CN103160310A - Composite solvent and extraction method for extracting and separating aromatic hydrocarbons - Google Patents
Composite solvent and extraction method for extracting and separating aromatic hydrocarbons Download PDFInfo
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- CN103160310A CN103160310A CN2013100819371A CN201310081937A CN103160310A CN 103160310 A CN103160310 A CN 103160310A CN 2013100819371 A CN2013100819371 A CN 2013100819371A CN 201310081937 A CN201310081937 A CN 201310081937A CN 103160310 A CN103160310 A CN 103160310A
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Abstract
The invention relates to a composite solvent and extraction method for extracting and separating aromatic hydrocarbons from a hydrocarbon mixture in industries of oil refining and chemical engineering, which can achieve the advantages of high aromatic hydrocarbon separation efficiency, favorable heat stability and convenient recovery process. The technical scheme is as follows: the composite solvent comprises the following solvents in percentage by mass: 45-95% of main solvent, 4.5-40% of auxiliary solvent and 0.5-15% of modifier, wherein the main solvent is one of sulfolane or N-formyl morpholine or dimethylsulfoxide or tetraethylene glycol, the auxiliary solvent is one of N-methylpyrrolidone or N,N-dimethylformamide, and the modifier is one of ethylene glycol or polyethyleneglycol; and a preparation method of the composite solvent comprises the following steps: proportionally adding the modifier into the auxiliary solvent, evenly mixing, proportionally adding the mixed solvent into the main solvent, and evenly mixing to prepare the composite solvent. The composite solvent obviously enhances the solubility and selectivity of the solvent on aromatic hydrocarbons, avoids the increase of energy consumption and the occurrence of hydrolysis reaction caused by the situation that water is contained in the solvent, reduces the consumption of the solvent and increases the aromatic hydrocarbon recovery rate.
Description
Technical field
The present invention relates to a kind of liquid for oil refining, chemical engineering industry-liquid extracting double solvents.More particularly, be a kind of from hydrocarbon mixture extracting and separating aromatic hydrocarbons double solvents and extracting process thereof used.
Background technology
Solvent extraction is the important sepn process of a class in oil refining, chemical engineering industry, is widely used in petroleum refining industry.From lube stock extraction condensed ring or polycyclic aromatic hydrocarbons, extract aromatic hydrocarbons all belong to solvent extraction process from reformed oil or catalytic cracking turning oil, for undesirable components is extracted, ideal composition is stayed in raffinate as much as possible, and the selection of solvent is just most important.
US3415739 discloses a kind of N-Methyl pyrrolidone and diglycolamine mixture of utilizing and has been solvent, adopts liquid-liquid extracting or extractive distillation to reclaim the method for aromatic hydrocarbons in hydrocarbon mixture.US3415741 discloses a kind of N-Methyl pyrrolidone and Monoethanolamine MEA BASF mixture of utilizing and has been solvent, adopts the method for aromatic hydrocarbons in liquid-liquid extracting and reclaiming hydrocarbon mixture.US3415742 discloses a kind of N-Methyl pyrrolidone and glycerol mixture of utilizing and has been solvent, adopts the method for aromatic hydrocarbons in liquid-liquid extracting and reclaiming hydrocarbon mixture.US4013549 discloses a kind of mixture of N-Methyl pyrrolidone and phenol that utilizes and has been solvent, and this solvent can contain a small amount of water, and aromatic hydrocarbons component in the extraction lube stock is to improve Quality of Lubricating Oil.The disclosed double solvents of US4909927, take N-Methyl pyrrolidone as main solvent, solubility promoter is ethylbenzene, butylbenzene or morpholine.US20100243533 discloses a kind of double solvents, and take N-Methyl pyrrolidone as main solvent, solubility promoter is N, dinethylformamide also can add a small amount of water, compares with N-Methyl pyrrolidone-water compounded solvents, adding of DMF improved raffinate oil yield.
CN1393507A discloses a kind of double solvents that utilizes the extractive distillation aromatics separation, comprises main solvent, solubility promoter and properties-correcting agent.Main solvent and properties-correcting agent are selected from respectively tetramethylene sulfone, N-formyl morpholine or N-Methyl pyrrolidone, but the acid-basicity of properties-correcting agent is opposite with main solvent, and solubility promoter is C
8– C
11Any one in aromatic hydrocarbons or two kinds of mixtures with different carbon number aromatic hydrocarbons, this double solvents are used for extractive distillation and reclaim aromatic hydrocarbons, can relax the solvent recuperation operational condition, improve aromatic recovery rate, and make the aromatic hydrocarbons of recovery be neutral.But the solubility promoter selectivity that adds is on the low side, and boiling point is generally lower than 200 ℃, and the waste when being used for the extractive distillation aromatics separation is larger, is unsuitable for the extractive distillation of wide fraction.
CN1660970A discloses a kind of separation of extractive distillation aromatic hydrocarbons double solvents used, comprises main solvent, solubility promoter and water.Main solvent is selected from sulfone compound, glycols compound, N-formyl morpholine or N-Methyl pyrrolidone; solubility promoter is selected from the hydrocarbon mixture with two phenyl ring; this double solvents is used for separation of extractive distillation aromatic hydrocarbons, can reduce solvent ratio, improves aromatic hydrocarbon product yield and purity.But water is easy and aromatic hydrocarbons forms azeotropic distillation, causes caloric requirement significantly to increase, and it is the generation of hydrolysis reaction that the existence of water also can cause.
Summary of the invention
The objective of the invention is: for extracting and separating aromatic hydrocarbons from hydrocarbon mixture, select that aromatics separation efficient is high, Heat stability is good, reclaim double solvents easily, the spy provides a kind of extracting and separating aromatic hydrocarbons double solvents and extracting process thereof used.
In order to achieve the above object, the present invention by the following technical solutions: a kind of extracting and separating aromatic hydrocarbons double solvents used is comprised of main solvent, solubility promoter and properties-correcting agent.This double solvents solvent for use component and mass percent be, quality in grams, main solvent is a kind of with tetramethylene sulfone or N-formyl morpholine or dimethyl sulfoxide (DMSO) or Tetraglycol 99, consumption is 45-95%; Solubility promoter is use N-Methyl pyrrolidone or DMF a kind of, and consumption is 4.5-40%; Properties-correcting agent is a kind of of spent glycol or poly(oxyethylene glycol) 400, and consumption is 0.5-15%; Its compound method is: first add properties-correcting agent in proportion in solubility promoter, after mixing, more above-mentioned mixed solvent is added in main solvent in proportion mix, make this double solvents.
Double solvents provided by the invention comprises main solvent, solubility promoter and properties-correcting agent.Main solvent occupies the majority in double solvents, has determined the main character of whole solvent, the adding of solubility promoter, can increase main solvent to the dissolving power of aromatic hydrocarbons, can form hydrogen bond between properties-correcting agent and solubility promoter, impel the polarity of solvent to become large, thereby improve double solvents to the selectivity of aromatic hydrocarbons.
The extracting process of this double solvents extracting and separating aromatic hydrocarbons from hydrocarbon mixture: the hydrocarbon mixture that first will contain aromatic hydrocarbons is inputted in the middle part of extraction tower by the stock oil import, the double solvents of above-mentioned preparation carries out liquid-liquid extraction in extraction tower from extraction tower top input tower; Raffinating oil through the second interchanger heat exchange from the water wash column bottom input of raffinating oil from the discharge of extracting tower top after extraction, to reclaim the washing water of return tank of top of the tower bottom from the water wash column top input of raffinating oil, wash, non-aromatics is discharged from the outlet of tower top non-aromatics, contain the solvent wash water and discharge at the bottom of tower, then from the top input of water separation column; First rich solvent that is rich in aromatic hydrocarbons of discharging at the bottom of the extraction tower, distills in stripping tower from stripping tower top input through the second interchanger and First Heat Exchanger heat exchange; After distillation, non-aromatics and part aromatic hydrocarbons are discharged from the stripping tower tower top, input stripping return tank of top of the tower, washing lotion is returned in introducing extraction tower bottom from the stripping return tank of top of the tower again, the second rich solvent is discharged from stripping tower bottom, input again in the middle part of solvent recovery tower aromatics separation and double solvents in the solvent recovery tower tower; The aromatic hydrocarbons of discharging from the solvent recuperation column overhead is at last introduced and is reclaimed return tank of top of the tower, aromatic hydrocarbons is discharged from the aromatic hydrocarbons outlet, that discharges at the bottom of the water wash column tower of raffinating oil contains aqueous solvent input water separation column, separate solvent and water, heat up in a steamer from moisture the water input stripping return tank of top of the tower that column overhead is discharged, the double solvents of discharging at the bottom of the water separation column tower mixes by the First Heat Exchanger heat exchange with the double solvents of discharging at the bottom of the solvent recovery tower tower, inputs extraction tower top recycle.
In above-mentioned liquid-liquid extracting flow process, the operational condition of extraction tower is: tower top pressure 0.60 – 0.80Mpa, double solvents enter 100 ℃ of tower temperature 60 –, and in tower, extraction temperature 40 – is 80 ℃, double solvents and stock oil mass ratio are 1.0 – 5.0, and returning washing lotion and stock oil mass ratio is 0.30 – 0.75; The operational condition of stripping tower is: working pressure 0.16 – 0.25Mpa, 110 ℃ of tower top temperature 90 –, 175 ℃ of column bottom temperature 150 –; The operational condition of solvent recovery tower is: working pressure 0.12 – 0.15Mpa, 115 ℃ of tower top temperature 105 –, 180 ℃ of column bottom temperature 170 –; The operational condition of water wash column of raffinating oil is: working pressure 0.40 – 0.60Mpa, and 40 ℃ of service temperature 20 –, washing water is 0.4 – 0.8 with the mass ratio of raffinating oil; The operational condition of water separation column is: working pressure 0.10-0.12Mpa, service temperature 100-120 ℃.
The present invention has following beneficial effect compared with prior art: (1) adds solubility promoter and properties-correcting agent in the liquid-liquid extraction solvent of routine, has significantly increased dissolving power and the selectivity of solvent to aromatic hydrocarbons; (2) this double solvents is fit to process the raw material that boiling spread is wider, aromaticity content is lower; (3) this double solvents and the traditional liquid-liquid extraction that adopts single solvent relatively, have avoided energy consumption that solvent comprises water causes to increase and the generation of hydrolysis reaction, have reduced solvent load, have increased the non-aromatics yield, have improved aromatic recovery rate.
Description of drawings
Accompanying drawing is that the present invention uses double solvents to carry out the extracting process schematic flow sheet of liquid-liquid extraction.
In figure: 1. stock oil import, 2. extraction tower, 3. non-aromatics outlet, the water wash column of 4. raffinating oil, 5. stripping return tank of top of the tower, 6. stripping tower, 7. solvent recovery tower, 8. reclaim return tank of top of the tower, 9. water separation column, 10. aromatic hydrocarbons outlet, 11. First Heat Exchangers, 12. second interchanger
Embodiment
Further illustrate the present invention below in conjunction with accompanying drawing.In accompanying drawing, from extraction tower 2 middle parts inputs, double solvents carries out liquid-liquid extraction to the hydrocarbon mixture that contains aromatic hydrocarbons in extraction tower 2 from extraction tower 2 tops input towers by stock oil import 1; Raffinating oil through the second interchanger 12 heat exchange from the water wash column 4 bottoms inputs of raffinating oil from extraction tower 2 tower tops discharges after extraction, to reclaim the washing water of return tank of top of the tower 8 bottoms from the water wash column 4 tops inputs of raffinating oil, wash, non-aromatics is discharged from tower top non-aromatics outlet 3, contain the solvent wash water from the water wash column 4 bottoms discharges of raffinating oil, then from the 9 tops inputs of water separation column; First rich solvent of discharging at the bottom of extraction tower 2 towers, distills in stripping tower 6 from stripping tower 6 tops inputs through the second interchanger 12 and First Heat Exchanger 11 heat exchange; After distillation, non-aromatics and part aromatic hydrocarbons are discharged from stripping tower 6 tower tops, input stripping return tank of top of the tower 5, washing lotion is returned in introducing extraction tower 2 bottoms from stripping return tank of top of the tower 5 again, after the second rich solvent is discharged at the bottom of stripping tower 6 towers, input again solvent recovery tower 7 middle parts, at the interior aromatics separation of solvent recovery tower 7 and double solvents, introduce recovery return tank of top of the tower 8 from the aromatic hydrocarbons that solvent recovery tower 7 tower tops are discharged, aromatic hydrocarbons is discharged from aromatic hydrocarbons outlet 10; At last, input stripping return tank of top of the tower 5 from the water that water separation column 9 tower tops are discharged, the double solvents of discharging at the bottom of water separation column 9 towers mixes by First Heat Exchanger 11 heat exchange with the double solvents of discharging at the bottom of solvent recovery tower 7 towers, inputs extraction tower 2 top recycles.
Further illustrate the present invention below by embodiment, but the present invention is not limited to this.
Embodiment 1
Take virgin naphtha as raw material, its composition is listed in table 1.Carry out liquid-liquid extracting and reclaiming benzene and toluene by flow process shown in accompanying drawing, the double solvents of employing consists of: 60g tetramethylene sulfone, 32gN-methyl-2-pyrrolidone and 8.0g poly(oxyethylene glycol) 400.The main operational condition of each tower sees Table 2, and the aromatic hydrocarbons separating resulting sees Table 3.
Embodiment 2
Take condensate oil as raw material, its composition is listed in table 1.Carry out liquid-liquid extracting and reclaiming benzene and toluene by flow process shown in accompanying drawing, the double solvents of employing consists of: 60gN-formyl morpholine, 32gN-methyl-2-pyrrolidone and 8.0g ethylene glycol.The main operational condition of each tower sees Table 2, and the aromatic hydrocarbons separating resulting sees Table 3.
Embodiment 3
Take reformed gasoline as raw material, its composition is listed in table 1.Carry out liquid-liquid extracting and reclaiming benzene and toluene by flow process shown in accompanying drawing, the double solvents of employing consists of: 60g tetramethylene sulfone, 32gN-methyl-2-pyrrolidone and 8.0g ethylene glycol.The main operational condition of each tower sees Table 2, and the aromatic hydrocarbons separating resulting sees Table 3.
Comparative Examples
Reclaim benzene and toluene with the disclosed double solvents extraction of CN1660970, the stock oil of use is with embodiment 3.Carry out liquid-liquid extracting by flow process shown in accompanying drawing, double solvents consists of: 84g tetramethylene sulfone, 15g1-methylnaphthalene and 1.0g water.The main operational condition of each tower sees Table 2, and the aromatic hydrocarbons separating resulting sees Table 3.
Table 1
Table 2
Table 3
Claims (3)
1. double solvents that extracting and separating aromatic hydrocarbons is used, formed by main solvent, solubility promoter and properties-correcting agent, it is characterized in that: this double solvents solvent for use component and mass percent are, quality in grams, main solvent is use tetramethylene sulfone or N-formyl morpholine or dimethyl sulfoxide (DMSO) or Tetraglycol 99 a kind of, and consumption is 45-95%; Solubility promoter is use N-Methyl pyrrolidone or DMF a kind of, and consumption is 4.5-40%; Properties-correcting agent is a kind of of spent glycol or poly(oxyethylene glycol) 400, and consumption is 0.5-15%; Its compound method is: first add properties-correcting agent in proportion in solubility promoter, after mixing, more above-mentioned mixed solvent is added in main solvent in proportion mix, make this double solvents.
2. double solvents according to claim 1, the extracting process of extracting and separating aromatic hydrocarbons from hydrocarbon mixture, it is characterized in that: the hydrocarbon mixture that first will contain aromatic hydrocarbons is inputted in the middle part of extraction tower (2) by stock oil import (1), the double solvents of above-mentioned preparation carries out liquid-liquid extraction in extraction tower (2) from extraction tower (2) top input tower; Raffinating oil through the second interchanger (12) heat exchange from the water wash column of raffinating oil (4) bottom input from the discharge of extraction tower (2) tower top after extraction, to reclaim the washing water of return tank of top of the tower (8) bottom from the water wash column of raffinating oil (4) top input, wash, non-aromatics is discharged from tower top non-aromatics outlet (3), contain the solvent wash water and discharge at the bottom of tower, then from water separation column (9) top input; First rich solvent that is rich in aromatic hydrocarbons of discharging at the bottom of extraction tower (2) tower is inputted from stripping tower (6) top through the second interchanger (12) and First Heat Exchanger (11) heat exchange, distills in stripping tower (6); After distillation, non-aromatics and part aromatic hydrocarbons are discharged from stripping tower (6) tower top, input stripping return tank of top of the tower (5), introduce again extraction tower (2) bottom and return washing lotion from the stripping return tank of top of the tower, after the second rich solvent is discharged at the bottom of stripping tower (6) tower, input again in the middle part of solvent recovery tower (7) aromatics separation and double solvents in solvent recovery tower (7); The aromatic hydrocarbons of discharging from solvent recovery tower (7) tower top is at last introduced and is reclaimed return tank of top of the tower (8), aromatic hydrocarbons is discharged from aromatic hydrocarbons outlet (10), that discharges at the bottom of the water wash column of raffinating oil (4) tower contains aqueous solvent input water separation column (9), separate solvent and water, input stripping return tank of top of the tower (5) from the water that water separation column (9) tower top is discharged, the double solvents of discharging at the bottom of water separation column (9) tower mixes by First Heat Exchanger (11) heat exchange with the double solvents of discharging at the bottom of solvent recovery tower (7) tower, inputs extraction tower (2) top recycle.
3. extracting process according to claim 2, it is characterized in that: in extraction tower (2), tower top pressure 0.60 – 0.80Mpa, double solvents enters 100 ℃ of tower temperature 60 –, in tower, extraction temperature 40 – is 80 ℃, double solvents and stock oil mass ratio are 1.0 – 5.0, and returning washing lotion and stock oil mass ratio is 0.30 – 0.75; In stripping tower (6), working pressure 0.16 – 0.25Mpa, 110 ℃ of tower top temperature 90 –, 175 ℃ of column bottom temperature 150 –; In solvent recovery tower (7), working pressure 0.12 – 0.15Mpa, 115 ℃ of tower top temperature 105 –, 180 ℃ of column bottom temperature 170 –; In the water wash column of raffinating oil (4), working pressure 0.40 – 0.60Mpa, 40 ℃ of service temperature 20 –, washing water is 0.4 – 0.8 with the mass ratio of raffinating oil; In water separation column (9), working pressure 0.10-0.12Mpa, service temperature 100-120 ℃.
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN105542834A (en) * | 2014-10-30 | 2016-05-04 | 中国石化扬子石油化工有限公司 | Composite solvent for extraction distillation separation of aromatic hydrocarbons, and applications thereof |
| CN107779224A (en) * | 2016-08-25 | 2018-03-09 | 北京安耐吉能源工程技术有限公司 | A kind of gasoline processing method |
| CN107779220A (en) * | 2016-08-25 | 2018-03-09 | 北京安耐吉能源工程技术有限公司 | A kind of gasoline processing method |
| CN108690658A (en) * | 2017-04-07 | 2018-10-23 | 中国石油天然气股份有限公司 | Method for recovering aromatic hydrocarbons in low aromatic hydrocarbon content oil |
| CN108728155A (en) * | 2017-04-13 | 2018-11-02 | 北京安耐吉能源工程技术有限公司 | A kind of double solvents and its application |
| CN109517625A (en) * | 2017-09-20 | 2019-03-26 | 北京安耐吉能源工程技术有限公司 | A kind of FCC gasoline processing method |
| CN111978143A (en) * | 2019-05-23 | 2020-11-24 | 中国石油化工股份有限公司 | Composite solvent for separating aromatic hydrocarbon by extractive distillation and application thereof |
| CN112704898A (en) * | 2021-01-05 | 2021-04-27 | 宁波科元精化股份有限公司 | Device for reducing sulfolane decomposition rate in extraction process and use method thereof |
| CN116144393A (en) * | 2023-04-06 | 2023-05-23 | 河北精致科技有限公司 | Composite solvent and method for producing low-aromatic special oil |
| WO2024145089A1 (en) * | 2022-12-28 | 2024-07-04 | Uop Llc | Improving aromatics extraction through integration of complementary co-solvents |
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Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
| CN105542834A (en) * | 2014-10-30 | 2016-05-04 | 中国石化扬子石油化工有限公司 | Composite solvent for extraction distillation separation of aromatic hydrocarbons, and applications thereof |
| CN107779220B (en) * | 2016-08-25 | 2019-11-29 | 北京安耐吉能源工程技术有限公司 | A kind of gasoline processing method |
| CN107779224A (en) * | 2016-08-25 | 2018-03-09 | 北京安耐吉能源工程技术有限公司 | A kind of gasoline processing method |
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| CN108728155A (en) * | 2017-04-13 | 2018-11-02 | 北京安耐吉能源工程技术有限公司 | A kind of double solvents and its application |
| CN108728155B (en) * | 2017-04-13 | 2020-04-17 | 北京安耐吉能源工程技术有限公司 | Composite solvent and application thereof |
| CN109517625A (en) * | 2017-09-20 | 2019-03-26 | 北京安耐吉能源工程技术有限公司 | A kind of FCC gasoline processing method |
| CN109517625B (en) * | 2017-09-20 | 2020-11-20 | 北京安耐吉能源工程技术有限公司 | FCC gasoline processing method |
| CN111978143A (en) * | 2019-05-23 | 2020-11-24 | 中国石油化工股份有限公司 | Composite solvent for separating aromatic hydrocarbon by extractive distillation and application thereof |
| CN111978143B (en) * | 2019-05-23 | 2023-05-05 | 中国石油化工股份有限公司 | Composite solvent for separating aromatic hydrocarbon by extractive distillation and application thereof |
| CN112704898A (en) * | 2021-01-05 | 2021-04-27 | 宁波科元精化股份有限公司 | Device for reducing sulfolane decomposition rate in extraction process and use method thereof |
| WO2024145089A1 (en) * | 2022-12-28 | 2024-07-04 | Uop Llc | Improving aromatics extraction through integration of complementary co-solvents |
| CN116144393A (en) * | 2023-04-06 | 2023-05-23 | 河北精致科技有限公司 | Composite solvent and method for producing low-aromatic special oil |
| CN116144393B (en) * | 2023-04-06 | 2023-08-22 | 河北精致科技有限公司 | Composite solvent and method for producing low-aromatic special oil |
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Application publication date: 20130619 |