CN116144393B - Composite solvent and method for producing low-aromatic special oil - Google Patents

Composite solvent and method for producing low-aromatic special oil Download PDF

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CN116144393B
CN116144393B CN202310360229.5A CN202310360229A CN116144393B CN 116144393 B CN116144393 B CN 116144393B CN 202310360229 A CN202310360229 A CN 202310360229A CN 116144393 B CN116144393 B CN 116144393B
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oil
glycol
composite
aromatic hydrocarbon
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CN116144393A (en
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王明东
郝天臻
崔欣
匡薇薇
李江柳
王涛
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Sinopec Luoyang Co
Hebei Refining Technology Co ltd
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Sinopec Luoyang Co
Hebei Refining Technology Co ltd
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    • 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
    • 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
    • C10G21/02—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents with two or more solvents, which are introduced or withdrawn separately
    • 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
    • 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
    • C10G21/16—Oxygen-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
    • C10G21/06—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
    • C10G21/06—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents characterised by the solvent used
    • C10G21/12—Organic compounds only
    • C10G21/22—Compounds containing sulfur, selenium, or tellurium
    • 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
    • C10G2300/10—Feedstock materials
    • C10G2300/1037—Hydrocarbon fractions
    • C10G2300/1044—Heavy gasoline or naphtha having a boiling range of about 100 - 180 °C
    • 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
    • C10G2300/10—Feedstock materials
    • C10G2300/1037—Hydrocarbon fractions
    • C10G2300/1048—Middle distillates
    • 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
    • C10G2300/10—Feedstock materials
    • C10G2300/1037—Hydrocarbon fractions
    • C10G2300/1048—Middle distillates
    • C10G2300/1051—Kerosene having a boiling range of about 180 - 230 °C

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  • 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)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

The invention relates to a composite solvent for producing low-aromatic special oil, which comprises, by mass, 10% -50% of a main solvent, 49% -89% of a reinforcing agent, 0.05% -0.5% of a stabilizing agent and the balance of water; the main solvent is a mixture of sulfone or sulfoxide and glycol solvents. The composite solvent has the advantages of good thermal stability, high aromatic hydrocarbon selectivity, strong heavy aromatic hydrocarbon removal capability and easy regeneration. The invention also relates to a method for producing low-aromatic special oil by separating aromatic hydrocarbon in distillate oil with the final distillation point less than or equal to 250 ℃ through liquid-liquid extraction by using the composite solvent. By adopting the composite solvent, under proper process conditions, the distillate oil with the final distillation point less than or equal to 250 ℃ such as naphtha, kerosene, diesel oil and the like is dearomatized, and the special oil with the content as low as 0.2 percent can be obtained.

Description

Composite solvent and method for producing low-aromatic special oil
Technical Field
The invention relates to the field of energy conservation and environmental protection, belongs to the technical field of separation of aromatic hydrocarbon from raw oil, in particular to a composite solvent for producing low-aromatic special oil, and especially relates to a composite solvent which is suitable for distillate oil with the final distillation point less than or equal to 250 ℃ such as naphtha, kerosene, diesel oil and the like and is used for producing low-aromatic special oil through liquid-liquid extraction dearomatization.
Background
With the increasing shortage of traditional energy and the increasingly prominent environmental pollution problem, new energy automobiles become a break for leading the transformation and upgrading of the automobile industry. With the rapid development of energy conservation quantity acceleration and alternative energy sources of the fuel oil vehicle, the domestic fuel oil consumption demand quantity is rapidly reduced. The transformation development of the fuel industry is imperative and the structural adjustment is urgent.
The national energy transformation development is supported, and the steps of promoting oil transformation and oil transformation are quickened. The oil transfer technology is not completely mature due to the characteristics of more related products, strong process uniqueness and the like. The aromatic hydrocarbon content in the special oil is used as an important measurement index, and has relatively strict requirements, so that the domestic 'oil-to-special' production technology is urgently required to be developed.
In the prior art, the aromatic hydrocarbon separation in naphtha and gasoline fraction usually adopts a liquid-liquid extraction dearomatization technology (also called extraction dearomatization). The method can effectively separate saturated hydrocarbon from aromatic hydrocarbon, and has the advantages of mild operation conditions, recycling of extractant, capability of obtaining aromatic hydrocarbon byproducts and the like. Typical liquid-liquid extraction processes exist as Sulfolane process from UOP company, udex process, tetra process from co-carbon company, etc. The separation of aromatic hydrocarbon in diesel oil fraction is mainly adsorption separation method.
CN 112552951A discloses a compound extractant suitable for removing aromatic hydrocarbon from low-content aromatic hydrocarbon straight-run naphtha and an application method thereof, wherein the compound extractant comprises dimethyl sulfoxide, N-Dimethylformamide (DMF) and propylene carbonate. The naphtha with low content of aromatic hydrocarbon is combined with a water scrubber and a stripper for aromatic hydrocarbon extraction after being subjected to prefractionation and extraction and dearomatization devices to produce dearomatization naphtha and aromatic hydrocarbon products, wherein the aromatic hydrocarbon content in the dearomatization naphtha products is about 1 percent.
CN104031674 a discloses a composite solvent for extracting and separating aromatic hydrocarbon from low aromatic naphtha, wherein the main solvent is propylene carbonate, and the main solvent is compounded with solvents such as N-methyl pyrrolidone, glycerol and the like, and after the aromatic hydrocarbon is removed by a proper process, the aromatic hydrocarbon content in the raffinate oil product is 0.8% -1%.
CN 104073285A discloses a method for separating aromatic hydrocarbon from diesel oil by liquid-liquid extraction, in the method, a first extraction solvent and a second extraction solvent are introduced, wherein the first extraction solvent and the second extraction solvent are both selected from N, N-dimethylformamide or ethylene glycol methyl ether, the boiling point of the solvents is lower than that of raw oil, and the solvents are regenerated by adopting a reduced pressure distillation method. The method needs to distill out the solvent, and has relatively high energy consumption. The aromatic hydrocarbon content in the raffinate oil is about 15%.
The common problems of the liquid-liquid extraction dearomatization solvent which is industrialized at present include: the method is not suitable for low aromatic hydrocarbon raw oil and has poor solvent selectivity, so that the product yield is low; the heavy aromatics removal capability above C10 is poor, so that the aromatics content of raffinate oil is 1% or above, and the requirements of the aromatics content of special oil are difficult to meet. Although the aromatic hydrocarbon content of raffinate oil in the prior art is 1% or more, which can meet the requirements of ethylene cracking raw materials, the existence of aromatic hydrocarbon can influence the yield of olefin and increase the coking amount of a cracking furnace. Therefore, it is necessary to develop a solvent having a high dearomatization ability and a high selectivity.
Disclosure of Invention
Aiming at the above fuel oil transformation requirement and the current solvent situation used in the prior art, the invention aims to provide a composite solvent suitable for producing low-aromatic special oil, and aromatic hydrocarbon is removed from distillate oil with the final distillation point less than or equal to 250 ℃ such as naphtha, kerosene, diesel oil and the like by adopting a liquid-liquid extraction mode, so that the aromatic hydrocarbon of raffinate oil can be removed to be less than 0.2%, and the aromatic hydrocarbon content requirement of the low-aromatic special oil can be met. The composite solvent is used for separating aromatic hydrocarbon and has the advantages of good thermal stability, strong heavy aromatic hydrocarbon removal capability, easy regeneration and the like.
In order to achieve the above object, the present invention adopts the following technical measures:
firstly, providing a composite solvent for producing low-aromatic special oil, which comprises the following components in percentage by mass:
10% -50% of main solvent, 49% -89% of reinforcing agent, 0.05% -0.5% of stabilizer and the balance of water; the main solvent is a mixture of sulfone or sulfoxide and glycol solvents.
The preferred composite solvent comprises the following components in percentage by mass: 10% -40% of main solvent, 59% -89% of reinforcing agent, 0.05% -0.5% of stabilizer and the balance of water.
In the further preferred composite solvent, the mass ratio of the sulfone or sulfoxide to the glycol solvent in the main solvent is 2:1-4:1; more preferably 2:1.
In a preferred embodiment of the invention, the composite solvent comprises the following components in percentage by mass: 5% -25% of sulfone or sulfoxide, 5% -25% of glycol solvent, 50% -89% of reinforcing agent, 0.05% -0.5% of stabilizer and the balance of water.
In a more preferred embodiment of the present invention, the composite solvent comprises the following components in percentage by mass: 10-20% of sulfone or sulfoxide, 5-10% of glycol solvent, 69-84% of reinforcing agent, 0.05-0.1% of stabilizer and the balance of water.
In the preferred composite solvent of the invention, the sulfone can be any one or more than two of dimethyl sulfone, diethyl sulfone or sulfolane; the sulfoxide can be any one or a mixture of two of dimethyl sulfoxide and diethyl sulfoxide.
In the preferred composite solvent of the present invention, the glycol solvent may be any one or a mixture of two or more of ethylene glycol, diethylene glycol, triethylene glycol and tetraethylene glycol.
In the preferred composite solvent of the invention, the enhancer is selected from any one or more than two of N-formyl morpholine, 2-pyrrolidone, propylene carbonate, N-methyl pyrrolidone, N-dimethylformamide or N, N-dimethylacetamide.
In the preferred composite solvent of the invention, the stabilizer is selected from any one or more than two of N, N-diphenyl-p-phenylenediamine, N- (1, 3-dimethylbutyl) -N' -phenyl-p-phenylenediamine or 4-butylamine-2, 6-tetramethylpiperidine.
The inventor researches find that the sulfone or sulfoxide and the glycol solvents have different selectivities to single-ring, multi-ring, tricyclic and above aromatic hydrocarbons, and the solvents have higher selectivities to mixed aromatic hydrocarbons through compounding. On the basis, the solubility and the selectivity of the composite solvent can be further enhanced through reasonable compounding with the reinforcing agent, so that the composite solvent has a very outstanding dearomatization effect. For low aromatic hydrocarbon raw oil, special oil with the aromatic hydrocarbon content of raffinate oil less than 0.2% and byproduct aromatic oil can be obtained by a liquid-liquid extraction mode. The invention solves the problems of low heavy aromatics removal rate and difficult regeneration, and can meet the aromatics index requirement in the low-aromatics special oil by liquid-liquid extraction, so that the invention is suitable for aromatic hydrocarbon and makes best use of the aromatic hydrocarbon.
The invention relates to a compound solvent for producing low-aromatic special oil, which comprises the following preparation method: firstly, adding glycol solvents into sulfone or sulfoxide, and uniformly stirring and mixing to obtain the main solvent; adding the reinforcing agent into the main solvent according to the proportion, and uniformly mixing again; and finally, adding the stabilizer according to a proportion, and uniformly mixing to obtain the composite solvent for producing the low-aromatic special oil.
On the basis, the invention also provides a method for separating aromatic hydrocarbon in distillate oil with the final distillation point less than or equal to 250 ℃ such as naphtha, kerosene, diesel oil and the like by using the composite solvent through liquid-liquid extraction, which comprises the following steps: taking the composite solvent and the raw oil according to the volume ratio of 3:1-4:1, carrying out multistage countercurrent contact in an extraction tower at the tower top temperature of 80-120 ℃, eluting the raffinate oil at the tower top with water to remove the solvent, and forming a low-aromatic special oil product; and (3) carrying out reduced pressure distillation on the tower bottom rich solvent to obtain aromatic-rich oil, and enabling the regenerated lean agent to serve as a composite solvent for producing low-aromatic special oil to enter an extraction tower for recycling.
Compared with the prior art, the invention has the following beneficial effects:
(1) The compound solvent in the invention has wide application range of raw oil, can be suitable for removing aromatic hydrocarbon in naphtha, kerosene and diesel oil with the final distillation point less than or equal to 250 ℃, and is mainly used for removing heavy aromatic hydrocarbon;
(2) The composite solvent in the invention has high selectivity and strong heavy aromatic hydrocarbon removal capability, and can remove the heavy aromatic hydrocarbon in naphtha, kerosene and diesel oil to less than 0.2 percent, thereby meeting the index requirement of aromatic hydrocarbon content in low-aromatic special oil, having high raffinate oil recovery rate and being a byproduct of aromatic-rich oil;
(3) The composite solvent has good stability and easy regeneration, can be used for high-temperature extraction, and can be regenerated through a conventional process. Solves the problems of difficult removal of aromatic hydrocarbon in raw oil with the final distillation point lower than 250 ℃ and difficult regeneration of solvent.
Drawings
FIG. 1 is a schematic diagram of the liquid-liquid extraction process for removing aromatic hydrocarbons using an extraction column described in test examples 1-3. The upward arrow indicates the flow direction of the raw oil, and the downward arrow indicates the flow direction of the extraction solvent.
Detailed Description
The technical solutions of the present invention are further illustrated by the following examples, which are merely illustrative and are not to be construed as limiting the scope of the present invention.
Example 1
The composite solvent for liquid-liquid extraction of aromatic hydrocarbon from naphtha, kerosene and diesel oil fraction to produce low-aromatic special oil comprises, by mass, sulfolane 20%, triethylene glycol 10%, reinforcing agent 2-pyrrolidone 69%, stabilizer N, N-diphenyl-p-phenylenediamine 0.05% and water in balance. The preparation method comprises the following steps: firstly, adding triethylene glycol into sulfolane according to a proportion, and uniformly stirring and mixing to obtain a main solvent; adding 2-pyrrolidone into the main solvent according to a certain proportion, and uniformly mixing again; and finally, adding N, N-diphenyl-p-phenylenediamine according to a proportion, and uniformly mixing to obtain the composite solvent-I for dearomatization.
Example 2
The composite solvent for liquid-liquid extraction of aromatic hydrocarbon from naphtha, kerosene and diesel oil fraction to produce low-aromatic special oil comprises, by mass, sulfolane 20%, triethylene glycol 10%, propylene carbonate as reinforcing agent 69%, N-diphenyl-p-phenylenediamine as stabilizer 0.05% and water as rest. The preparation method comprises the following steps: firstly, adding triethylene glycol into sulfolane according to a proportion, and uniformly stirring and mixing to obtain a main solvent; adding propylene carbonate into the main solvent according to the proportion, and uniformly mixing again; and finally, adding N, N-diphenyl-p-phenylenediamine according to a proportion, and uniformly mixing to obtain the composite solvent-II for dearomatization.
Example 3
The composite solvent for liquid-liquid extraction of aromatic hydrocarbon in naphtha, kerosene and diesel oil fraction to produce low-aromatic special oil comprises, by mass, sulfolane 10%, diethylene glycol 5%, N-formylmorpholine as reinforcing agent 84%, N-diphenyl-p-phenylenediamine as stabilizer 0.05% and water as rest. The preparation method comprises the following steps: firstly, adding diethylene glycol into sulfolane according to a proportion, and uniformly stirring and mixing to obtain a main solvent; adding N-formylmorpholine into the main solvent according to a certain proportion, and uniformly mixing again; and finally, adding N, N-diphenyl-p-phenylenediamine according to a proportion, and uniformly mixing to obtain the composite solvent-III for dearomatization.
Example 4
The composite solvent for liquid-liquid extraction of aromatic hydrocarbon from naphtha, kerosene and diesel oil fraction to produce low-aromatic special oil comprises, by mass, sulfolane 20%, triethylene glycol 10%, reinforcing agent 2-pyrrolidone 69%, stabilizer N- (1, 3-dimethylbutyl) -N' -phenyl-p-phenylenediamine 0.1% and water in balance. The preparation method comprises the following steps: firstly, adding triethylene glycol into sulfolane according to a proportion, and uniformly stirring and mixing to obtain a main solvent; adding 2-pyrrolidone into the main solvent according to a certain proportion, and uniformly mixing again; and finally, adding N- (1, 3-dimethylbutyl) -N' -phenyl-p-phenylenediamine according to a proportion, and uniformly mixing to obtain the composite solvent-IV for dearomatization.
Example 5
The composite solvent for liquid-liquid extraction of aromatic hydrocarbon from naphtha, kerosene and diesel oil fraction to produce low-aromatic special oil comprises, by mass, 32% of sulfolane, 16% of triethylene glycol, 49% of reinforcing agent 2-pyrrolidone, 0.1% of stabilizer N- (1, 3-dimethylbutyl) -N' -phenyl-p-phenylenediamine and the balance of water. The preparation method comprises the following steps: firstly, adding triethylene glycol into sulfolane according to a proportion, and uniformly stirring and mixing to obtain a main solvent; adding 2-pyrrolidone into the main solvent according to a certain proportion, and uniformly mixing again; and finally, adding N- (1, 3-dimethylbutyl) -N' -phenyl-p-phenylenediamine according to a proportion, and uniformly mixing to obtain the composite solvent-V for dearomatization.
Example 6
The composite solvent for liquid-liquid extraction of aromatic hydrocarbon from naphtha, kerosene and diesel oil fraction to produce low-aromatic special oil comprises, by mass, 27% of sulfolane, 13% of triethylene glycol, 59% of reinforcing agent 2-pyrrolidone, 0.05% of stabilizer N- (1, 3-dimethylbutyl) -N' -phenyl-p-phenylenediamine and the balance of water. The preparation method comprises the following steps: firstly, adding triethylene glycol into sulfolane according to a proportion, and uniformly stirring and mixing to obtain a main solvent; adding 2-pyrrolidone into the main solvent according to a certain proportion, and uniformly mixing again; and finally, adding the N- (1, 3-dimethylbutyl) -N' -phenyl-p-phenylenediamine according to a proportion, and uniformly mixing to obtain the composite solvent-VI for dearomatization.
Example 7
The composite solvent for liquid-liquid extraction of aromatic hydrocarbon from naphtha, kerosene and diesel oil fraction to produce low-aromatic special oil comprises, by mass, sulfolane 30%, triethylene glycol 10%, reinforcing agent 2-pyrrolidone 59%, stabilizer N- (1, 3-dimethylbutyl) -N' -phenyl-p-phenylenediamine 0.05% and water in balance. The preparation method comprises the following steps: firstly, adding triethylene glycol into sulfolane according to a proportion, and uniformly stirring and mixing to obtain a main solvent; adding 2-pyrrolidone into the main solvent according to a certain proportion, and uniformly mixing again; and finally, adding N- (1, 3-dimethylbutyl) -N' -phenyl-p-phenylenediamine according to a proportion, and uniformly mixing to obtain the composite solvent-VII for dearomatization.
Example 8
The composite solvent for liquid-liquid extraction of aromatic hydrocarbon from naphtha, kerosene and diesel oil fraction to produce low-aromatic special oil comprises, by mass, 32% of sulfolane, 8% of triethylene glycol, 59% of reinforcing agent 2-pyrrolidone, 0.05% of stabilizer N- (1, 3-dimethylbutyl) -N' -phenyl-p-phenylenediamine and the balance of water. The preparation method comprises the following steps: firstly, adding triethylene glycol into sulfolane according to a proportion, and uniformly stirring and mixing to obtain a main solvent; adding 2-pyrrolidone into the main solvent according to a certain proportion, and uniformly mixing again; and finally, adding N- (1, 3-dimethylbutyl) -N' -phenyl-p-phenylenediamine according to a proportion, and uniformly mixing to obtain the composite solvent-VIII for dearomatization.
Comparative example 1
The composite solvent comprises, by mass, 30% of sulfolane, 69% of reinforcing agent 2-pyrrolidone, 0.05% of stabilizer N, N-diphenyl-p-phenylenediamine and the balance of water. And uniformly mixing the components according to a proportion to obtain the control compound solvent-I.
Comparative example 2
The composite solvent comprises, by mass, 30% of triethylene glycol, 69% of a reinforcing agent 2-pyrrolidone, 0.05% of a stabilizer N, N-diphenyl-p-phenylenediamine and the balance of water. And uniformly mixing the components according to a proportion to obtain the control compound solvent-II.
Comparative example 3
The composite solvent comprises, by mass, 99% of sulfolane, 0.05% of stabilizer N, N-diphenyl-p-phenylenediamine and the balance of water. And uniformly mixing the components according to a proportion to obtain the control compound solvent-III.
Comparative example 4
The composite solvent comprises, by mass, 66% of sulfolane, 33% of triethylene glycol, 0.05% of stabilizer N, N-diphenyl-p-phenylenediamine and the balance of water. With reference to the preparation method of example 1, the components are mixed uniformly step by step according to the proportion to obtain the control compound solvent-IV.
Comparative example 5
The composite solvent comprises, by mass, 50% of sulfolane, 25% of triethylene glycol, 24% of a reinforcing agent 2-pyrrolidone, 0.05% of a stabilizer N, N-diphenyl-p-phenylenediamine and the balance of water. With reference to the preparation method of example 1, the components are mixed uniformly step by step according to the proportion to obtain the control compound solvent-V.
Comparative example 6
The composite solvent comprises, by mass, 5% of sulfolane, 2.5% of triethylene glycol, 91.5% of 2-pyrrolidone serving as a reinforcing agent, 0.05% of N, N-diphenyl-p-phenylenediamine serving as a stabilizing agent and the balance of water. And uniformly mixing the components according to a proportion to obtain the control compound solvent-VI.
Comparative example 7
The composite solvent comprises, by mass, 20% of sulfolane, 10% of triethylene glycol, 69% of a reinforcing agent 2-pyrrolidone and the balance of water. With reference to the preparation method of example 1, the components are mixed uniformly step by step according to the proportion to obtain the control compound solvent-VII.
Comparative example 8
The composite solvent comprises, by mass, 20% of sulfolane, 20% of triethylene glycol, 59% of reinforcing agent 2-pyrrolidone, 0.05% of stabilizer N, N-diphenyl-p-phenylenediamine and the balance of water. With reference to the preparation method of example 1, the components are mixed uniformly step by step according to the proportion to obtain the control compound solvent-VIII.
Comparative example 9
The composite solvent comprises, by mass, 15% of sulfolane, 25% of triethylene glycol, 59% of reinforcing agent 2-pyrrolidone, 0.05% of stabilizer N, N-diphenyl-p-phenylenediamine and the balance of water. With reference to the preparation method of example 1, the components are mixed uniformly step by step according to the proportion to obtain the control compound solvent-IX.
The technical effects of the technical solution of the present invention will be further described below by a plurality of test examples.
The solvent properties were characterized during the implementation of each test example by the following parameters.
The solvent extraction performance refers to the dissolution performance of the composite solvent on aromatic hydrocarbon and non-aromatic hydrocarbon in the raw oil under the condition of a certain solvent-to-oil ratio, and is characterized by using selectivity and removal rate parameters.
The selectivity and removal rate were calculated using the following formulas (1) and (2), respectively:
in the formula, S represents selectivity, ρ represents removal rate,represents the concentration of component i in the extracted oil, < >>Represents the concentration of component i in the raffinate,/-, in the raffinate>Indicating the total concentration of component i in the feed oil. For ease of data comparison, selectivity is expressed in terms of S '(S' =s/10) data. Beta represents raffinate oil recovery.
Where solvent stability refers to hydrolysis and high temperature degradation of the solvent, and is characterized using purity parameters.
The properties of the raw oil 1, the raw oil 2 and the raw oil 3 used in each test example of the present invention are as follows:
TABLE 1 essential properties of raw oil
。
Test example 1
According to the countercurrent extraction mode shown in FIG. 1, countercurrent extraction test is carried out on the raw oil and the composite solvent at the extraction temperature of 90 ℃ and the hydrocarbon volume ratio of 3:1, the aromatic hydrocarbon content of the raffinate oil is measured by an ultraviolet-visible spectrophotometry, and the aromatic hydrocarbon content of the raw oil and the raffinate oil is measured by a gravimetric method. The extraction performance of the composite solvent is characterized by calculating the selectivity and the removal rate of aromatic hydrocarbon. After the raw oil is extracted, the lower the aromatic hydrocarbon content in the raffinate oil is, the higher the aromatic hydrocarbon content in the extract oil is, which means that the better the selectivity and the dissolution performance of the solvent to the aromatic hydrocarbon are, the better the solvent extraction performance is.
The above extraction tests were carried out using the four complex solvents of example 1, comparative example 2 and comparative example 3, respectively, and the test results are shown in table 2:
table 2: test results of dearomatization of sulfones or sulfoxides and glycol solvents in different compounding proportions
。
As shown in table 2 above, the dearomatization effect of the composite solvent of example 1 is significantly higher than that of the composite solvents of comparative examples 1 and 2, which indicates that the solubility and selectivity of the sulfolane and triethylene glycol to heavy aromatics can be significantly improved after the sulfolane and triethylene glycol are compounded, and the dearomatization effect is significantly enhanced compared with the case that sulfolane and triethylene glycol are respectively used as main solvents alone; in addition, as can be seen from the difference of the dearomatization effect of the comparative example 1 and the comparative example 3, the addition of the enhancer 2-pyrrolidone can further improve the heavy aromatics removal capability. Therefore, the compound solvent obtained by further compounding the reinforcing agent with the main solvent composed of sulfolane and triethylene glycol in the embodiment 1 has excellent dearomatization effect, high selectivity and strong heavy aromatics removal capability, and the aromatics removal rate reaches 99.45 percent.
Experimental example 2
Extraction tests were performed using five complex solvents of example 6, example 7, example 8, comparative example 8 and comparative example 9, respectively, according to the extraction method and analysis method described in test example 1, and the test results are shown in table 3:
table 3: dearomatization test results of different main agent ratios
。
As shown in the table 3, when the concentration of the strengthening agent is the same (59%), the main solvent sulfolane and triethylene glycol are compounded in the same ratio as that of the comparative example 9 (0.6:1), the sulfolane ratio is smaller, and the aromatic hydrocarbon selectivity and the removal rate are low; when the compounding ratio of sulfolane and triethylene glycol serving as main solvents is increased to 1:1 of comparative example 8, the extraction performance is improved; when the compounding ratio of sulfolane and triethylene glycol serving as main solvents is increased to about 2:1 of the embodiment 6, the extraction performance is remarkably improved, the aromatic hydrocarbon selectivity reaches 52.34, and the removal rate reaches 99.42%; as the compounding ratio of sulfolane and triethylene glycol, the main solvents, continues to rise to 3:1 for example 7 and 4:1 for example 8, the extractability remains better, but there is a trend towards a decrease in selectivity and removal relative to about 2:1 for example 6. Therefore, the composite solvent provided by the invention can bring excellent aromatic hydrocarbon extraction performance and selectivity when the compounding ratio of sulfolane to triethylene glycol is 2-4:1, and especially has the best dearomatization comprehensive performance when the compounding ratio is 2:1.
Test example 3
Extraction tests were performed using seven kinds of complex solvents of example 1, example 2, example 3, example 5, comparative example 4, comparative example 5 and comparative example 6, respectively, according to the extraction method and analysis method described in test example 1, and the test results are shown in table 4:
table 4: dearomatization test results of different concentrations of reinforcing agent
。
As shown in the above Table 4, in the case that the compounding ratio of sulfolane and triethylene glycol as main solvents is the same (both are 2:1), the selectivity and removal rate of aromatic hydrocarbon are worst in the case that comparative example 4 does not contain the enhancer, and the extraction performance is improved to some extent but still at a lower level when the concentration of the enhancer is increased to 24% of comparative example 5; when the concentration of the enhancer reaches 49% of the embodiment 5, the extraction performance is obviously improved, the aromatic hydrocarbon selectivity reaches 41.50, the removal rate reaches 99.27%, when the content of the enhancer is improved to 69% of the embodiments 1 and 2, the extraction performance reaches the optimum, and when the content of the enhancer is improved to 84% of the embodiment 3, the extraction performance is equivalent to 69% of the embodiments 1 and 2; however, when the concentration of the reinforcing agent was further increased to 91.5% of that of comparative example 6, both the extraction performance and selectivity of the solvent were significantly lowered. Therefore, the method proves that the enhancer can bring excellent aromatic extraction performance and selectivity to the composite solvent when the enhancer accounts for 49-84%, and particularly has the best dearomatization comprehensive performance when the enhancer accounts for 69-84%.
Test example 4
Multiple extractions and regeneration runs were performed using the three complex solvents of example 1, example 4 and comparative example 7, respectively, in the manner described in test example 1. The purity determination method is a gas chromatography composition analysis method, and the calibration method is an area normalization method. The water removal treatment is carried out by anhydrous sodium sulfate before the determination of the composite solvent, and the total peak area of the organic solvent (sulfone or sulfoxide, glycol solvent and enhancer) is 100 percent. The test results are shown in Table 5:
table 5: results of solvent stability test
。
The stabilizer added in the composite solvent can inhibit peroxide from generating under high-temperature and micro-oxygen environment, so that the problem that even under the condition of high vacuum degree, trace oxygen exists in the system to cause high-temperature deterioration of the solvent is avoided. As shown in table 5 above, the composite solvents of example 1 and example 4 both maintained good thermal stability after the addition of the stabilizer, compared to the composite solvent of comparative example 7 without the stabilizer; in comparative example 7 without the stabilizer, the purity of the complex solvent was reduced at the time of 5 extractions, and the purity of the complex solvent was significantly reduced at the time of extractions similar to those of examples 1 and 4.
Test example 5
And carrying out reduced pressure distillation regeneration on the extracted rich solvent, wherein the lean agent can meet the extraction requirement when the aromatic hydrocarbon content in the regenerated lean agent is lower than 0.05%. Extraction and regeneration tests were performed using the complex solvents of example 1, example 2 and example 3. And (3) measuring the aromatic hydrocarbon content in the regenerated lean agent by an ultraviolet spectrophotometry. The lean regeneration effect is shown in table 6.
Table 6: composite solvent regeneration effect
。
The results in Table 6 show that the complex solvents of examples 1-3 of the present invention can all be regenerated by conventional distillation.
Experimental example 6
The test was carried out in the manner described in test example 1 using the complex solvent of example 1 and raw materials 1, 2 and 3, respectively, and the test results are shown in Table 7:
table 7: extraction test results of different raw oil
。
The results in Table 7 show that the compound solvent of example 1 of the present invention has a wide range of application for low aromatic hydrocarbon feedstock to produce specialty oils, and is suitable for feedstock with a final boiling point of less than or equal to 250deg.C.

Claims (6)

1. The composite solvent for producing the low-aromatic special oil is characterized by comprising the following components in percentage by mass: 10% -50% of main solvent, 49% -89% of reinforcing agent, 0.05% -0.5% of stabilizer and the balance of water; the main solvent is a mixture of sulfone or sulfoxide and glycol solvents; the mass ratio of the sulfone or sulfoxide to the glycol solvent is 2:1-4:1; the sulfone is any one or more than two of dimethyl sulfone, diethyl sulfone or sulfolane; the sulfoxide is any one or a mixture of two of dimethyl sulfoxide and diethyl sulfoxide; the glycol solvent is any one or more than two of ethylene glycol, diethylene glycol, triethylene glycol or tetraethylene glycol; the strengthening agent is selected from any one or more than two of N-formylmorpholine, 2-pyrrolidone, propylene carbonate, N-methylpyrrolidone, N-dimethylformamide or N, N-dimethylacetamide; the stabilizer is selected from any one or more than two of N, N-diphenyl-p-phenylenediamine, N- (1, 3-dimethylbutyl) -N' -phenyl-p-phenylenediamine or 4-butylamine-2, 6-tetramethylpiperidine.
2. The composite solvent according to claim 1, comprising the following components in mass percent: 10% -40% of main solvent, 59% -89% of reinforcing agent, 0.05% -0.5% of stabilizer and the balance of water.
3. The composite solvent according to any one of claims 1 or 2, wherein the mass ratio of sulfone or sulfoxide to glycol solvent in the main solvent is 2:1.
4. The composite solvent according to any one of claims 1 or 2, comprising the following components in mass percent: 5% -25% of sulfone or sulfoxide; 5% -25% of the glycol solvent; 50% -89% of the reinforcing agent; 0.05% -0.5% of stabilizer and the balance of water.
5. The composite solvent according to any one of claims 1 or 2, comprising the following components in mass percent: 10% -20% of sulfone or sulfoxide; 5% -10% of the glycol solvent; 69% -84% of the reinforcing agent; 0.05% -0.1% of stabilizer and the balance of water.
6. A method for producing low aromatic special oil by separating aromatic hydrocarbon in distillate oil with a final distillation point of less than or equal to 250 ℃ by liquid-liquid extraction using the composite solvent according to any one of claims 1 to 5, characterized by comprising the following steps: taking the composite solvent and raw oil according to the volume ratio of hydrocarbon to 3:1-4:1, wherein the raw oil is selected from naphtha, kerosene or diesel oil; the compound solvent and the raw oil are in multistage countercurrent contact in an extraction tower at the tower top temperature of 80-120 ℃, and the low-aromatic special oil product is formed after the solvent is removed by eluting the raffinate oil at the tower top.
CN202310360229.5A 2023-04-06 2023-04-06 Composite solvent and method for producing low-aromatic special oil Active CN116144393B (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103160310A (en) * 2013-03-15 2013-06-19 西南石油大学 Composite solvent and extraction method for extracting and separating aromatic hydrocarbons
CN104031674A (en) * 2014-06-20 2014-09-10 西南石油大学 Composite solvent for extracting and separating aromatics in low-aromatic naphtha
CN112552951A (en) * 2020-11-25 2021-03-26 北方华锦化学工业股份有限公司 Composite extracting agent suitable for removing aromatic hydrocarbons in low-content aromatic hydrocarbon straight-run naphtha and application method thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103160310A (en) * 2013-03-15 2013-06-19 西南石油大学 Composite solvent and extraction method for extracting and separating aromatic hydrocarbons
CN104031674A (en) * 2014-06-20 2014-09-10 西南石油大学 Composite solvent for extracting and separating aromatics in low-aromatic naphtha
CN112552951A (en) * 2020-11-25 2021-03-26 北方华锦化学工业股份有限公司 Composite extracting agent suitable for removing aromatic hydrocarbons in low-content aromatic hydrocarbon straight-run naphtha and application method thereof

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