid Substances 0.000 claims description 3
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- 235000010233 benzoic acid Nutrition 0.000 claims description 3
- 239000004202 carbamide Substances 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims 2
- 239000000295 fuel oil Substances 0.000 abstract description 22
- 239000003921 oil Substances 0.000 abstract description 17
- 239000007800 oxidant agent Substances 0.000 abstract description 9
- 230000001590 oxidative effect Effects 0.000 abstract description 9
- 239000003054 catalyst Substances 0.000 abstract description 3
- 239000000047 product Substances 0.000 description 13
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 12
- 230000003647 oxidation Effects 0.000 description 7
- 238000007254 oxidation reaction Methods 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000002608 ionic liquid Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 5
- 150000002430 hydrocarbons Chemical group 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- OEYIOHPDSNJKLS-UHFFFAOYSA-N choline Chemical compound C[N+](C)(C)CCO OEYIOHPDSNJKLS-UHFFFAOYSA-N 0.000 description 3
- 229960001231 choline Drugs 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000004880 explosion Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 3
- 239000006228 supernatant Substances 0.000 description 3
- KEQXNNJHMWSZHK-UHFFFAOYSA-L 1,3,2,4$l^{2}-dioxathiaplumbetane 2,2-dioxide Chemical compound [Pb+2].[O-]S([O-])(=O)=O KEQXNNJHMWSZHK-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- IYYZUPMFVPLQIF-UHFFFAOYSA-N dibenzothiophene Chemical compound C1=CC=C2C3=CC=CC=C3SC2=C1 IYYZUPMFVPLQIF-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- ZMANZCXQSJIPKH-UHFFFAOYSA-N triethylamine Natural products CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- UCRRAKUBCJKPHT-UHFFFAOYSA-N 1-(dimethylamino)pentan-3-ol Chemical class CCC(O)CCN(C)C UCRRAKUBCJKPHT-UHFFFAOYSA-N 0.000 description 1
- WUMJCTFQUXKJOM-UHFFFAOYSA-N 3-hydroxypropyl(dimethyl)azanium;chloride Chemical compound Cl.CN(C)CCCO WUMJCTFQUXKJOM-UHFFFAOYSA-N 0.000 description 1
- OXAMBMYXAGPEHI-UHFFFAOYSA-N CN(C)CCCO.O Chemical compound CN(C)CCCO.O OXAMBMYXAGPEHI-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- 229910001429 cobalt ion Inorganic materials 0.000 description 1
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
Classifications
-
- 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
- C10G27/00—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation
-
- 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
- C10G21/12—Organic compounds only
- C10G21/27—Organic compounds not provided for in a single one of groups C10G21/14 - C10G21/26
-
- 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
Landscapes
- 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)
- Extraction Or Liquid Replacement (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
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.
Description
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 is
Wherein 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 is
Wherein 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 is
Wherein 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 is
Wherein 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.
Claims (10)
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 is
Wherein 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 is
Wherein 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.
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