CN112745888A - Method for removing oxygen-containing compounds in Fischer-Tropsch synthesis light oil - Google Patents

Method for removing oxygen-containing compounds in Fischer-Tropsch synthesis light oil Download PDF

Info

Publication number
CN112745888A
CN112745888A CN201911048205.6A CN201911048205A CN112745888A CN 112745888 A CN112745888 A CN 112745888A CN 201911048205 A CN201911048205 A CN 201911048205A CN 112745888 A CN112745888 A CN 112745888A
Authority
CN
China
Prior art keywords
fischer
extraction
oxygen
tropsch synthesis
solvent
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201911048205.6A
Other languages
Chinese (zh)
Other versions
CN112745888B (en
Inventor
邹琥
刘欢
史军军
李林玥
葸雷
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
Original Assignee
Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sinopec Research Institute of Petroleum Processing, China Petroleum and Chemical Corp filed Critical Sinopec Research Institute of Petroleum Processing
Priority to CN201911048205.6A priority Critical patent/CN112745888B/en
Publication of CN112745888A publication Critical patent/CN112745888A/en
Application granted granted Critical
Publication of CN112745888B publication Critical patent/CN112745888B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING 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
    • C10G21/00Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents
    • C10G21/06Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents characterised by the solvent used
    • C10G21/12Organic compounds only
    • C10G21/20Nitrogen-containing compounds
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING 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
    • C10G2300/00Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10Feedstock materials
    • C10G2300/1022Fischer-Tropsch products
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING 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
    • C10G2300/00Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/20Characteristics of the feedstock or the products
    • C10G2300/201Impurities
    • C10G2300/202Heteroatoms content, i.e. S, N, O, P

Landscapes

  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

The invention relates to a method for removing oxygen-containing compounds in Fischer-Tropsch synthesis light oil. The method comprises liquid-liquid extraction, water washing and solvent recovery, wherein the liquid-liquid extraction adopts ionic liquid as an extraction solvent. The extraction solvent adopted by the method has the characteristics of high selectivity to oxygen-containing compounds, good stability, large density difference with Fischer-Tropsch synthesis light oil and the like, and the method has good removal effect on the oxygen-containing compounds, is easy to recover and has high recovery efficiency.

Description

Method for removing oxygen-containing compounds in Fischer-Tropsch synthesis light oil
Technical Field
The invention belongs to a separation method of impurities in indirect coal liquefaction products, and particularly relates to a method for removing oxygen-containing compounds in Fischer-Tropsch synthesis light oil.
Background
Fischer-Tropsch synthesis (Fischer-Tropsch synthesis) is a coal indirect liquefaction technology, is the core composition of a coal gasification process, and the content of sulfur and nitrogen in Fischer-Tropsch synthesis products is almost zero, so that the Fischer-Tropsch synthesis products are direct raw materials for downstream oil product processing. Wherein, the olefin composition in the Fischer-Tropsch synthetic oil is mostly linear chain linear alpha-olefin (LAOs), and the LAOs serving as important petrochemical raw materials is widely applied to a plurality of fields such as comonomer, surfactant synthetic intermediate, plasticizer alcohol, synthetic lubricating oil, oil additives and the like.
The Fischer-Tropsch synthesis oil has the characteristics of wide carbon number distribution, complex composition and the like. The Fischer-Tropsch synthetic oil product contains hydrocarbon components and oxygen-containing compounds such as alcohol, aldehyde, ketone, acid, ester and the like, and the hydrocarbon and the oxygen-containing compounds can form an azeotrope and can not be effectively separated by simple rectification. Therefore, the LAOs in the fischer-tropsch oil is separated and purified by first removing the acids and oxygen-containing compounds from the fischer-tropsch oil. At present, the removal of oxygen-containing compounds in oil mainly comprises a hydrofining method, a solvent extraction method and an azeotropic distillation method.
CN102380391A discloses a selective deacidification catalyst, which comprises CuO and Al2O3And a metal additive selected from ZnO, NiO and Cr2O3The fischer-tropsch oil may be deacidified by selective hydrogenation of one or more transition metal oxides selected from MgO and BaO, one or more alkaline earth metal oxides selected from MgO and BaO and/or a noble metal selected from Pd, while about 65% of the olefins are not hydrogenated.
CN106753546A discloses a Fischer-Tropsch synthesis light distillate oil refining process, wherein Fischer-Tropsch synthesis oil is firstly subjected to solid phase adsorption unit to remove metal ion impurities and partial oxygen-containing compounds, and then a strong alkaline aqueous thionyl dimethyl methane solution is used as a composite extractant to further remove the oxygen-containing compounds. The process can treat the fraction C4-C21 of the Fischer-Tropsch synthetic oil, the content of oxygen-containing compounds in the oil product after extraction can be reduced to below 50ppm, and the extracting agent can be recycled.
CN1764619A discloses a feasible method for extracting oxygen-containing compounds from hydrocarbon streams and simultaneously ensuring the olefin content of products, which takes a mixture of methanol and water as a solvent, adopts an azeotropic distillation method to extract the oxygen-containing compounds from the hydrocarbon streams of C8-C16, and can reduce the oxygen-containing compound content in oil products to 0.2w percent, but the total recovery rate of olefin and alkane is lower.
CN102452886A discloses a method for purifying 1-octene from Fischer-Tropsch synthesis oil, which adopts azeotropic distillation to simultaneously remove acid and other organic oxygen-containing compounds in Fischer-Tropsch synthesis C8 fraction by using an ethanol and water binary entrainer.
The hydrofining method, the solvent extraction method and the azeotropic distillation method can effectively remove oxygen-containing compounds in the Fischer-Tropsch synthetic oil, but the process of hydrofining oxygen-containing compound removal is often accompanied with olefin hydrogenation saturation, so that the loss of LAOs with high added value is caused; the azeotropic distillation needs a subsequent extractive distillation process to separate the entrainer and the hydrocarbon products, the process is more complex, and the method is suitable for removing the oxygen-containing compounds of the narrow fraction of the Fischer-Tropsch synthetic oil.
Disclosure of Invention
The invention aims to provide a method for removing oxygen-containing compounds in Fischer-Tropsch synthesis light oil, which can effectively remove the oxygen-containing compounds in the Fischer-Tropsch synthesis light oil through liquid phase extraction to obtain hydrocarbon compounds.
In order to achieve the above object, the present invention provides a method for removing oxygen-containing compounds from light oil of fischer-tropsch synthesis, comprising:
contacting Fischer-Tropsch synthesis light oil with an extraction solvent in an extraction tower for liquid-liquid extraction to obtain a raffinate phase and an extract phase rich in oxygen-containing compounds, wherein the raffinate phase is the Fischer-Tropsch synthesis light oil without the oxygen-containing compounds;
carrying out reduced pressure distillation on the extract phase in a solvent recovery tower, discharging oxygen-containing compounds from the top of the tower, and returning a lean solvent discharged from the bottom of the tower to the extraction tower;
wherein the extraction solvent is ionic liquid, and the cation of the ionic liquid has a structure shown in a formula (I) or a formula (II);
Figure BDA0002254646210000031
in the formula (I), R2、R4And R5Each independently is H, R1And R3Are respectively selected from C1~C4One of alkyl, aminoethyl, aminopropyl, carboxymethyl, carboxyethyl and carboxypropyl of (a); in the formula (II), R7、R8、R9、R10And R11Each independently is H or C1~C3Alkyl of R6One selected from alkyl with 6-8 carbon atoms, aminoethyl, aminopropyl, carboxymethyl, carboxyethyl and carboxypropyl.
Through the technical scheme, the ionic liquid with a proper structure is used as the extraction solvent, the oxygen-containing compounds in the Fischer-Tropsch synthesis light oil are removed by a liquid-liquid extraction method, and the used extraction solvent has high selectivity and good stability on the oxygen-containing compounds, has large density difference with the Fischer-Tropsch synthesis light oil, has a good removal effect on the oxygen-containing compounds, is easy to recover, and has high recovery efficiency.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention. In the drawings:
FIG. 1 is a schematic flow chart of an embodiment of the method for removing oxygenates from Fischer-Tropsch synthesis light oil of the present invention.
Detailed Description
The following detailed description of embodiments of the invention refers to the accompanying drawings. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
As shown in FIG. 1, the present invention provides a method for removing oxygen-containing compounds from Fischer-Tropsch synthesis light oil, comprising:
contacting Fischer-Tropsch synthesis light oil with an extraction solvent in an extraction tower 1 for liquid-liquid extraction to obtain a raffinate phase and an extract phase rich in oxygen-containing compounds, wherein the raffinate phase is the Fischer-Tropsch synthesis light oil without the oxygen-containing compounds;
carrying out reduced pressure distillation on the extract phase in a solvent recovery tower 2, discharging oxygen-containing compounds from the top of the tower, and returning a lean solvent discharged from the bottom of the tower to the extraction tower 1;
wherein the extraction solvent is ionic liquid, and the cation of the ionic liquid has a structure shown in a formula (I) or a formula (II);
Figure BDA0002254646210000041
in the formula (I), R2、R4And R5Each independently is H, R1And R3Are respectively selected from C1~C4One of alkyl, aminoethyl, aminopropyl, carboxymethyl, carboxyethyl and carboxypropyl of (a); in the formula (II), R7、R8、R9、R10And R11Each independently is H or C1~C3Alkyl of R6One selected from alkyl with 6-8 carbon atoms, aminoethyl, aminopropyl, carboxymethyl, carboxyethyl and carboxypropyl.
The method adopts the ionic liquid with the cation with the structure shown in the formula (I) or the formula (II) as an extraction solvent, and the N atom on the imidazole ring or the pyridine ring of the cation is provided with a polar group or a proper alkyl group, so that the selectivity and the solubility to oxygen-containing compounds can be improved, and the ionic liquid has good stability, large density difference with Fischer-Tropsch synthesis light oil and easy separation. The ionic liquid is used as an extraction solvent, and the oxygen-containing compounds in the Fischer-Tropsch synthesis light oil are removed by liquid-liquid extraction, so that the removal effect is good, the operation is easy, the solvent is convenient to recover, and the recovery efficiency is high.
According to the invention, the Fischer-Tropsch synthesis light oil is a fraction with 4-16 carbon atoms. The method has no requirement on the content of oxygen-containing compounds in Fischer-Tropsch synthesis light oil, the content of the oxygen-containing compounds in the Fischer-Tropsch synthesis light oil is 1-15% by mass, the total content of normal alkane and olefin can be 20-90% by mass, preferably 70-90% by mass, and the total acid value can be 3-150 mgKOH/g. The oxygenate may include at least one of an alcohol, an aldehyde, a ketone, an acid, and an ester.
According to the invention, in formula (I), R1And R3Each independently may be one of an alkyl group having 1 to 4 carbon atoms, an aminoethyl group, an aminopropyl group, a carboxymethyl group, a carboxyethyl group and a carboxypropyl group. R1And R3May be the same or different. Wherein the alkyl group having 1 to 4 carbon atoms is at least one of methyl, ethyl, n-propyl, n-butyl and isobutyl.
According to the invention, in the formula (II), on the pyridine ring, C1~C3The number and position of the alkyl group of (A) are not particularly limited, R7、R8、R9、R10And R11For example, one or two or three or four of these are H, the remainder are each C1~C3For example, methyl, ethyl, n-propyl or isopropyl.
In a preferred embodiment, in formula (II), R6Is alkyl with 6-8 carbon atoms, such as n-hexyl, n-heptyl or n-octyl, R8、R9And R10Any one of them is an alkyl group having 1 to 3 carbon atoms, and the others are H. In another embodiment, R6Is one of aminoethyl, aminopropyl, carboxymethyl, carboxyethyl and carboxypropyl, R8、R9And R10Any one of them is an alkyl group having 1 to 3 carbon atoms, and the others are H.
The anion of the ionic liquid described herein can be any anion capable of forming an ionic liquid. In a preferred embodiment, the anion of the ionic liquid is BF4 -、PF6 -At least one of bistrifluoromethanesulfonylimide, sulfonate and oxalate, more preferably BF4 -Or PF6 -
In the process according to the present invention, a preferred ionic liquid may be at least one of 1-carboxyethyl-4-methylpyridine tetrafluoroborate, 1-aminoethyl-4-methylpyridine hexafluorophosphate, 1-aminoethyl-3-methylpyridine hexafluorophosphate, 1, 3-dibutylimidazolium tetrafluoroborate, 1-butyl-3-methylimidazolium hexafluoroborate, 1-heptyl-4-methylpyridine hexafluorophosphate, 1-heptyl-3-methylpyridine hexafluorophosphate, 1-carboxypropyl-4-methylpyridine bistrifluoromethylsulfonylimide salt and 1-aminopropyl-4-methylpyridine p-toluenesulfonate.
According to an embodiment of the present invention, the extraction solvent may further include a cosolvent, and the cosolvent may be an amide compound, a pyrrolidone compound, or a sulfone compound, and is preferably one or more of sulfolane, N-dimethylformamide, N-dimethylacetamide, dimethylsulfoxide, and N-methylpyrrolidone. In this embodiment, the relative content of the ionic liquid and the cosolvent in the extraction solvent can vary within a wide range, for example, the mass ratio of the cosolvent to the ionic liquid can be 0.01 to 0.1, preferably 0.02 to 0.08.
In a preferred embodiment, as shown in fig. 1, the extraction solvent and the fischer-tropsch synthesis light oil can be contacted countercurrently in the extraction column 1, i.e. countercurrent extraction is performed; for example, the Fischer-Tropsch light oil may be introduced into the extraction column 1 from the bottom, the extraction solvent may be introduced into the extraction column 1 from the top, and the extraction solvent may be brought into countercurrent contact with the Fischer-Tropsch light oil, whereby the raffinate phase may be discharged from the top of the extraction column 1, and the extract phase may be discharged from the bottom of the extraction column. The extraction column may be conventional in the art, and the present invention is not particularly limited, for example, a packed extraction column or a sieve plate extraction column.
The dosage of the extraction solvent can be changed in a large range, and in one embodiment, the mass ratio of the extraction solvent to the Fischer-Tropsch synthesis light oil can be (0.5-5): 1, preferably (1-4): 1. the liquid-liquid extraction conditions can also be changed within a large range, and in one embodiment, the temperature of the tower kettle of the extraction tower 1 can be 20-120 ℃, and is preferably 30-100 ℃; the operating pressure of the extraction tower is 0.1-0.5 MPa, preferably 0.1-0.3 MPa.
According to the present invention, the raffinate phase obtained from the extraction column 1 is a Fischer-Tropsch synthesis light oil from which oxygenates have been removed, is a hydrocarbon compound, and can be discharged as a product. The method has high yield of hydrocarbon compounds in Fischer-Tropsch synthesis light oil, and the obtained Fischer-Tropsch synthesis light oil product without oxygen compounds has low acid value and low oxygen compounds content, and in one embodiment, the total acid value of the Fischer-Tropsch synthesis light oil product is less than 0.05mgKOH/g, for example less than 0.02 mgKOH/g; the content of oxygen-containing compounds in the Fischer-Tropsch synthesis light oil product can be below 0.15 mass%; the yield of the hydrocarbon compound may be 95% by mass or more, for example 96% by mass or more.
According to the invention, the extraction phase obtained from the extraction column 1, i.e. rich solvent, mainly contains extraction solvent and oxygen-containing compound dissolved in the extraction solution, the extraction phase can be subjected to solvent recovery, the oxygen-containing compound and the extraction solvent are separated, and the extraction solvent obtained by separation is lean solvent and can be recycled; for example, in one embodiment, the extract phase may be fed to a solvent recovery column where a reduced pressure distillation process is used to separate the oxygenate from the extraction solvent in the extract phase; the operation method of performing the vacuum distillation may be conventional in the art, and is not limited herein, and in one embodiment of the present invention, as shown in fig. 1, the extract phase may enter the solvent recovery column 2 from the lower part to perform the vacuum distillation, an oxygen-containing compound may be obtained from the top of the solvent recovery column 2, the oxygen-containing compound may further be separated into higher alcohols and other products as required, a lean solvent may be obtained from the bottom of the solvent recovery column 2, and the lean solvent may be returned to the extraction column 1 for recycling.
According to the invention, the operation conditions of the solvent recovery tower can be changed within a large range, and in one embodiment, the temperature of the tower kettle of the solvent recovery tower 2 is 100-300 ℃, preferably 150-250 ℃; the pressure of the solvent recovery tower is 0.01 to 0.08MPa, preferably 0.03 to 0.06 MPa. The solvent recovery column may be a vacuum distillation column as is conventional in the art.
In one embodiment, as shown in FIG. 1, the method of the present invention may comprise the steps of:
Fischer-Tropsch synthesis light oil enters the extraction tower 1 from the lower part through a pipeline 4, an extraction solvent enters the extraction tower from the upper part through a pipeline 3, and through countercurrent extraction, a raffinate phase is discharged from the top of the extraction tower 1 through a pipeline 5, so that the Fischer-Tropsch synthesis light oil product with oxygen-containing compounds removed is obtained. The rich solvent (extract phase) rich in the oxygen-containing compound is discharged from the bottom of the extraction column, enters the lower part of the solvent recovery column 2 through a line 6, is subjected to reduced pressure distillation, the lean solvent is discharged from the bottom of the solvent recovery column and returns to the extraction column 1 through a line 7 for recycling, the oxygen-containing compound is discharged from a line 8 at the top of the solvent recovery column, and products such as higher alcohols and the like are further separated as required.
The following examples further illustrate the invention but are not intended to limit the invention thereto.
Examples
The oxygen-containing compounds in the Fischer-Tropsch synthesis light oil are removed according to the flow shown in figure 1.
The Fischer-Tropsch synthesis light oil enters the extraction tower 1 from the lower part through a pipeline 4, the solvent enters the extraction tower from the upper part through a pipeline 3, and through countercurrent extraction, the raffinate phase is discharged from the top of the extraction tower 1 through a pipeline 5, so that the Fischer-Tropsch synthesis light oil product with the oxygen-containing compounds removed is obtained. The rich solvent is discharged from the bottom of the extraction tower, enters the lower part of the solvent recovery tower 2 through a pipeline 6, is subjected to reduced pressure distillation, the poor solvent is discharged from the bottom of the solvent recovery tower and returns to the extraction tower 1 for recycling through a pipeline 7, and the oxygen-containing compound is discharged from a pipeline 8 at the top of the solvent recovery tower.
The composition and properties of Fischer-Tropsch synthesis light oil are shown in Table 1, wherein the composition of Fischer-Tropsch synthesis light oil is tested by using a method for measuring the carbon number distribution (gas chromatography) of normal paraffin and non-normal paraffin of SH/T0653-1998 petroleum wax, and the acid value is tested by using a potentiometric titration method for measuring the acid value of GB/T7304-; the extraction solvent used for removing the oxygen-containing compound by liquid-liquid extraction and the operation conditions of each column are shown in tables 2-1 and 2-2, and the composition and acid value of the Fischer-Tropsch synthesis light oil product from which the oxygen-containing compound is removed by extraction and separation and the yield of the hydrocarbon compound in the Fischer-Tropsch synthesis light oil after extraction and separation are shown in tables 3-1 and 3-2.
TABLE 1
N-alkanes,% by mass 38.032
Olefin, mass% 41.628
Oxygen-containing compound(s)% by mass 6.791
Others, by mass% 13.549
Acid value of mgKOH/g 5.11
Boiling range, < DEG C 89.4~231.1
TABLE 2-1
Figure BDA0002254646210000081
The mass ratio of the solvent to the oil of the extraction tower is the mass ratio of the extraction solvent to the Fischer-Tropsch synthesis light oil.
Tables 2 to 2
Figure BDA0002254646210000082
TABLE 3-1
Figure BDA0002254646210000091
TABLE 3-2
Example number 8 9 10
N-alkanes,% by mass 44.138 44.105 43.627
Olefin, mass% 47.105 47.138 47.616
Oxygen-containing compound(s)% by mass 0.130 0.127 0.120
Others, by mass% 8.627 8.630 8.637
Acid value of mgKOH/g <0.02 <0.02 <0.02
Yield of hydrocarbon compound,% by mass 97.4 96.8 97.2
The data of the examples show that the method of the invention has good effect of removing the oxygen-containing compounds in the Fischer-Tropsch synthesis light oil, the total acid value of the Fischer-Tropsch synthesis light oil product can be reduced to below 0.02mgKOH/g, the content of the oxygen-containing compounds can be reduced to below 0.14 mass percent, and the yield of the hydrocarbon compounds can reach above 96 mass percent.
The preferred embodiments of the present invention have been described in detail with reference to the accompanying drawings, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications can be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various features described in the above embodiments may be combined in any suitable manner without departing from the scope of the invention. The invention is not described in detail in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.

Claims (10)

1. A method for removing oxygen-containing compounds in Fischer-Tropsch synthesis light oil comprises the following steps:
contacting Fischer-Tropsch synthesis light oil with an extraction solvent in an extraction tower (1) for liquid-liquid extraction to obtain a raffinate phase and an extract phase rich in oxygen-containing compounds, wherein the raffinate phase is the Fischer-Tropsch synthesis light oil without the oxygen-containing compounds;
carrying out reduced pressure distillation on the extract phase in a solvent recovery tower (2), discharging oxygen-containing compounds from the top of the tower, and returning a lean solvent discharged from the bottom of the tower to the extraction tower (1);
wherein the extraction solvent is ionic liquid, and the cation of the ionic liquid has a structure shown in a formula (I) or a formula (II);
Figure FDA0002254646200000011
in the formula (I), R2、R4And R5Each independently is H, R1And R3Are respectively selected from C1~C4One of alkyl, aminoethyl, aminopropyl, carboxymethyl, carboxyethyl and carboxypropyl of (a); in the formula (II), R7、R8、R9、R10And R11Each independently is H or C1~C3Alkyl of R6One selected from alkyl with 6-8 carbon atoms, aminoethyl, aminopropyl, carboxymethyl, carboxyethyl and carboxypropyl.
2. The process of claim 1, wherein in formula (II), R6Selected from alkyl with 6-8 carbon atoms, R8、R9And R10Any one of them is an alkyl group having 1 to 3 carbon atoms, and the others are H.
3. The process of claim 1, wherein in formula (II), R6Is one of aminoethyl, aminopropyl, carboxymethyl, carboxyethyl and carboxypropyl, R8、R9And R10Any one of them is an alkyl group having 1 to 3 carbon atoms, and the others are H.
4. A process according to any one of claims 1 to 3, wherein the anion of the ionic liquid is BF4 -、PF6 -One or more of bis (trifluoromethanesulfonyl) imide, sulfonate and oxalate.
5. The process of claim 1, wherein the extraction solvent further comprises a co-solvent selected from one or more of sulfolane, N-dimethylformamide, N-dimethylacetamide, dimethylsulfoxide, and N-methylpyrrolidone; the mass ratio of the cosolvent to the ionic liquid is 0.01-0.1.
6. The process according to claim 1, wherein the light fischer-tropsch synthesis oil is fed into an extraction column (1) from below, the extraction solvent is fed into the extraction column (1) from above, and is contacted with the light fischer-tropsch synthesis oil in a countercurrent manner, the raffinate phase is discharged from the top of the extraction column (1), and the extract phase is discharged from the bottom of the extraction column; the mass ratio of the extraction solvent to the Fischer-Tropsch synthesis light oil is (0.5-5): 1.
7. the method of claim 1, wherein the temperature of the bottom of the extraction column (1) is 20-120 ℃ and the pressure is 0.1-0.5 MPa.
8. The method according to claim 1, wherein the temperature of the bottom of the solvent recovery column (2) is 100 to 300 ℃ and the pressure is 0.01 to 0.08 MPa.
9. The method according to claim 1, wherein the Fischer-Tropsch light oil is a fraction having a hydrocarbon carbon number of 4 to 16.
10. The method according to claim 1 or 9, wherein the Fischer-Tropsch light oil contains 1 to 15% by mass of an oxygen-containing compound, has a total content of normal paraffins and olefins of 20 to 90% by mass, and has a total acid value of 3 to 150 mgKOH/g.
CN201911048205.6A 2019-10-30 2019-10-30 Method for removing oxygen-containing compounds in Fischer-Tropsch synthesis light oil Active CN112745888B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201911048205.6A CN112745888B (en) 2019-10-30 2019-10-30 Method for removing oxygen-containing compounds in Fischer-Tropsch synthesis light oil

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201911048205.6A CN112745888B (en) 2019-10-30 2019-10-30 Method for removing oxygen-containing compounds in Fischer-Tropsch synthesis light oil

Publications (2)

Publication Number Publication Date
CN112745888A true CN112745888A (en) 2021-05-04
CN112745888B CN112745888B (en) 2022-05-03

Family

ID=75640946

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201911048205.6A Active CN112745888B (en) 2019-10-30 2019-10-30 Method for removing oxygen-containing compounds in Fischer-Tropsch synthesis light oil

Country Status (1)

Country Link
CN (1) CN112745888B (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115820294A (en) * 2022-11-28 2023-03-21 国家能源集团宁夏煤业有限责任公司 Method for removing oxygen-containing compounds in Fischer-Tropsch synthetic oil

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102381776A (en) * 2010-08-26 2012-03-21 中科合成油技术有限公司 Catalytic hydrogenation desorption method for oxygenated compound in Fischer-Tropsch synthesized water phase and application thereof
CN105777467A (en) * 2016-04-13 2016-07-20 上海兖矿能源科技研发有限公司 Method for separating oxygenated chemicals and 1-hexene from Fischer-Tropsch synthesis oil product
CN109022027A (en) * 2017-06-12 2018-12-18 神华集团有限责任公司 The method of F- T synthesis light oil production poly alpha olefin and the poly alpha olefin obtained by this method
CN109096033A (en) * 2018-07-17 2018-12-28 天津大学 Remove the method and apparatus of oxygenatedchemicals in Fischer-Tropsch synthesis oil narrow fraction

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102381776A (en) * 2010-08-26 2012-03-21 中科合成油技术有限公司 Catalytic hydrogenation desorption method for oxygenated compound in Fischer-Tropsch synthesized water phase and application thereof
CN105777467A (en) * 2016-04-13 2016-07-20 上海兖矿能源科技研发有限公司 Method for separating oxygenated chemicals and 1-hexene from Fischer-Tropsch synthesis oil product
CN109022027A (en) * 2017-06-12 2018-12-18 神华集团有限责任公司 The method of F- T synthesis light oil production poly alpha olefin and the poly alpha olefin obtained by this method
CN109096033A (en) * 2018-07-17 2018-12-28 天津大学 Remove the method and apparatus of oxygenatedchemicals in Fischer-Tropsch synthesis oil narrow fraction

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115820294A (en) * 2022-11-28 2023-03-21 国家能源集团宁夏煤业有限责任公司 Method for removing oxygen-containing compounds in Fischer-Tropsch synthetic oil

Also Published As

Publication number Publication date
CN112745888B (en) 2022-05-03

Similar Documents

Publication Publication Date Title
CN112745909B (en) Method for removing oxygen-containing compounds in Fischer-Tropsch synthesis light oil
CN112745907B (en) Method for removing oxygen-containing compounds in Fischer-Tropsch synthetic oil
CN113862023A (en) Method and device for removing oxygen-containing compounds from Fischer-Tropsch oil
CN112745912B (en) Method for removing oxygen-containing compounds in Fischer-Tropsch synthesis light oil
CN112745888B (en) Method for removing oxygen-containing compounds in Fischer-Tropsch synthesis light oil
CN102452886A (en) Method for purifying 1-octylene from Fischer-Tropsch synthetic oil products
CN112745913B (en) Method for removing oxygen-containing compounds in Fischer-Tropsch synthetic oil
CN104945328B (en) The double solvents and application process of aromatic hydrocarbons and alkane in extracting separation diesel oil distillate
CN104945327B (en) A kind of extracting separates the solvent and method of aromatic hydrocarbons and alkane in diesel oil distillate
US5675043A (en) Process for the selective removal of nitrogen-containing compounds from hydrocarbon blends
CN112745908B (en) Method for removing oxygen-containing compounds in Fischer-Tropsch synthesis light oil
CN108822885B (en) Composite extracting agent for Fischer-Tropsch oil deoxidizer and preparation method thereof
CN112625732B (en) Composite extractant for extracting oxygen-containing compounds in C5 hydrocarbon raw material and method for treating oxygen-containing compounds in C5 hydrocarbon
CN113621402A (en) Separation method of Fischer-Tropsch synthetic oil
KR102375735B1 (en) Process for the production of butadiene from ethanol comprising purification of a butadiene-rich effluent by extractive distillation
WO2024060399A1 (en) Separation method for high-temperature fischer-tropsch synthesized light oil
CN116144393B (en) Composite solvent and method for producing low-aromatic special oil
CN114057535B (en) Composite solvent for extracting, rectifying and separating aromatic hydrocarbon from hydrocarbon mixture and application method
CN116199556A (en) Method for separating mixture containing oxygen-containing compound, alkane and alkene
RU2275413C1 (en) Vacuum gas oil and mazut purification process
CN117821108A (en) Process for separating diesel oil fraction
CN116924875A (en) Method for purifying polymerization grade 1-heptene from Fischer-Tropsch oil product
CN115491222A (en) Composite extracting agent and Fischer-Tropsch synthesis distillate oil separation method using same
CN114736094A (en) Method for separating alkane and olefin by liquid-liquid extraction
CN114736091A (en) Method and apparatus for separating 1-hexene from hydrocarbon stream containing C6 olefins

Legal Events

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