CN113856572A - Preparation method of supramolecular ionic liquid gel and application of supramolecular ionic liquid gel in deep sulfur removal of fuel oil - Google Patents

Preparation method of supramolecular ionic liquid gel and application of supramolecular ionic liquid gel in deep sulfur removal of fuel oil Download PDF

Info

Publication number
CN113856572A
CN113856572A CN202111154181.XA CN202111154181A CN113856572A CN 113856572 A CN113856572 A CN 113856572A CN 202111154181 A CN202111154181 A CN 202111154181A CN 113856572 A CN113856572 A CN 113856572A
Authority
CN
China
Prior art keywords
ionic liquid
liquid gel
product
supramolecular
fuel oil
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN202111154181.XA
Other languages
Chinese (zh)
Other versions
CN113856572B (en
Inventor
陈世鹏
李峥
樊燕鸽
王蜀江
王惠峰
曹长青
王红星
赵俊宏
何婷
薛宝玉
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Institute of Chemistry Henan Academy of Sciences Co Ltd
Henan Academy of Sciences
Original Assignee
Institute of Chemistry Henan Academy of Sciences Co Ltd
Henan Academy of Sciences
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Institute of Chemistry Henan Academy of Sciences Co Ltd, Henan Academy of Sciences filed Critical Institute of Chemistry Henan Academy of Sciences Co Ltd
Priority to CN202111154181.XA priority Critical patent/CN113856572B/en
Publication of CN113856572A publication Critical patent/CN113856572A/en
Application granted granted Critical
Publication of CN113856572B publication Critical patent/CN113856572B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/0052—Preparation of gels
    • B01J13/0065—Preparation of gels containing an organic phase
    • 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
    • C10G21/20—Nitrogen-containing compounds
    • 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
    • C10G21/28—Recovery of used solvent
    • 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)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

The invention discloses a preparation method of a supramolecular ionic liquid gel and application of the supramolecular ionic liquid gel in deep sulfur removal of fuel oil. Adding 2, 4- (4-nitrobenzylidene) -D-gluconic acid methyl ester, a catalyst, a solvent and organic amine into a container to react at room temperature; and washing and filtering the product by adopting methyl tert-butyl ether, airing the obtained product, adding methanol, stirring to be pasty, washing and filtering by adopting methyl tert-butyl ether again, airing and vacuumizing the obtained product, and thus obtaining the supermolecule ionic liquid gel product. And heating and mixing the obtained gel and the ionic liquid to prepare the ionic liquid gel, and then fully contacting the ionic liquid gel with a simulated fuel oil system of the prepared thiophene, benzothiophene or dibenzothiophene, thereby measuring the sulfur removal effect of the ionic liquid gel in the fuel oil system. The supermolecule ionic liquid gel prepared by the method can effectively remove sulfides in fuel oil, can ensure the quality of oil products, and is green and environment-friendly.

Description

Preparation method of supramolecular ionic liquid gel and application of supramolecular ionic liquid gel in deep sulfur removal of fuel oil
The technical field is as follows:
the invention relates to a preparation method of an ionic liquid gel, in particular to a preparation method of a supramolecular ionic liquid gel and application of the supramolecular ionic liquid gel in deep sulfur removal of fuel oil.
Secondly, background art:
the current regulations of various countries in the world show that the allowable sulfur concentration in fuel oil needs to be controlled to be below 15ppm or even 10ppm, but in the current mature sulfur removal method, no method can economically, rapidly and effectively remove the sulfur concentration in oil products to the standard. Therefore, it is of great practical significance to research and develop a method for deeply removing the sulfur content in the oil product with low cost, greenness and high efficiency.
The hydrodesulfurization process is the most commonly used method for removing sulfur compounds in oil products in the petroleum industry at present, but under the conventional process conditions, the method is difficult to remove aromatic sulfur compounds in oil products, and the aromatic sulfur compounds can be removed to a certain extent only under the conditions of high temperature and high pressure, so that the safety problem in production is avoided, and the cost is directly increased and the effective components (such as olefin) of the oil products are directly lost; in addition, the hydrogenation process tends to produce hydrogen sulfide (H)2S) gas, there is a certain pollution hidden danger. Therefore, the temperature of the molten metal is controlled,there is a need to develop a new technology capable of effectively removing sulfur-containing compounds from fuel oil.
Thirdly, the invention content:
the technical problem to be solved by the invention is as follows: aiming at the defects in the prior art for removing sulfur-containing compounds in oil products, the invention provides a preparation method of a supramolecular ionic liquid gel and application thereof in deep sulfur removal of fuel oil. The supermolecule ionic liquid gel prepared by the method can effectively remove sulfides in fuel oil, can ensure the quality of oil products, and is green and environment-friendly.
In order to solve the problems, the invention adopts the technical scheme that:
the invention provides a preparation method of a supramolecular ionic liquid gel, which comprises the following steps:
a. under the condition of room temperature, adding a raw material compound 2, 4- (4-nitrobenzylidene) -D-methyl gluconate, a catalyst, a solvent and organic amines into a container with stirring equipment for reaction for 12-18 h;
b. and a, adding 5-15 ℃ methyl tert-butyl ether into the product obtained after the reaction in the step a for washing and filtering, washing out unreacted impurities after primary rough washing, filtering the product with the methyl tert-butyl ether, airing the product, placing the aired product in a container, adding methanol in an amount of 0.5mL or 1mL per time until the product is stirred into paste, continuously stirring for 20min, washing with the 5-15 ℃ methyl tert-butyl ether, filtering, airing the filtered product, and vacuumizing to obtain the supermolecule ionic liquid gel product.
According to the preparation method of the supramolecular ionic liquid gel, the molar ratio of the added amount of the compound 2, 4- (4-nitrobenzylidene) -D-methyl gluconate to the added amount of the organic amine in the step a is 1: 1-3;
the molar ratio of the added amount of the compound 2, 4- (4-nitrobenzylidene) -D-methyl gluconate to the added amount of the catalyst is 15-30: 1;
the molar ratio of the added amount of the 2, 4- (4-nitrobenzylidene) -D-gluconic acid methyl ester compound to the solvent is 1: 10 to 20.
According to the preparation method of the supramolecular ionic liquid gel, in the step a, the organic amine is any one of N-hexylamine, dodecylamine, tetradecylamine, hexadecylamine, octadecylamine and oleylamine, the catalyst is 4-dimethylaminopyridine, triethylamine or pyridine, and the solvent is N, N-dimethylformamide, methanol, ethanol or dimethyl sulfoxide.
In addition, the application of the supermolecule ionic liquid gel prepared by the method in deep sulfur removal of fuel oil is provided.
According to the application of the supramolecular ionic liquid gel in deep sulfur removal of fuel oil, the preparation method of the simulated liquid fuel system in the application process comprises the following steps:
a sulfur-containing compound is used as a solute, and n-hexane is used as a solvent, so that a simulated fuel oil system with the concentration of 100-3000 ppm is prepared.
According to the application of the supermolecule ionic liquid gel in deep sulfur removal of fuel oil, the sulfur-containing compound is thiophene, benzothiophene or dibenzothiophene.
According to the application of the supramolecular ionic liquid gel in deep sulfur removal of fuel oil, the adsorption time between the supramolecular ionic liquid gel and a simulated liquid fuel system is 12-48 h, and the adsorption temperature is 15-35 ℃.
According to the application of the supramolecular ionic liquid gel in deep sulfur removal of fuel oil, the concentration of the supramolecular ionic liquid gel is 10-60 mg/mL in the application process.
The synthetic route involved in the preparation method of the supramolecular ionic liquid gel is shown in formula I:
Figure BDA0003288007800000031
wherein R ═ CnH2n+1And n is 6,12,14,16,18 and the like.
The invention has the following positive beneficial effects:
1. the supermolecule ionic liquid gel prepared by the invention is used for removing sulfides in fuel oil, the removal rate of the sulfides is more than 55 percent and can reach 100 percent at most, and sulfur-containing compounds in the fuel oil can be effectively removed.
2. Compared with the prior ionic liquid applied to fuel oil desulfurization, the supermolecule ionic liquid gel prepared by the invention has remarkable advantages, aromatic sulfur-containing compounds in oil products are effectively removed by an extraction method, and the whole process is not accompanied with any chemical change, so that the quality of the oil products is ensured. The quasi-solid gel prepared by the invention not only solves the problem of leakage of the ionic liquid in the processes of storage, transportation and use, but also is convenient to process in the use process, is environment-friendly and green, has the advantages of being renewable and reusable, and greatly improves the practicability.
In addition, the supermolecule ionic liquid gel prepared by the invention is formed by adsorbing ionic liquid in a three-dimensional network structure formed by self-assembling organic micromolecules in the ionic liquid, and the internal porosity of the supermolecule ionic liquid gel enables the supermolecule ionic liquid gel to have obvious adsorption capacity, so that the desulfurization capacity of a system is improved.
3. The supermolecule ionic liquid gel prepared by the invention can effectively remove sulfur-containing compounds in fuel oil, and the ionic liquid gel after removal has the capability of regeneration and reuse, and can be recycled for multiple times. The extracted sulfur-containing compounds can be removed by a distillation method, and the ionic liquid with high boiling point can be left for being reused for extraction desulfurization; or the sulfur-containing compounds are extracted and removed by a back extraction method by using a solvent with better extraction capability, and the ionic liquid is reused for extraction and desulfurization.
In conclusion, the supermolecule ionic liquid gel prepared by the invention can effectively remove sulfides in fuel oil, can ensure the quality of oil products, and is green and environment-friendly. Therefore, the method has remarkable economic and social benefits.
Fourthly, the specific implementation mode:
the invention is further illustrated by the following examples, which do not limit the scope of the invention.
Example 1:
the preparation method of the supramolecular ionic liquid gel comprises the following detailed steps:
a. under the condition of room temperature, adding 1.715g of raw material compound 2, 4- (4-nitrobenzylidene) -D-methyl gluconate, 0.0305g of catalyst 4-dimethylaminopyridine, 5.450mL of solvent N, N-dimethylformamide and 0.990mL of N-hexylamine into a flask, and stirring for reaction for 14 h;
b. and c, washing and filtering the product obtained after the reaction in the step a by using methyl tert-butyl ether at the temperature of 5-15 ℃, washing out unreacted impurities after primary rough washing, filtering the product by using methyl tert-butyl ether, airing the product, placing the aired product in a round-bottom flask, adding methanol in an amount of 0.5mL per time until the product is stirred into paste, continuously stirring for 20min, washing by using methyl tert-butyl ether at the temperature of 5-15 ℃, filtering, airing the filtered product, and vacuumizing to obtain the supermolecule ionic liquid gel product.
Example 2:
the preparation method of the supramolecular ionic liquid gel comprises the following detailed steps:
a. under the condition of room temperature, adding 1.715g of raw material compound 2, 4- (4-nitrobenzylidene) -D-methyl gluconate, 0.0305g of catalyst 4-dimethylaminopyridine, 5.450mL of solvent N, N-dimethylformamide and 2.78g of dodecylamine into a flask, and stirring for reaction for 12 hours;
b. and c, washing and filtering the product obtained after the reaction in the step a by using methyl tert-butyl ether at the temperature of 5-15 ℃, washing out unreacted impurities after primary rough washing, filtering the product by using methyl tert-butyl ether, airing the product, placing the aired product in a round-bottom flask, adding methanol in an amount of 1.0mL each time until the product is stirred into paste, continuously stirring for 20min, washing and filtering the product by using methyl tert-butyl ether at the temperature of 5-15 ℃, airing and vacuumizing the filtered product, and thus obtaining the supermolecule ionic liquid gel product.
Example 3:
the preparation method of the supramolecular ionic liquid gel comprises the following detailed steps:
a. under the condition of room temperature, adding 1.715g of raw material compound 2, 4- (4-nitrobenzylidene) -D-methyl gluconate, 0.0305g of catalyst 4-dimethylaminopyridine, 5.450mL of solvent N, N-dimethylformamide and 2.02g of octadecylamine into a flask, and stirring for reaction for 16 h;
b. and c, washing and filtering the product obtained after the reaction in the step a by using methyl tert-butyl ether at the temperature of 5-15 ℃, washing out unreacted impurities after primary rough washing, filtering the product by using methyl tert-butyl ether, airing the product, placing the aired product in a round-bottom flask, adding methanol in an amount of 1.0mL each time until the product is stirred into paste, continuously stirring for 20min, washing and filtering the product by using methyl tert-butyl ether at the temperature of 5-15 ℃, airing and vacuumizing the filtered product, and thus obtaining the supermolecule ionic liquid gel product.
Example 4:
the preparation method of the supramolecular ionic liquid gel comprises the following detailed steps:
a. under the condition of room temperature, adding 1.715g of raw material compound 2, 4- (4-nitrobenzylidene) -D-methyl gluconate, 0.0305g of catalyst 4-dimethylaminopyridine, 5.450mL of solvent N, N-dimethylformamide and 2g of oleylamine into a flask, and stirring for reacting for 12 hours;
b. and c, washing and filtering the product obtained after the reaction in the step a by using methyl tert-butyl ether at the temperature of 5-15 ℃, washing out unreacted impurities after primary rough washing, filtering the product by using methyl tert-butyl ether, airing the product, placing the aired product in a round-bottom flask, adding methanol in an amount of 0.5mL per time until the product is stirred into paste, continuously stirring for 20min, washing by using methyl tert-butyl ether at the temperature of 5-15 ℃, filtering, airing the filtered product, and vacuumizing to obtain the supermolecule ionic liquid gel product.
Example 5:
the preparation method of the supramolecular ionic liquid gel comprises the following detailed steps:
a. under the condition of room temperature, adding 1.715g of raw material compound 2, 4- (4-nitrobenzylidene) -D-methyl gluconate, 0.0305g of catalyst 4-dimethylaminopyridine, 5.450mL of solvent N, N-dimethylformamide and 0.990mL of N-hexylamine into a flask, and stirring for reaction for 13 h;
b. and c, washing and filtering the product obtained after the reaction in the step a by using methyl tert-butyl ether at the temperature of 5-15 ℃, washing out unreacted impurities after primary rough washing, filtering the product by using methyl tert-butyl ether, airing the product, placing the aired product in a round-bottom flask, adding methanol in an amount of 1.0mL each time until the product is stirred into paste, continuously stirring for 20min, washing and filtering the product by using methyl tert-butyl ether at the temperature of 5-15 ℃, airing and vacuumizing the filtered product, and thus obtaining the supermolecule ionic liquid gel product.
Example 1 the application of the supramolecular ionic liquid gel prepared in the example 1 in the sulfur removal of fuel oil comprises the following specific operation processes:
1) the normal hexane solution of the sulfur-containing compound simulates the preparation of a liquid fuel system: taking thiophene, benzothiophene and dibenzothiophene as solutes and n-hexane as a solvent respectively, and preparing into a simulated fuel oil system with the concentration of 1500 ppm;
2) the obtained supermolecule ionic liquid gel has the following application:
ionic liquid tributylmethylammonium bis (trifluoromethanesulfonyl) imide salt (N)4441NTF2) N-butyl-N-methylpiperidine bis (trifluoromethanesulfonyl) imide salt (PP)14NTF2) And N-butyl-N-methylpyriolo-lidine bis (trifluoromethanesulfonyl) imide salt (Py)14NTF2) Respectively adding the gel prepared in the example 1 and a test tube to carry out heating vibration (the heating temperature is 80-100 ℃), and uniformly mixing to prepare clear ionic liquid gel with the concentration of 10mg/mL (three parts are prepared for each ionic liquid gel); after cooling, respectively taking 250mg of the prepared ionic liquid gel with the concentration of 10mg/mL, putting the ionic liquid gel into a small bottle (nine parts), then taking 500uL of the thiophene, benzothiophene and dibenzothiophene fuel oil system prepared in the step 1), and putting the thiophene, benzothiophene and dibenzothiophene fuel oil system into the prepared ionic liquid gel for full contact (after contact)In the process, the adsorption time is 24 hours, the adsorption temperature is 20-25 ℃), and a fuel oil system is taken after standing for 12 hours, 24 hours and 48 hours to respectively determine the adsorption efficiency of thiophene, benzothiophene and dibenzothiophene. Through experimental determination, the N-butyl-N-methyl pyrronium bis (trifluoromethanesulfonyl) imide salt (Py)14NTF2) The sulfur removal efficiency of the supermolecule ionic liquid gel to thiophene is as high as 84 percent, and tributyl methyl ammonium bis (trifluoromethanesulfonyl) imide salt (N)4441NTF2) The sulfur removal efficiency of the supermolecule ionic liquid gel on benzothiophene is as high as 83 percent, and tributylmethylammonium bis (trifluoromethanesulfonyl) imide salt (N)4441NTF2) The sulfur removal efficiency of the supermolecule ionic liquid gel on dibenzothiophene is as high as 90%.
Example 2 application of the supramolecular ionic liquid gel prepared in the method for removing sulfur from fuel oil, the specific operation process of the application is as follows:
1) the normal hexane solution of the sulfur-containing compound simulates the preparation of a liquid fuel system: taking thiophene, benzothiophene and dibenzothiophene as solutes and n-hexane as a solvent respectively, and preparing into a simulated fuel oil system with the concentration of 1500 ppm;
2) the obtained supermolecule ionic liquid gel has the following application:
ionic liquid tributylmethylammonium bis (trifluoromethanesulfonyl) imide salt (N)4441NTF2) N-butyl-N-methylpiperidine bis (trifluoromethanesulfonyl) imide salt (PP)14NTF2) And N-butyl-N-methylpyriolo-lidine bis (trifluoromethanesulfonyl) imide salt (Py)14NTF2) Respectively adding the gel prepared in the example 2 and a test tube to carry out heating vibration (the heating temperature is 80-100 ℃), and uniformly mixing to prepare clear ionic liquid gel with the concentration of 10mg/mL (three parts are prepared for each ionic liquid gel); cooling, respectively taking 250mg of the prepared ionic liquid gel with the concentration of 10mg/mL, putting the ionic liquid gel into a small bottle (nine parts), then taking 500uL of the thiophene, benzothiophene and dibenzothiophene fuel oil system prepared in the step 1), putting the thiophene, benzothiophene and dibenzothiophene fuel oil system into the prepared ionic liquid gel, fully contacting (the adsorption time in the contact process is 24 hours, the adsorption temperature is 20-25 ℃), taking the fuel oil system after standing for 12 hours, 24 hours and 48 hours, respectively measuringThe adsorption efficiency of thiophene, benzothiophene, and dibenzothiophene. By experiment, tributylmethylammonium bis (trifluoromethanesulfonyl) imide salt (N)4441NTF2) The sulfur removal efficiency of the supermolecule ionic liquid gel to thiophene is as high as 98%, and N-butyl-N-methylpiperidine bis (trifluoromethanesulfonyl) imide (PP)14NTF2) The sulfur removal efficiency of the supermolecule ionic liquid gel on benzothiophene is as high as 62 percent, and N-butyl-N-methylpiperidine bis (trifluoromethanesulfonyl) imide salt (PP)14NTF2) The sulfur removal efficiency of the supermolecule ionic liquid gel on dibenzothiophene is as high as 57%.
Example 3 application of the prepared supramolecular ionic liquid gel in sulfur removal of fuel oil, the specific operation process of the application is as follows:
1) the normal hexane solution of the sulfur-containing compound simulates the preparation of a liquid fuel system: taking thiophene, benzothiophene and dibenzothiophene as solutes and n-hexane as a solvent respectively, and preparing into a simulated fuel oil system with the concentration of 1500 ppm;
2) the obtained supermolecule ionic liquid gel has the following application:
ionic liquid tributylmethylammonium bis (trifluoromethanesulfonyl) imide salt (N)4441NTF2) N-butyl-N-methylpiperidine bis (trifluoromethanesulfonyl) imide salt (PP)14NTF2) And N-butyl-N-methylpyriolo-lidine bis (trifluoromethanesulfonyl) imide salt (Py)14NTF2) Respectively adding the gel prepared in the example 3 and a test tube to carry out heating vibration (the heating temperature is 80-100 ℃), and uniformly mixing to prepare clear ionic liquid gel with the concentration of 10mg/mL (three parts are prepared for each ionic liquid gel); and (2) after cooling, respectively taking 250mg of the prepared ionic liquid gel with the concentration of 10mg/mL, putting the ionic liquid gel into a small bottle (nine parts), then taking 500uL of the thiophene, benzothiophene and dibenzothiophene fuel oil system prepared in the step 1), putting the thiophene, benzothiophene and dibenzothiophene fuel oil system into the prepared ionic liquid gel, fully contacting (the adsorption time in the contact process is 24 hours, the adsorption temperature is 20-25 ℃), taking the fuel oil system after standing for 12 hours, 24 hours and 48 hours, and respectively measuring the adsorption efficiency of thiophene, benzothiophene and dibenzothiophene. Experimentally determined, N-butyl-N-methylpiperidine bis (Trifluoromethanesulfonyl) imide salt (PP)14NTF2) The sulfur removal efficiency of the supermolecule ionic liquid gel to thiophene is up to 83 percent, and tributyl methyl ammonium bis (trifluoromethanesulfonyl) imide salt (N)4441NTF2) The desulfurization efficiency of the supramolecular ionic liquid gel on benzothiophene is up to 61%, and N-butyl-N-methyl-quinolyl bis (trifluoromethanesulfonyl) imide salt (Py)14NTF2) The sulfur removal efficiency of the supermolecule ionic liquid gel on dibenzothiophene is as high as 81%.
Example 4 application of the supramolecular ionic liquid gel prepared in the method for removing sulfur from fuel oil, the specific operation process of the application is as follows:
1) the normal hexane solution of the sulfur-containing compound simulates the preparation of a liquid fuel system: taking thiophene, benzothiophene and dibenzothiophene as solutes and n-hexane as a solvent respectively, and preparing into a simulated fuel oil system with the concentration of 1500 ppm;
2) the obtained supermolecule ionic liquid gel has the following application:
ionic liquid tributylmethylammonium bis (trifluoromethanesulfonyl) imide salt (N)4441NTF2) N-butyl-N-methylpiperidine bis (trifluoromethanesulfonyl) imide salt (PP)14NTF2) And N-butyl-N-methylpyriolo-lidine bis (trifluoromethanesulfonyl) imide salt (Py)14NTF2) Respectively adding the gel prepared in the example 4 and a test tube to carry out heating vibration (the heating temperature is 55-65 ℃), and uniformly mixing to prepare clear ionic liquid gel with the concentration of 10mg/mL (three parts are prepared for each ionic liquid gel); and (2) after cooling, respectively taking 250mg of the prepared ionic liquid gel with the concentration of 10mg/mL, putting the ionic liquid gel into a small bottle (nine parts), then taking 500uL of the thiophene, benzothiophene and dibenzothiophene fuel oil system prepared in the step 1), putting the thiophene, benzothiophene and dibenzothiophene fuel oil system into the prepared ionic liquid gel, fully contacting (the adsorption time in the contact process is 24 hours, the adsorption temperature is 20-25 ℃), taking the fuel oil system after standing for 12 hours, 24 hours and 48 hours, and respectively measuring the adsorption efficiency of thiophene, benzothiophene and dibenzothiophene. By experiment, tributylmethylammonium bis (trifluoromethanesulfonyl) imide salt (N)4441NTF2) Sulfur removal efficiency of supramolecular ionic liquid gel on thiopheneUp to 78% tributylmethylammonium bis (trifluoromethanesulfonyl) imide salt (N)4441NTF2) The sulfur removal efficiency of the supramolecular ionic liquid gel on benzothiophene is as high as 63%, and N-butyl-N-methyl-quinolyl bis (trifluoromethanesulfonyl) imide salt (Py)14NTF2) The sulfur removal efficiency of the supermolecule ionic liquid gel on dibenzothiophene is as high as 64%.
Example 5 application of the prepared supramolecular ionic liquid gel in sulfur removal of fuel oil, the specific operation process of the application is as follows:
1) the normal hexane solution of the sulfur-containing compound simulates the preparation of a liquid fuel system: taking thiophene, benzothiophene and dibenzothiophene as solutes and n-hexane as a solvent respectively, and preparing into a simulated fuel oil system with the concentration of 1500 ppm;
2) the obtained supermolecule ionic liquid gel has the following application:
ionic liquid tributylmethylammonium bis (trifluoromethanesulfonyl) imide salt (N)4441NTF2) N-butyl-N-methylpiperidine bis (trifluoromethanesulfonyl) imide salt (PP)14NTF2) And N-butyl-N-methylpyriolo-lidine bis (trifluoromethanesulfonyl) imide salt (Py)14NTF2) Respectively adding the gel prepared in the example 5 and a test tube to carry out heating vibration (the heating temperature is 80-100 ℃), and uniformly mixing to prepare clear ionic liquid gel with the concentration of 10mg/mL (three parts are prepared for each ionic liquid gel); and (2) after cooling, respectively taking 250mg of the prepared ionic liquid gel with the concentration of 10mg/mL, putting the ionic liquid gel into a small bottle (nine parts), then taking 500uL of the thiophene, benzothiophene and dibenzothiophene fuel oil system prepared in the step 1), putting the thiophene, benzothiophene and dibenzothiophene fuel oil system into the prepared ionic liquid gel, fully contacting (the adsorption time in the contact process is 24 hours, the adsorption temperature is 20-25 ℃), taking the fuel oil system after standing for 12 hours, 24 hours and 48 hours, and respectively measuring the adsorption efficiency of thiophene, benzothiophene and dibenzothiophene. Through experimental determination, the N-butyl-N-methyl pyrronium bis (trifluoromethanesulfonyl) imide salt (Py)14NTF2) The sulfur removal efficiency of the supermolecule ionic liquid gel to thiophene is as high as 92 percent, and tributyl methyl ammonium bis (trifluoromethanesulfonyl) imide salt (N)4441NTF2) SupramoleculesThe sulfur removal efficiency of the ionic liquid gel on benzothiophene is up to 91 percent, and tributylmethylammonium bis (trifluoromethanesulfonyl) imide salt (N)4441NTF2) The sulfur removal efficiency of the supermolecule ionic liquid gel on dibenzothiophene is as high as 100%.

Claims (8)

1. The preparation method of the supramolecular ionic liquid gel is characterized by comprising the following steps:
a. under the condition of room temperature, adding a raw material compound 2, 4- (4-nitrobenzylidene) -D-methyl gluconate, a catalyst, a solvent and organic amines into a container with stirring equipment for reaction for 12-18 h;
b. and a, adding 5-15 ℃ methyl tert-butyl ether into the product obtained after the reaction in the step a for washing and filtering, washing out unreacted impurities after primary rough washing, filtering the product with the methyl tert-butyl ether, airing the product, placing the aired product in a container, adding methanol in an amount of 0.5mL or 1mL per time until the product is stirred into paste, continuously stirring for 20min, washing with the 5-15 ℃ methyl tert-butyl ether, filtering, airing the filtered product, and vacuumizing to obtain the supermolecule ionic liquid gel product.
2. The method of preparing supramolecular ionic liquid gels as claimed in claim 1, characterized in that: in the step a, the molar ratio of the added amount of the compound 2, 4- (4-nitrobenzylidene) -D-gluconic acid methyl ester to the added amount of the organic amine is 1: 1-3;
the molar ratio of the added amount of the compound 2, 4- (4-nitrobenzylidene) -D-methyl gluconate to the added amount of the catalyst is 15-30: 1;
the molar ratio of the added amount of the 2, 4- (4-nitrobenzylidene) -D-gluconic acid methyl ester compound to the solvent is 1: 10 to 20.
3. The method of preparing supramolecular ionic liquid gels as claimed in claim 1, characterized in that: in the step a, the organic amine is any one of N-hexylamine, dodecylamine, tetradecylamine, hexadecylamine, octadecylamine and oleylamine, the catalyst is 4-dimethylaminopyridine, triethylamine or pyridine, and the solvent is N, N-dimethylformamide, methanol, ethanol or dimethyl sulfoxide.
4. The use of the supramolecular ionic liquid gel prepared in claim 1 for deep sulfur removal from fuel oils.
5. The application of the supramolecular ionic liquid gel in deep sulfur removal of fuel oil, which is characterized in that the preparation method of the simulated liquid fuel system in the application process comprises the following steps:
a sulfur-containing compound is used as a solute, and n-hexane is used as a solvent, so that a simulated fuel oil system with the concentration of 100-3000 ppm is prepared.
6. The use of supramolecular ionic liquid gel as claimed in claim 5 for deep sulfur removal from fuel oils, characterized in that: the sulfur-containing compound is thiophene, benzothiophene or dibenzothiophene.
7. The use of supramolecular ionic liquid gel as claimed in claim 5 for deep sulfur removal from fuel oils, characterized in that: the adsorption time between the supermolecule ionic liquid gel and the simulated liquid fuel system is 12-48 h, and the adsorption temperature is 15-35 ℃.
8. The use of supramolecular ionic liquid gel as claimed in claim 4 for deep sulfur removal from fuel oils, characterized in that: the concentration of the supramolecular ionic liquid gel in the application process is 10-60 mg/mL.
CN202111154181.XA 2021-09-29 2021-09-29 Preparation method of supramolecular ionic liquid gel and application of supramolecular ionic liquid gel in deep sulfur removal of fuel oil Active CN113856572B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202111154181.XA CN113856572B (en) 2021-09-29 2021-09-29 Preparation method of supramolecular ionic liquid gel and application of supramolecular ionic liquid gel in deep sulfur removal of fuel oil

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202111154181.XA CN113856572B (en) 2021-09-29 2021-09-29 Preparation method of supramolecular ionic liquid gel and application of supramolecular ionic liquid gel in deep sulfur removal of fuel oil

Publications (2)

Publication Number Publication Date
CN113856572A true CN113856572A (en) 2021-12-31
CN113856572B CN113856572B (en) 2022-06-24

Family

ID=79000729

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202111154181.XA Active CN113856572B (en) 2021-09-29 2021-09-29 Preparation method of supramolecular ionic liquid gel and application of supramolecular ionic liquid gel in deep sulfur removal of fuel oil

Country Status (1)

Country Link
CN (1) CN113856572B (en)

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20130123375A1 (en) * 2010-05-11 2013-05-16 National Research Council Of Canada Organogel Compositions Comprising Alkylated Benzimidazolones
CN104478847A (en) * 2014-12-10 2015-04-01 天津大学 Acetal-substituted glucosamide, preparation method and method for preparing supramolecular gel
CN104560120A (en) * 2014-11-13 2015-04-29 青岛科技大学 Method for extracting removal of sulfides from fuel oil by using polyether type octadecylamine ionic liquid
CN106536606A (en) * 2014-05-19 2017-03-22 巴斯夫欧洲公司 Process for producing porous alginate-based aerogels
CN107188881A (en) * 2017-06-11 2017-09-22 天津大学 Acetal replaces glucose amide and preparation method and purposes
CN108473658A (en) * 2016-01-18 2018-08-31 巴斯夫欧洲公司 The method for preparing porous material

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20130123375A1 (en) * 2010-05-11 2013-05-16 National Research Council Of Canada Organogel Compositions Comprising Alkylated Benzimidazolones
CN106536606A (en) * 2014-05-19 2017-03-22 巴斯夫欧洲公司 Process for producing porous alginate-based aerogels
CN104560120A (en) * 2014-11-13 2015-04-29 青岛科技大学 Method for extracting removal of sulfides from fuel oil by using polyether type octadecylamine ionic liquid
CN104478847A (en) * 2014-12-10 2015-04-01 天津大学 Acetal-substituted glucosamide, preparation method and method for preparing supramolecular gel
CN108473658A (en) * 2016-01-18 2018-08-31 巴斯夫欧洲公司 The method for preparing porous material
CN107188881A (en) * 2017-06-11 2017-09-22 天津大学 Acetal replaces glucose amide and preparation method and purposes

Also Published As

Publication number Publication date
CN113856572B (en) 2022-06-24

Similar Documents

Publication Publication Date Title
Le Bui et al. Synthesis, characterization and application of some non-halogen ionic liquids as green solvents for deep desulfurization of diesel oil
DE102009022284A1 (en) Desulphurization of hydrocarbons by ionic liquids and manufacturing processes
CN101376842B (en) Method for reducing sulfur content in gasoline
CN100453622C (en) Method for removing sulfide from gasoline and diesel oil through extraction of ion liquid
CN101260314A (en) Oil oxidation-extraction desulfurization technique based on ionic liquid composite solvent
CN104560120A (en) Method for extracting removal of sulfides from fuel oil by using polyether type octadecylamine ionic liquid
Duan et al. Three different types of heterocycle of nitrogen-containing alkaline ionic liquids treatment of acid oil to remove naphthenic acids
CN111808631A (en) Catalytic oxidation desulfurization method for choline ternary eutectic solvent
CN113856572B (en) Preparation method of supramolecular ionic liquid gel and application of supramolecular ionic liquid gel in deep sulfur removal of fuel oil
US2878181A (en) Method of preparing neutral oils
CN103146415A (en) Novel method for removing indole in oil product through ionic liquid
Khalilov et al. Selective treatment methods of the refinery and petrochemical products by solvent extraction with ionic liquids
KR100979686B1 (en) Process for eliminating sulfur-containing compounds from hydrocarbons using iron-containing imidazolium type ionic liquids
CN101284211A (en) Glyoxaline ion liquid reclaiming agent regeneration and cyclic utilization method
KR101022818B1 (en) Process for eliminating nitrogen-containing compounds from hydrocarbons using zinc-containing imidazolium type ionic liquids
CN104130853A (en) Method for regenerating waste oil by extracting novel combination solvent
CN105694945A (en) Preparation method and application of protic ionic liquid
CN116676101A (en) Sulfur-containing low-temperature molten salt and application thereof in removal of aromatic sulfides in fuel oil
CN113082769A (en) Preparation method of amide III type eutectic solvent and application of amide III type eutectic solvent in fuel oil extraction and desulfurization
CN104962312B (en) Application of 1-butyl-2, 3, 5-trimethylpyrazole tetrafluoroborate in removing organic nitrides in diesel oil
JP2010215737A (en) Method of purifying hydrocarbon oil by desulfurization or denitrification
CN115305109B (en) Temperature response type porous liquid extractant, and preparation method and application thereof
CN1850947A (en) Removal of naphthenic acid in oil using composite deacidifying agent
CN104650956A (en) Method for removing dibenzothiophene in oil products by extracting
CN102040553A (en) Preparation method of gasoline extraction and desulfurization agent

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant