CN114437756B - Method for removing oxygen-containing compound in high-carbon Fischer-Tropsch synthesis oil - Google Patents

Method for removing oxygen-containing compound in high-carbon Fischer-Tropsch synthesis oil Download PDF

Info

Publication number
CN114437756B
CN114437756B CN202011226911.8A CN202011226911A CN114437756B CN 114437756 B CN114437756 B CN 114437756B CN 202011226911 A CN202011226911 A CN 202011226911A CN 114437756 B CN114437756 B CN 114437756B
Authority
CN
China
Prior art keywords
fischer
tropsch
oil
entrainer
tower
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.)
Active
Application number
CN202011226911.8A
Other languages
Chinese (zh)
Other versions
CN114437756A (en
Inventor
钱震
武靖为
李俊诚
张越
寇海庭
菅青娥
张晓龙
关怀
刘宏宇
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.)
Inner Mongolia Yitai Coal Based New Materials Research Institute Co Ltd
Original Assignee
Inner Mongolia Yitai Coal Based New Materials Research Institute Co Ltd
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 Inner Mongolia Yitai Coal Based New Materials Research Institute Co Ltd filed Critical Inner Mongolia Yitai Coal Based New Materials Research Institute Co Ltd
Priority to CN202011226911.8A priority Critical patent/CN114437756B/en
Publication of CN114437756A publication Critical patent/CN114437756A/en
Application granted granted Critical
Publication of CN114437756B publication Critical patent/CN114437756B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • C10G7/00—Distillation of hydrocarbon oils
    • C10G7/08—Azeotropic or extractive distillation
    • 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
    • C10G53/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes
    • C10G53/02—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes plural serial stages only
    • C10G53/08—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes plural serial stages only including at least one sorption step
    • 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
    • C10G53/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes
    • C10G53/02—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes plural serial stages only
    • C10G53/12—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes plural serial stages only including at least one alkaline treatment step
    • 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
    • C10G2300/1022—Fischer-Tropsch products
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/201—Impurities

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)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

A process for removing oxygenates from a high carbon fischer-tropsch synthesis oil comprising: the Fischer-Tropsch synthesis oil is subjected to azeotropic distillation in a rectifying tower, wherein the entrainer is one or more of ethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, 1, 2-butanediol, 1, 3-butanediol, 2-3-butanediol, n-amyl alcohol, isoprene glycol and isomers thereof. The invention can improve the removal effect of the oxygen-containing compound in the high-carbon Fischer-Tropsch synthetic oil.

Description

Method for removing oxygen-containing compound in high-carbon Fischer-Tropsch synthesis oil
Technical Field
The invention belongs to the technical field of chemical industry, and particularly relates to a method for removing oxygen-containing compounds in high-carbon Fischer-Tropsch synthetic oil.
Background
The Fischer-Tropsch oil has abundant downstream applications due to the rich alpha-olefin, but about 5wt% of the oxygenate is produced during the Fischer-Tropsch reaction, which is mainly classified as aldehyde, acid, alcohol, ketone, or ester 5. The inclusion of such impurities in the product can interfere with downstream product applications and means are required to remove the oxygenates.
In CN109054886a, methanol, ethanol, isopropanol and organic base are used as solvents for extraction to remove oxygen-containing compounds, and these solvents are slightly dissolved in the fischer-tropsch oil; CN100413824C uses methanol and water as extractant; the method introduces new impurities, and the boiling points of methanol, ethanol and isopropanol are contained in the distillation range of Fischer-Tropsch synthetic oil, so that the impurities cannot be removed by rectification, and the separation is more difficult. Oxygenates in the vicinity of the boiling point of Fischer-Tropsch oils having a carbon number below 10 are generally less polar and more polar and readily soluble in polar solvents for removal. However, the fischer-tropsch synthesis oil having a carbon number of more than 10 usually has an atmospheric boiling point of more than 190 ℃, and the oxygenates having a carbon number in the vicinity of the boiling point thereof have a high carbon number and a low polarity, are not easily soluble in polar solvents, but are easily soluble in nonpolar oil phases, and are therefore not easily removed by extraction means.
CN201210150208.2 uses porous metal organic compounds as solid adsorbents to remove oxygenate impurities from hydrocarbon streams. Adsorption processes are generally limited by the adsorption capacity of the adsorbent and require regeneration after saturation of the adsorbent, and are energy intensive, most of which are used with oxygenate contents below 1%, otherwise are inefficient and costly to operate.
CN105272809a passivates oxygen-containing impurities containing active hydrogen atoms in alpha-olefins produced by coal into metal alkoxide by using active alkaline earth metals, precipitates the metal alkoxide from the material to remove the metal alkoxide, and removes residual ketone compounds by adsorption. The method consumes large amount of alkaline earth metal and has high cost.
CN201010526998.0 uses ethanol to azeotrope with hydrocarbons below C8 to remove oxygenates. CN201310303047.0 azeotropically removes oxygenates from 1-octene using one of ethanol, isopropanol, n-propanol, isobutanol, t-butanol, n-butanol. The method is suitable for low-carbon hydrocarbons, and can not effectively remove oxygen-containing compounds in high-carbon hydrocarbons.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a method for removing oxygen-containing compounds in Fischer-Tropsch synthetic oil, which is particularly suitable for effectively removing oxygen-containing compounds in high-carbon Fischer-Tropsch synthetic oil with carbon number of more than 10.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
a process for removing oxygenates from a high carbon fischer-tropsch synthesis oil comprising:
the Fischer-Tropsch synthesis oil is subjected to azeotropic distillation in a rectifying tower, wherein the entrainer is one or more of ethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, 1, 2-butanediol, 1, 3-butanediol, 2-3-butanediol, n-amyl alcohol, isoprene glycol and isomers thereof.
In some embodiments, the volume ratio of the fischer-tropsch synthesis oil to the entrainer is 1:0.2 to 1:10 (e.g., 1:0.5, 1:1, 1:2, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, or 1:9).
In some embodiments, the number of trays in the rectification column ranges from 5 to 60 (e.g., 10, 20, 30, 40, or 50); preferably, the feed tray of the entrainer in the rectification column is located above the feed tray of the Fischer-Tropsch synthesis oil; the reflux ratio at the top of the column ranges from 1:1 to 10:1 (e.g., 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, or 9:1).
In some embodiments, the operating pressure of the rectification column is atmospheric and the column bottoms operating temperature is 190-250 ℃ (e.g., 200 ℃, 210 ℃, 220 ℃, 230 ℃, or 240 ℃); alternatively, the operating pressure of the rectification column is from 0.1 to 15kpa (e.g., 1kpa, 2kpa, 5kpa, 8kpa, 10kpa, or 12 kpa); the temperature of the tower kettle is 130-160 ℃ (such as 135 ℃, 140 ℃, 145 ℃, 150 ℃ or 155 ℃).
In some embodiments, the method further comprises removing oxygenates after azeotropic distillation using molecular sieve adsorption.
In some embodiments, the molecular sieve type is one or more of 3A, 4A, 5A, 10X, 13X.
In some embodiments, the temperature at which the oxygenate is removed by adsorption using molecular sieves is 50-80 ℃ (e.g., 55 ℃, 60 ℃, 65 ℃, 70 ℃, or 75 ℃) and the pressure is 0.1-0.5Mpa (e.g., 0.2Mpa, 0.3Mpa, or 0.4 Mpa).
In some embodiments, the process further comprises caustic washing the Fischer-Tropsch oil with a caustic solution to remove sour species from the Fischer-Tropsch oil prior to azeotropic distillation, followed by water washing; preferably, the base is selected from inorganic bases, preferably comprising KOH, naOH, na, and/or organic bases 2 CO 3 、K2CO 3 、Ca(OH) 2 、NaHCO 3 、KHCO 3 Preferably, the organic base comprises an amine compound (e.g., alkylamine), and the alkali solution has a mass concentration of 5% to 40% (for exampleSuch as 10%, 15%, 20%, 25%, 30% or 35%) of the Fischer-Tropsch oil to caustic solution in a volume ratio of 1:0.2 to 1:5 (e.g., 1:0.5, 1:1, 1:2, 1:3 or 1:4) and caustic wash agitation times of 30 minutes to 4 hours (e.g., 1h, 1.5h, 2h, 2.5h, 3h or 3.5 h).
In some embodiments, the volume ratio of Fischer-Tropsch oil to water is from 1:0.2 to 1:5 (e.g., 1:0.5, 1:1, 1:2, 1:3, or 1:4) when washed with water, and the agitation time for the washing is from 30 minutes to 2 hours (e.g., 1 hour or 1.5 hours).
In some embodiments, the caustic wash and/or the water wash are performed in a static mixer having a reflux/pick-up ratio of 1:1 to 10:1 (e.g., 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, or 9:1).
Because the oxygenated compounds in the high-carbon Fischer-Tropsch synthesis oil products have higher boiling points, higher carbon numbers and lower polarity, the oxygenated compounds are not easy to remove by an extraction means, and the technological difficulty of removing the oxygenated compounds by an azeotropic distillation means is to find a proper entrainer. At present, the entrainer for the low-carbon Fischer-Tropsch synthetic oil comprises ethanol, propanol, butanol and the like, but the entrainer hardly forms an azeotrope with the Fischer-Tropsch synthetic oil with carbon number of more than or equal to 10, so the entrainer has poor effect of removing the oxygen-containing compound with the boiling point higher than 190 ℃.
The invention provides an effective removal means for oxygen-containing compounds in high-carbon-number Fischer-Tropsch synthesis oil products with carbon numbers more than or equal to 10, which has good removal effect for oxygen-containing compounds with boiling points higher than 190 ℃ and the removal rate can reach more than 98%.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments in order to make the objects, technical solutions and advantages of the present invention more apparent.
Reference throughout this specification to "one embodiment" or "an embodiment" means that a particular feature, structure, or parameter, step, or the like described in the embodiment is included in at least one embodiment according to the present invention. Thus, references to "one embodiment according to the present invention," "in an embodiment," and the like, in this specification are not intended to specify the presence of stated features but rather are intended to be included in particular embodiments, if they are used in the same sense. It will be appreciated by those of skill in the art that the specific features, structures or parameters, steps, etc. disclosed in one or more of the embodiments of the invention may be combined in any suitable manner.
The invention removes the oxygen-containing compound in the high-carbon Fischer-Tropsch synthetic oil with the carbon number more than or equal to 10 by azeotropic means, and the removal rate is up to more than 98 percent, thereby effectively solving the difficult problem of removing the oxygen-containing compound in the high-carbon Fischer-Tropsch synthetic oil.
According to an embodiment of the invention, the invention provides a method for removing an oxygen-containing compound in high-carbon Fischer-Tropsch synthetic oil, which comprises the following steps:
(1) Deacidifying: alkali washing is carried out on Fischer-Tropsch synthetic oil by using alkali solution, acidic substances are converted into salts which are easy to dissolve in water, and meanwhile, lipid is hydrolyzed and removed by subsequent water washing. Wherein the base may be an inorganic base and/or an organic base, the inorganic base mainly including but not limited to KOH, naOH, na 2 CO 3 、K 2 CO 3 、Ca(OH) 2 、NaHCO 3 、KHCO 3 And the like, the organic base can comprise amine compounds, such as alkylamine (e.g. methylamine, ethylamine) and the like, the mass concentration of the alkali solution is 5% -40% (e.g. 10%, 15%, 20%, 25%, 30% or 35%), the volume ratio of Fischer-Tropsch synthetic oil to alkali solution is 1:0.2 to 1:5 (e.g. 1:0.5, 1:1, 1:2, 1:3 or 1:4), the alkali washing stirring time is 30 min-4 hours (e.g. 1h, 1.5h, 2h, 2.5h, 3h or 3.5 h), and the mixture is kept stand for 15-60min for layering. When water washed, the volume ratio of Fischer-Tropsch oil to water is from 1:0.2 to 1:5 (e.g., 1:0.5, 1:1, 1:2, 1:3, or 1:4). The water washing and stirring time is 30min-2h (for example, 1h or 1.5 h), and the mixture is kept stand for 15-60min for layering. The stirring mode can also be replaced by a static mixer, the outlet of the static mixer is refluxed to the inlet, and the reflux amount/extraction amount ratio is 1:1-10:1 (for example, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1 or 9:1).
(2) The deacidified Fischer-Tropsch synthetic oil is subjected to azeotropic distillation in a rectifying tower, the entrainer is one or more of ethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, 1, 2-butanediol, 1, 3-butanediol, 2-butanediol, n-amyl alcohol, isopentane diol and isomers thereof, the entrainer is selected according to the carbon number of an oxygen-containing compound, the higher the boiling point of the oxygen-containing compound is, the higher the carbon number of the corresponding entrainer is to obtain better effect, and the entrainer is preferably ethylene glycol for the oxygen-containing compound with the boiling point of 190-220 ℃. The volume ratio of Fischer-Tropsch oil to entrainer is from 1:0.2 to 1:10 (e.g. 1:0.5, 1:1, 1:2, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8 or 1:9), preferably 1:3.
The number of the rectification stages is in the range of 5 to 60 (e.g., 10, 20, 30, 40 or 50), preferably 35. The feed tray for the entrainer in the rectification column should be above the feed tray for the Fischer-Tropsch synthesis oil. The entrainer feed position is preferably 8 and the Fischer-Tropsch oil feed position is preferably 16 (default overhead 1 tray). The Fischer-Tropsch synthesis oil product and the entrainer form an azeotrope to reduce the boiling point, and the azeotrope is distilled from the top of the tower; the oxygenates flow from the bottom of the column. The reflux ratio at the top of the column ranges from 1:1 to 10:1 (e.g., 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, or 9:1), preferably 3:1.
the column bottoms are operated at a temperature of 190-250deg.C (e.g., 200deg.C, 210deg.C, 220deg.C, 230deg.C or 240 deg.C), preferably 205 deg.C, at atmospheric pressure. However, since Fischer-Tropsch oils are rich in valuable alpha olefins, which are readily isomerised and cracked at high temperatures, reduced pressure operations are typically employed, operating at pressures of from 0.1 to 15kpa absolute (e.g. 1kpa, 2kpa, 5kpa, 8kpa, 10kpa or 12 kpa), preferably 10kpa; the temperature of the bottom of the column at 10kpa is 130-160 c (e.g., 135 c, 140 c, 145 c, 150 c or 155 c), preferably 140 c.
(3) The steps can reduce about 50000ppm of oxygen-containing compounds in Fischer-Tropsch synthesis oil to about 500ppm, and the method belongs to the coarse removal process of the oxygen-containing compounds. Fischer-Tropsch oils, which contain less than 500ppm oxygenates, may already meet some of the needs of downstream applications. But some fine chemical processes require higher fine removal processes.
The fine removal in the embodiment of the invention comprises the following steps of; the molecular sieve adsorption is utilized to remove the oxygen-containing compound from 500ppm to less than 1 ppm. Wherein the molecular sieve type is one or more of 3A, 4A, 5A, 10X and 13X. The adsorption temperature is 50-80deg.C (such as 55deg.C, 60deg.C, 65deg.C, 70deg.C or 75deg.C), and the adsorption pressure is 0.1-0.5Mpa (such as 0.2Mpa, 0.3Mpa or 0.4 Mpa).
Example 1
(1) The Fischer-Tropsch oil is subjected to an alkaline wash with aqueous NaOH to convert the acidic material to readily water soluble salts, while the lipids are hydrolysed and removed by subsequent water washes. Wherein the mass concentration of the NaOH aqueous solution is 40%, the volume ratio of the Fischer-Tropsch synthetic oil to the NaOH aqueous solution is 1:0.2, the alkali washing and stirring time is 30min, and the mixture is stood for 40min for layering. When washing, the volume ratio of Fischer-Tropsch synthetic oil to water is 1:0.2, and the mixture is stirred for 30min after washing, and is kept stand for 40min for layering.
(2) And (3) carrying out azeotropic distillation on the deacidified Fischer-Tropsch synthetic oil in a rectifying tower, wherein the entrainer is glycol. The volume ratio of Fischer-Tropsch synthetic oil to glycol is 1:0.2. The operating pressure is 10kpa absolute; the temperature of the column bottom was 130 ℃.
The number of rectifying plates was 22. The feeding position of the corresponding entrainer is 6 plates, and the feeding position of the corresponding Fischer-Tropsch synthetic oil is 10 plates (the tower top is the 1 st plate by default). The Fischer-Tropsch synthesis oil product and the entrainer form an azeotrope to reduce the boiling point, and the azeotrope is distilled from the top of the tower; the oxygenates flow from the bottom of the column. The reflux ratio at the top of the column is 5:1.
The content of oxygen-containing compounds in the Fischer-Tropsch synthesis oil product is 450ppm through detection.
(3) The 13X molecular sieve is used for absorbing and removing the oxygen-containing compound, the operating temperature is 50 ℃, and the operating pressure is 0.2Mpa.
The content of oxygen-containing compounds in the Fischer-Tropsch synthesis oil product is 10ppm through detection.
Example 2
(1) The Fischer-Tropsch oil is subjected to an alkaline wash with aqueous NaOH to convert the acidic material to readily water soluble salts, while the lipids are hydrolysed and removed by subsequent water washes. Wherein the mass concentration of the NaOH aqueous solution is 35%, the volume ratio of the Fischer-Tropsch synthetic oil to the NaOH aqueous solution is 1:0.5, the alkali washing and stirring time is 30min, and the mixture is stood for 40min for layering. When washing, the volume ratio of Fischer-Tropsch synthetic oil to water is 1:0.2, and the mixture is stirred for 30min after washing, and is kept stand for 40min for layering.
(2) And (3) carrying out azeotropic distillation on the deacidified Fischer-Tropsch synthetic oil in a rectifying tower, wherein an entrainer is 1, 3-butanediol. The volume ratio of Fischer-Tropsch synthetic oil to 1, 3-butanediol is 1:2.5. The operating pressure is 10kpa absolute; the temperature of the column bottom was 140 ℃.
The number of the rectification column plates is 22. The feeding position of the corresponding entrainer is 6 plates, and the feeding position of the corresponding Fischer-Tropsch synthetic oil is 10 plates (the tower top is the 1 st plate by default). The Fischer-Tropsch synthesis oil product and the entrainer form an azeotrope to reduce the boiling point, and the azeotrope is distilled from the top of the tower; the oxygenates flow from the bottom of the column. The reflux ratio at the top of the column is 5:1.
The content of the oxygen-containing compound in the Fischer-Tropsch synthesis oil product is detected to be 410ppm.
(3) The 13X molecular sieve is used for absorbing and removing the oxygen-containing compound, the operating temperature is 50 ℃, and the operating pressure is 0.2Mpa.
The content of oxygen-containing compounds in the Fischer-Tropsch synthesis oil product is 10ppm through detection.
Example 3
(1) Using NaHCO 3 The aqueous solution is used for alkaline washing of Fischer-Tropsch oil, converting acidic substances into salts which are easily soluble in water, hydrolyzing lipids, and removing the lipids through subsequent water washing. Wherein NaHCO 3 The mass concentration of the aqueous solution is 10%, and the Fischer-Tropsch synthesis oil and NaHCO 3 The volume ratio of the aqueous solution is 1:2, the alkali washing and stirring time is 30min, and the aqueous solution is kept stand for 40min for layering. When washing, the volume ratio of Fischer-Tropsch synthetic oil to water is 1:5, and the mixture is stirred for 30min after washing, and is kept stand for 40min for layering.
(2) And (3) carrying out azeotropic distillation on the deacidified Fischer-Tropsch synthetic oil in a rectifying tower, wherein the entrainer is glycol. The volume ratio of Fischer-Tropsch synthetic oil to glycol is 1:2.5. The operating pressure is 10kpa absolute; the temperature of the tower kettle is 150 ℃.
The number of the rectification column plates is 22. The feeding position of the corresponding entrainer is 6 plates, and the feeding position of the corresponding Fischer-Tropsch synthetic oil is 10 plates (the tower top is the 1 st plate by default). The Fischer-Tropsch synthesis oil product and the entrainer form an azeotrope to reduce the boiling point, and the azeotrope is distilled from the top of the tower; the oxygenates flow from the bottom of the column. The reflux ratio at the top of the column is 5:1.
The content of oxygen-containing compounds in the Fischer-Tropsch synthesis oil product is 420ppm through detection.
(3) The 13X molecular sieve is used for absorbing and removing the oxygen-containing compound, the operating temperature is 50 ℃, and the operating pressure is 0.2Mpa.
The content of oxygen-containing compounds in the Fischer-Tropsch synthesis oil product is 10ppm through detection.
Example 4
(1) The Fischer-Tropsch oil is subjected to an alkaline wash with aqueous NaOH to convert the acidic material to readily water soluble salts, while the lipids are hydrolysed and removed by subsequent water washes. Wherein the mass concentration of the NaOH aqueous solution is 40%, the volume ratio of the Fischer-Tropsch synthetic oil to the NaOH aqueous solution is 1:0.2, the alkali washing and stirring time is 30min, and the mixture is stood for 40min for layering. When washing, the volume ratio of Fischer-Tropsch synthetic oil to water is 1:0.2, and the mixture is stirred for 30min after washing, and is kept stand for 40min for layering.
(2) And (3) carrying out azeotropic distillation on the deacidified Fischer-Tropsch synthetic oil in a rectifying tower, wherein the entrainer is glycol. The volume ratio of Fischer-Tropsch synthetic oil to glycol is 1:2.5. The operating pressure is 10kpa absolute; the temperature of the column bottom was 160 ℃.
The number of the rectifying tower plates is 45. The feeding position of the corresponding entrainer is 11 plates, and the feeding position of the corresponding Fischer-Tropsch synthesis oil is 22 plates (the tower top is the 1 st tower plate by default). The Fischer-Tropsch synthesis oil product and the entrainer form an azeotrope to reduce the boiling point, and the azeotrope is distilled from the top of the tower; the oxygenates flow from the bottom of the column. The reflux ratio at the top of the column is 5:1.
The content of oxygen-containing compounds in the Fischer-Tropsch synthesis oil product is 350ppm through detection.
(3) The 13X molecular sieve is used for absorbing and removing the oxygen-containing compound, the operating temperature is 50 ℃, and the operating pressure is 0.2Mpa.
The content of oxygen-containing compounds in the Fischer-Tropsch synthesis oil product is 10ppm through detection.
Example 5
(1) The Fischer-Tropsch oil is subjected to an alkaline wash with aqueous NaOH to convert the acidic material to readily water soluble salts, while the lipids are hydrolysed and removed by subsequent water washes. Wherein the mass concentration of the NaOH aqueous solution is 40%, the volume ratio of the Fischer-Tropsch synthetic oil to the NaOH aqueous solution is 1:0.2, the alkali washing and stirring time is 30min, and the mixture is stood for 40min for layering. When washing, the volume ratio of Fischer-Tropsch synthetic oil to water is 1:0.2, and the mixture is stirred for 30min after washing, and is kept stand for 40min for layering.
(2) And (3) carrying out azeotropic distillation on the deacidified Fischer-Tropsch synthetic oil in a rectifying tower, wherein the entrainer is isoprene glycol. The volume ratio of Fischer-Tropsch synthetic oil to isoprene glycol is 1:2.5. The operating pressure is 10kpa absolute; the temperature of the column bottom was 140 ℃.
The number of rectifying plates was 22. The feeding position of the corresponding entrainer is 6 plates, and the feeding position of the corresponding Fischer-Tropsch synthetic oil is 10 plates (the tower top is the 1 st plate by default). The Fischer-Tropsch synthesis oil product and the entrainer form an azeotrope to reduce the boiling point, and the azeotrope is distilled from the top of the tower; the oxygenates flow from the bottom of the column. The reflux ratio at the top of the column is 10:1.
The content of the oxygen-containing compound in the Fischer-Tropsch synthesis oil product is 310ppm through detection.
(3) The 13X molecular sieve is used for absorbing and removing the oxygen-containing compound, the operating temperature is 50 ℃, and the operating pressure is 0.2Mpa.
The content of oxygen-containing compounds in the Fischer-Tropsch synthesis oil product is 9ppm through detection.
Example 6
(1) The Fischer-Tropsch oil is subjected to an alkaline wash with aqueous NaOH to convert the acidic material to readily water soluble salts, while the lipids are hydrolysed and removed by subsequent water washes. Wherein the mass concentration of the NaOH aqueous solution is 40%, the volume ratio of the Fischer-Tropsch synthetic oil to the NaOH aqueous solution is 1:0.2, the alkali washing and stirring time is 30min, and the mixture is stood for 40min for layering. When washing, the volume ratio of Fischer-Tropsch synthetic oil to water is 1:0.2, and the mixture is stirred for 30min after washing, and is kept stand for 40min for layering.
(2) And (3) carrying out azeotropic distillation on the deacidified Fischer-Tropsch synthetic oil in a rectifying tower, wherein the entrainer is glycol. The volume ratio of Fischer-Tropsch synthetic oil to glycol is 1:0.2. The operating pressure is 10kpa absolute; the temperature of the tower kettle is 150 ℃.
The number of rectifying plates was 22. The feeding position of the corresponding entrainer is 6 plates, and the feeding position of the corresponding Fischer-Tropsch synthetic oil is 10 plates (the tower top is the 1 st plate by default). The Fischer-Tropsch synthesis oil product and the entrainer form an azeotrope to reduce the boiling point, and the azeotrope is distilled from the top of the tower; the oxygenates flow from the bottom of the column. The reflux ratio at the top of the column is 5:1.
The content of oxygen-containing compounds in the Fischer-Tropsch synthesis oil product is 450ppm through detection.
(3) The 5A molecular sieve is used for absorbing and removing the oxygen-containing compound, the operating temperature is 50 ℃, and the operating pressure is 0.2Mpa.
The content of oxygen-containing compounds in the Fischer-Tropsch synthesis oil product is 20ppm through detection.
Comparative example 1
(1) The Fischer-Tropsch oil is subjected to an alkaline wash with aqueous NaOH to convert the acidic material to readily water soluble salts, while the lipids are hydrolysed and removed by subsequent water washes. Wherein the mass concentration of the NaOH aqueous solution is 40%, the volume ratio of the Fischer-Tropsch synthetic oil to the NaOH aqueous solution is 1:0.2, the alkali washing and stirring time is 30min, and the mixture is stood for 40min for layering. When washing, the volume ratio of Fischer-Tropsch synthetic oil to water is 1:0.2, and the mixture is stirred for 30min after washing, and is kept stand for 40min for layering.
(2) And (3) carrying out azeotropic distillation on the deacidified Fischer-Tropsch synthetic oil in a rectifying tower, wherein the entrainer is ethanol. The volume ratio of Fischer-Tropsch synthetic oil to ethanol is 1:2.5. The operating pressure is 10kpa absolute; the temperature of the column bottom was 140 ℃.
The number of rectifying plates was 22. The feeding position of the corresponding entrainer is 6 plates, and the feeding position of the corresponding Fischer-Tropsch synthetic oil is 10 plates (the tower top is the 1 st plate by default). The Fischer-Tropsch synthesis oil product and the entrainer form an azeotrope to reduce the boiling point, and the azeotrope is distilled from the top of the tower; the oxygenates flow from the bottom of the column. The reflux ratio at the top of the column is 5:1.
The content of oxygen-containing compounds in the Fischer-Tropsch synthesis oil product is 32000ppm through detection.
Comparative example 2
(1) The Fischer-Tropsch oil is subjected to an alkaline wash with aqueous NaOH to convert the acidic material to readily water soluble salts, while the lipids are hydrolysed and removed by subsequent water washes. Wherein the mass concentration of the NaOH aqueous solution is 40%, the volume ratio of the Fischer-Tropsch synthetic oil to the NaOH aqueous solution is 1:0.2, the alkali washing and stirring time is 30min, and the mixture is stood for 40min for layering. When washing, the volume ratio of Fischer-Tropsch synthetic oil to water is 1:0.2, and the mixture is stirred for 30min after washing, and is kept stand for 40min for layering.
(2) And (3) carrying out azeotropic distillation on the deacidified Fischer-Tropsch synthetic oil in a rectifying tower, wherein the entrainer is methanol. The volume ratio of Fischer-Tropsch oil to methanol is 1:2.5. The operating pressure is 10kpa absolute; the temperature of the tower kettle is 150 ℃.
The number of rectifying plates was 22. The feeding position of the corresponding entrainer is 6 plates, and the feeding position of the corresponding Fischer-Tropsch synthetic oil is 10 plates (the tower top is the 1 st plate by default). The Fischer-Tropsch synthesis oil product and the entrainer form an azeotrope to reduce the boiling point, and the azeotrope is distilled from the top of the tower; the oxygenates flow from the bottom of the column. The reflux ratio at the top of the column is 5:1.
The content of oxygen-containing compounds in the Fischer-Tropsch synthesis oil product is 34000ppm through detection.
The invention can be found to significantly reduce the oxygenate content in Fischer-Tropsch synthesis oil products.
The foregoing description of the embodiments has been provided for the purpose of illustrating the general principles of the invention, and is not meant to limit the invention thereto, but to limit the invention thereto, and any modifications, equivalents, improvements and equivalents thereof may be made without departing from the spirit and principles of the invention.

Claims (12)

1. A process for removing oxygenates from a fischer-tropsch synthesis oil comprising:
carrying out azeotropic distillation on Fischer-Tropsch synthetic oil in a rectifying tower, wherein the used entrainer is one or more of ethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, 1, 2-butanediol, 1, 3-butanediol, 2-3-butanediol, n-amyl alcohol, isoprene glycol and isomers thereof;
wherein, in the azeotropic distillation process, the entrainer is positioned on the feeding tower plate of the rectifying tower above the feeding tower plate of the Fischer-Tropsch synthetic oil, the Fischer-Tropsch synthetic oil and the entrainer form an azeotrope to reduce the boiling point, the entrainer is distilled from the top of the tower, and the oxygen-containing compound flows out from the bottom of the tower;
the Fischer-Tropsch synthetic oil is the Fischer-Tropsch synthetic oil with carbon number more than or equal to 10.
2. The process of claim 1, wherein the volume ratio of the fischer-tropsch synthesis oil to the entrainer is from 1:0.2 to 1:10.
3. The process according to claim 1 or 2, wherein the number of trays of the rectification column is in the range of 5-60, the feed tray of the entrainer in the rectification column being located above the feed tray of the fischer-tropsch synthesis oil; the reflux ratio of the tower top is 1:1-10:1.
4. The method of claim 1, wherein the rectifying column is operated at normal pressure and the column bottom is operated at 190-250 ℃; or the operating pressure of the rectifying tower is 0.1-15kpa absolute; the temperature of the tower kettle is 130-160 ℃.
5. The process of claim 1, wherein the process further comprises removing oxygenates after azeotropic distillation using molecular sieve adsorption.
6. The method of claim 5, wherein the molecular sieve type is one or more of 3A, 4A, 5A, 10X, 13X.
7. The method according to claim 5 or 6, wherein the temperature for adsorption removal of the oxygen-containing compound by molecular sieve is 50-80 ℃ and the pressure is 0.1-0.5Mpa.
8. The process of claim 1, further comprising caustic washing the fischer-tropsch oil with a caustic solution to remove sour species from the fischer-tropsch oil prior to azeotropic distillation, followed by water washing.
9. The method according to claim 8, wherein the alkali is selected from inorganic alkali and/or organic alkali, the mass concentration of the alkali solution is 5% -40%, the volume ratio of the Fischer-Tropsch synthetic oil to the alkali solution is 1:0.2-1:5, and the alkali washing stirring time is 30 min-4 hours.
10. The method of claim 9, wherein the inorganic base comprises KOH, naOH, na 2 CO 3 、K 2 CO 3 、Ca(OH) 2 、NaHCO 3 、KHCO 3 The organic base includes an amine compound.
11. The method according to claim 8, wherein the volume ratio of Fischer-Tropsch oil to water is 1:0.2 to 1:5 when washing with water, and the stirring time of washing with water is 30min-2h.
12. The method according to any one of claims 8 to 11, wherein the alkaline washing and/or the water washing is performed in a static mixer, and the reflux/pick-up ratio of the static mixer is 1:1 to 10:1.
CN202011226911.8A 2020-11-05 2020-11-05 Method for removing oxygen-containing compound in high-carbon Fischer-Tropsch synthesis oil Active CN114437756B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202011226911.8A CN114437756B (en) 2020-11-05 2020-11-05 Method for removing oxygen-containing compound in high-carbon Fischer-Tropsch synthesis oil

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202011226911.8A CN114437756B (en) 2020-11-05 2020-11-05 Method for removing oxygen-containing compound in high-carbon Fischer-Tropsch synthesis oil

Publications (2)

Publication Number Publication Date
CN114437756A CN114437756A (en) 2022-05-06
CN114437756B true CN114437756B (en) 2023-09-22

Family

ID=81360644

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202011226911.8A Active CN114437756B (en) 2020-11-05 2020-11-05 Method for removing oxygen-containing compound in high-carbon Fischer-Tropsch synthesis oil

Country Status (1)

Country Link
CN (1) CN114437756B (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115572614B (en) * 2022-09-23 2024-01-26 内蒙古伊泰煤基新材料研究院有限公司 Method for removing narrow-cut oxygen-containing compound in Fischer-Tropsch oil

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111647424A (en) * 2019-03-04 2020-09-11 内蒙古伊泰煤基新材料研究院有限公司 Linear olefin production method capable of being monitored on line

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111647424A (en) * 2019-03-04 2020-09-11 内蒙古伊泰煤基新材料研究院有限公司 Linear olefin production method capable of being monitored on line

Also Published As

Publication number Publication date
CN114437756A (en) 2022-05-06

Similar Documents

Publication Publication Date Title
US9950969B2 (en) Method for the production of butadiene from ethanol in one low-water- and low-energy-consumption reaction step
RU2594159C2 (en) Method of separating ethylene glycol and 1,2-butanediol
CN105622337B (en) Novel reactive distillation coupling process and device for separating liquid-phase product of ethylene glycol prepared from coal
EP2338865A1 (en) Process for removing oxygenated contaminants from an hydrocarbon stream
CN107915612B (en) Method for preparing purified MIBK from industrial byproduct waste liquid acetone
CN107098810B (en) Separation and purification method for preparing electronic-grade propylene glycol monomethyl ether acetate
US20140350319A1 (en) Process for removing oxygenated contaminants from an hydrocarbonstream
CN114437756B (en) Method for removing oxygen-containing compound in high-carbon Fischer-Tropsch synthesis oil
CN1094025A (en) From phenol tar, extract the method for phenol
CN118308145A (en) Process for preparing high-carbon internal olefins by taking Fischer-Tropsch oil as raw material
CN109970684B (en) Method for removing aldehyde impurities in epoxypropane by oxidation process
CN107915615B (en) Method for preparing purified MIBK from industrial byproduct waste liquid acetone
JP2003002852A (en) Method for producing isobutylene and methanol
CN1226262C (en) Separation method of dimethyl ether prepared with synthetic gas through one-step process
CN1288118C (en) Clean reclaiming process for byproduct chloromethane of glyphosate acid
CN112679352B (en) Refining method and system for mixed material flow containing dimethyl carbonate
CN112851601B (en) Method for purifying alkylene oxide
EA007711B1 (en) Extraction of oxygenates from a hydrocarbon stream
CN218980483U (en) Purification device of Fischer-Tropsch synthesized normal alkane olefin and high-purity hydrocarbon production system
CN100364942C (en) Liquid hydrocarbon absorbing and distilling depuration process
CN112126461A (en) Method for removing oxide in Fischer-Tropsch oil
CN110041292A (en) A kind of method that modified resin removes aldoketones impurity in propylene oxide
CN115491229B (en) Separation method of high-temperature Fischer-Tropsch synthesis light oil
CN113429261B (en) System, method and application for separating and purifying ethanol from crude ethanol product
CN216303677U (en) System for butyl octanol production tail gas treatment

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