CN114106870B - Method for extracting denitrification from fuel oil by using triethylene glycol-metal nitrate composite solvent - Google Patents
Method for extracting denitrification from fuel oil by using triethylene glycol-metal nitrate composite solvent Download PDFInfo
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- CN114106870B CN114106870B CN202111190296.4A CN202111190296A CN114106870B CN 114106870 B CN114106870 B CN 114106870B CN 202111190296 A CN202111190296 A CN 202111190296A CN 114106870 B CN114106870 B CN 114106870B
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- 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
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Abstract
The invention relates to a method for extracting denitrification from fuel oil by using a triethylene glycol-metal nitrate composite solvent. The metal nitrate and triethylene glycol are uniformly mixed according to a specific proportion and then are used as a composite extractant, the composite extractant is mixed with fuel oil for extraction under the stirring condition of 20-50 ℃, the denitrified fuel oil is obtained after standing delamination and liquid-liquid separation operation, and a large number of test results show that the denitrifying rate of the method is up to 99%. The invention utilizes the strong Lewis acidity of the metal nitrate to lead the compound extractant to generate stronger Lewis acid-base complex reaction with the organic nitrogen in the fuel oil, thereby obviously improving the denitrification performance. The novel composite extractant has the advantages of high selectivity, thorough and rapid denitrification, low cost and the like, and has wide industrial application prospect.
Description
Technical Field
The invention relates to the technical field of petrochemical industry and environmental protection, in particular to a method for extracting and denitrifying fuel oil by using a triethylene glycol-metal nitrate compound solvent.
Background
With the rapid development of the economy in China, the demands for fuel oil such as gasoline, diesel oil and the like are greatly increased. Organic nitrogen in fuel oil not only affects chromaticity and oxidation stability of the product, but also releases a large amount of nitrogen oxides during combustion, and once the polluted gas is discharged into the atmosphere, haze (PM 2.5) is extremely easy to form, so that serious environmental problems are caused, and therefore, the nitrogen in the fuel oil needs to be removed as much as possible. The analysis result shows that the organic nitride in the fuel oil mainly comprises pyridine, quinoline, pyrrole, indole and the like. Hydrogenation technology is generally adopted in industry to remove nitrogen in fuel oil, but hydrogenation reaction conditions are harsh (high temperature and high pressure), high requirements on catalysts, equipment investment and running cost are too high, and the defects and the shortcomings cause the hydrogenation technology to be limited in industrial production.
In order to make the fuel denitrification process conditions milder, alternative non-hydrodenitrogenation technologies such as extraction, adsorption, oxidation, photocatalysis and the like have been developed. The extraction process can denitrify the fuel oil under mild conditions, and is simple to operate, so that the extraction process is widely focused. For this reason, the inventor group has already proposed a method for extracting denitrification from fuel oil by using polyethylene glycol and its modified compound (see chinese patent CN 107937013B) in 2017, wherein ether bond and hydroxyl group in polyethylene glycol and its modified compound can react with N in fuel oil, but the strength of the action is insufficient, so that denitrification performance and selectivity still remain to be improved, and at the same time polyethylene glycol dicarboxylic acid shows excellent denitrification performance due to strong acidity of carboxyl group. Polyethylene glycol is cheaper but has relatively poor denitrification performance, while polyethylene glycol dicarboxylic acid has good denitrification performance but has higher raw material cost, and all the adverse factors limit the industrial application prospect of polyethylene glycol and modified compounds thereof in the aspect of denitrification of fuel oil. The inventors have subsequently developed a series of different types of fuel denitrification extractants including polyetheramine-formic acid (CN 109355091B), polyethyleneglycol dicarboxylic acid-quaternary ammonium salt (CN 109181747B), polyethyleneimine (CN 108059972B), and the like.
Based on the above, the inventor continues to develop and take continuous efforts, and successfully develops a fuel oil extraction denitrification method based on triethylene glycol-metal nitrate composite solvent. According to the method, the metal nitrate is uniformly dispersed in the triethylene glycol, the defect of insufficient acidity of the pure triethylene glycol is well overcome by utilizing the characteristics of strong Lewis acidity and high polarity of the metal nitrate, and the obtained triethylene glycol-metal nitrate composite solvent and alkaline nitrogen in the fuel oil can undergo a strong Lewis acid-base complexation reaction, so that removal of nitride (especially alkaline nitrogen) in the fuel oil is promoted, and a higher denitrification rate is realized.
Disclosure of Invention
The invention aims to provide a fuel oil denitrification compound extractant which comprises triethylene glycol and metal nitrate.
Further, the metal nitrate is specifically at least one of silver nitrate, ferric nitrate, cobalt nitrate, nickel nitrate, copper nitrate, zinc nitrate, palladium nitrate, chromium nitrate and manganese nitrate. The selected metal salt has stronger Lewis acidity and has better mutual solubility with triethylene glycol, so that other metal salts such as sulfate and the like are eliminated.
Furthermore, the metal nitrate does not contain crystal water and free water, so that the raw materials need to be sufficiently dried before being used.
Further, the mass fraction of the metal nitrate in the composite extractant is 0.5% -3%.
Further, the composite extractant is formed by mixing triethylene glycol and metal nitrate, namely a double-component.
Another object of the present invention is to provide a method for denitriding fuel oil by using the above composite extractant, which comprises the following specific steps: mixing the composite extractant with fuel oil, extracting, standing and separating liquid.
Further, the mass ratio of the composite extractant to the fuel oil is 0.02-2.
Further, the molar ratio of the metal nitrate in the composite extractant to the N in the fuel oil is 0.5-4.
Further, the extraction temperature is 20-50 ℃, the extraction time is 5-30min, and stirring is kept during the extraction process.
Further, the boiling range of the fuel oil is 70-350 ℃, and the nitrogen content is 50-600 mug/g.
According to the invention, the composite solvent of triethylene glycol and metal nitrate is used as an extracting agent, and the strong Lewis acidity of the metal nitrate is used to enable the composite solvent to rapidly perform a stronger Lewis acid-base complexation reaction with organic nitrogen, so that the efficient removal of the organic nitrogen in the fuel oil is realized. Compared with the prior art, the invention has the beneficial effects that: (1) The proper amount of metal nitrate is highly dispersed in triethylene glycol, can quickly and efficiently generate stronger complexation with organic nitrogen in fuel oil, has a denitrification rate as high as 99 percent, and shows high selectivity; (2) The whole extraction denitrification operation condition is mild, high temperature and high pressure are not needed, the time required for achieving a better denitrification effect is short, and the denitrification efficiency is high; (3) The raw material triethylene glycol has low cost, the addition amount of metal nitrate is low, and the production and use cost of the whole composite extractant is moderate comprehensively, so that the application prospect is good.
Detailed Description
In order for those of ordinary skill in the art to fully understand the technical solutions and advantageous effects of the present invention, the following description will be given with reference to specific embodiments.
Example 1
Composite extractant: a homogeneous mixture of silver nitrate and triethylene glycol, wherein the mass fraction of silver nitrate is 2.4%. If the metal nitrate raw material contains bound water or absorbs moisture in the air, it is necessary to remove water before use.
Fuel oil: the initial nitrogen content of the simulated gasoline formed by mixing pyrrole with n-octane is controlled to be 500 mug/g.
The process conditions are as follows: the extraction temperature is 30 ℃, the extraction time is 30min, and the mixing mass ratio of the extractant to the fuel oil is 2. Stirring continuously in the extraction process, standing and layering after extraction is completed, and separating liquid from liquid to obtain a denitrification oil phase and a nitrogen-rich extraction phase.
After the extraction operation, the nitrogen content in the fuel oil is reduced to 3.25 mug/g, the calculated denitrification rate is 99.35%, and the mass distribution coefficient is 75.22.
Example 2
Composite extractant: a homogeneous mixture of silver nitrate and triethylene glycol, wherein the mass fraction of silver nitrate is 2.4%.
Fuel oil: the simulated gasoline formed by mixing indole and n-octane has an initial nitrogen content of 500 mug/g.
The process conditions are as follows: the extraction temperature is 30 ℃, the extraction time is 30min, and the mixing mass ratio of the extractant to the fuel oil is 2. Stirring continuously in the extraction process, standing and layering after extraction is completed, and separating liquid from liquid to obtain a denitrification oil phase and a nitrogen-rich extraction phase.
After the extraction operation, the nitrogen content in the fuel oil is reduced to 1.93 mug/g, the calculated denitrification rate is 99.61%, and the mass distribution coefficient is 126.98.
Example 3
Composite extractant: a homogeneous mixture of silver nitrate and triethylene glycol, wherein the mass fraction of silver nitrate is 2.4%.
Fuel oil: the initial nitrogen content of the simulated gasoline formed by mixing pyridine and n-octane is controlled to be 500 mug/g.
The process conditions are as follows: the extraction temperature is 30 ℃, the extraction time is 30min, and the mixing mass ratio of the extractant to the fuel oil is 2. Stirring continuously in the extraction process, standing and layering after extraction is completed, and separating liquid from liquid to obtain a denitrification oil phase and a nitrogen-rich extraction phase.
After the extraction operation, the nitrogen content in the fuel oil is reduced to 4.11 mug/g, the calculated denitrification rate is 99.18%, and the mass distribution coefficient is 59.48.
Example 4
Composite extractant: a homogeneous mixture of cobalt nitrate and triethylene glycol, wherein the mass fraction of cobalt nitrate is 2.6%.
Fuel oil: the simulated gasoline formed by mixing indole and n-octane has an initial nitrogen content of 500 mug/g.
The process conditions are as follows: the extraction temperature is 30 ℃, the extraction time is 30min, and the mixing mass ratio of the extractant to the fuel oil is 1. Stirring continuously in the extraction process, standing and layering after extraction is completed, and separating liquid from liquid to obtain a denitrification oil phase and a nitrogen-rich extraction phase.
After the extraction operation, the nitrogen content in the fuel oil is reduced to 2.69 mug/g, the calculated denitrification rate is 99.46%, and the mass distribution coefficient is 180.12.
Example 5
Composite extractant: a homogeneous mixture of cobalt nitrate and triethylene glycol, wherein the mass fraction of cobalt nitrate is 2.6%.
Fuel oil: the initial nitrogen content of the simulated gasoline formed by mixing pyridine and n-octane is controlled to be 500 mug/g.
The process conditions are as follows: the extraction temperature is 30 ℃, the extraction time is 30min, and the mixing mass ratio of the extractant to the fuel oil is 1. Stirring continuously in the extraction process, standing and layering after extraction is completed, and separating liquid from liquid to obtain a denitrification oil phase and a nitrogen-rich extraction phase.
After the extraction operation, the nitrogen content in the fuel oil is reduced to 12.9 mug/g, the calculated denitrification rate is 97.42%, and the mass distribution coefficient is 36.76.
Example 6
Composite extractant: a homogeneous mixture of nickel nitrate and triethylene glycol, wherein the mass fraction of nickel nitrate is 2.6%.
Fuel oil: the simulated gasoline formed by mixing indole and n-octane has an initial nitrogen content of 500 mug/g.
The process conditions are as follows: the extraction temperature is 30 ℃, the extraction time is 30min, and the mixing mass ratio of the extractant to the fuel oil is 1. Stirring continuously in the extraction process, standing and layering after extraction is completed, and separating liquid from liquid to obtain a denitrification oil phase and a nitrogen-rich extraction phase.
After the extraction operation, the nitrogen content in the fuel oil is reduced to 3.33 mug/g, the calculated denitrification rate is 99.33%, and the mass distribution coefficient is 145.99.
Example 7
Composite extractant: a homogeneous mixture of nickel nitrate and triethylene glycol, wherein the mass fraction of nickel nitrate is 2.6%.
Fuel oil: the initial nitrogen content of the simulated gasoline formed by mixing pyrrole with n-octane is controlled to be 500 mug/g.
The process conditions are as follows: the extraction temperature is 30 ℃, the extraction time is 30min, and the mixing mass ratio of the extractant to the fuel oil is 1. Stirring continuously in the extraction process, standing and layering after extraction is completed, and separating liquid from liquid to obtain a denitrification oil phase and a nitrogen-rich extraction phase.
After the extraction operation, the nitrogen content in the fuel oil is reduced to 6.56 mug/g, the calculated denitrification rate is 98.69%, and the mass distribution coefficient is 73.89.
Example 8
Composite extractant: a homogeneous mixture of zinc nitrate and triethylene glycol, wherein the mass fraction of zinc nitrate is 2.7%.
Fuel oil: the initial nitrogen content of the simulated gasoline formed by mixing pyridine and n-octane is controlled to be 500 mug/g.
The process conditions are as follows: the extraction temperature is 30 ℃, the extraction time is 30min, and the mixing mass ratio of the extractant to the fuel oil is 2. Stirring continuously in the extraction process, standing and layering after extraction is completed, and separating liquid from liquid to obtain a denitrification oil phase and a nitrogen-rich extraction phase.
After the extraction operation, the nitrogen content in the fuel oil is reduced to 6.14 mug/g, the calculated denitrification rate is 98.77%, and the mass distribution coefficient is 39.47.
Example 9
Composite extractant: a homogeneous mixture of zinc nitrate and triethylene glycol, wherein the mass fraction of zinc nitrate is 1.4%.
Fuel oil: the initial nitrogen content of the simulated gasoline formed by mixing pyrrole with n-octane is controlled to be 500 mug/g.
The process conditions are as follows: the extraction temperature is 30 ℃, the extraction time is 30min, and the mixing mass ratio of the extractant to the fuel oil is 1. Stirring continuously in the extraction process, standing and layering after extraction is completed, and separating liquid from liquid to obtain a denitrification oil phase and a nitrogen-rich extraction phase.
After the extraction operation, the nitrogen content in the fuel oil is reduced to 7.85 mug/g, the calculated denitrification rate is 98.43%, and the mass distribution coefficient is 61.03.
Example 10
Composite extractant: a homogeneous mixture of zinc nitrate and triethylene glycol, wherein the mass fraction of zinc nitrate is 2.7%.
Fuel oil: the initial nitrogen content of the catalytic cracking diesel produced by a certain refinery is controlled to be 282 mug/g.
The process conditions are as follows: the extraction temperature is 30 ℃, the extraction time is 30min, and the mixing mass ratio of the extractant to the fuel oil is 1. Stirring continuously in the extraction process, standing and layering after extraction is completed, and separating liquid from liquid to obtain a denitrification oil phase and a nitrogen-rich extraction phase.
After the extraction operation, the nitrogen content in the fuel oil is reduced to 80.36 mug/g, the calculated denitrification rate is 71.96%, and the mass distribution coefficient is 2.49.
Example 11
Composite extractant: a homogeneous mixture of nickel nitrate and triethylene glycol, wherein the mass fraction of nickel nitrate is 2.7%.
Fuel oil: the initial nitrogen content of the catalytic cracking diesel produced by a certain refinery is controlled to be 282 mug/g.
The process conditions are as follows: the extraction temperature is 30 ℃, the extraction time is 30min, and the mixing mass ratio of the extractant to the fuel oil is 1. Stirring continuously in the extraction process, standing and layering after extraction is completed, and separating liquid from liquid to obtain a denitrification oil phase and a nitrogen-rich extraction phase.
After the extraction operation, the nitrogen content in the fuel oil is reduced to 79.85 mug/g, the calculated denitrification rate is 72.14%, and the mass distribution coefficient is 2.51.
Experiments show that besides the metal nitrate such as silver nitrate, cobalt nitrate, nickel nitrate, zinc nitrate and the like, the organic nitrogen in the simulated oil and the actual fuel oil can be efficiently and rapidly removed after the ferric nitrate, the copper nitrate, the palladium nitrate, the chromium nitrate, the manganese nitrate and the triethylene glycol are mixed according to a specific proportion.
In addition, in order to further illustrate the denitrification effect of the compound extractant, a comparison experiment is performed by taking pure triethylene glycol as the extractant.
Comparative example 1
The extractant comprises: pure triethylene glycol.
Fuel oil: the initial nitrogen content of the simulated gasoline formed by mixing pyridine and n-octane is controlled to be 500 mug/g.
The process conditions are as follows: the extraction temperature is 30 ℃, the extraction time is 30min, and the mixing mass ratio of the extractant to the fuel oil is 1. Stirring continuously in the extraction process, standing and layering after extraction is completed, and separating liquid from liquid to obtain a denitrification oil phase and a nitrogen-rich extraction phase.
After the extraction operation, the nitrogen content in the fuel oil is reduced to 77.49 mug/g, the calculated denitrification rate is 84.5%, and the mass distribution coefficient is 5.33.
Comparative example 2
The extractant comprises: pure triethylene glycol.
Fuel oil: the simulated gasoline formed by mixing quinoline and n-octane has an initial nitrogen content of 500 mug/g.
The process conditions are as follows: the extraction temperature is 30 ℃, the extraction time is 30min, and the mixing mass ratio of the extractant to the fuel oil is 1. Stirring continuously in the extraction process, standing and layering after extraction is completed, and separating liquid from liquid to obtain a denitrification oil phase and a nitrogen-rich extraction phase.
After the extraction operation, the nitrogen content in the fuel oil is reduced to 71.18 mug/g, the calculated denitrification rate is 85.76%, and the mass distribution coefficient is 5.92.
Claims (3)
1. The method for denitrifying the fuel oil by utilizing the composite extractant is characterized by comprising the following steps of: mixing the composite extractant with fuel oil, extracting, standing and separating liquid; wherein the mass ratio of the composite extractant to the fuel oil is 0.02-2, and the molar ratio of the metal nitrate in the composite extractant to the N in the fuel oil is 0.5-4; the composite extractant is formed by mixing triethylene glycol and metal nitrate, wherein the mass fraction of the metal nitrate is 0.5% -3%, the metal nitrate is at least one of silver nitrate, ferric nitrate, cobalt nitrate, nickel nitrate, copper nitrate, zinc nitrate, palladium nitrate, chromium nitrate and manganese nitrate, and the metal nitrate is required to be sufficiently dried before use so as to be free of crystal water and free water.
2. The method of claim 1, wherein: the extraction temperature is 20-50deg.C, the extraction time is 5-30min, and stirring is maintained during extraction.
3. The method of claim 1, wherein: the boiling range of the fuel oil is 70-350 ℃, and the nitrogen content is 50-600 mug/g.
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