WO2020048444A1 - 一种非石油基乙二醇的精制方法 - Google Patents

一种非石油基乙二醇的精制方法 Download PDF

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WO2020048444A1
WO2020048444A1 PCT/CN2019/104167 CN2019104167W WO2020048444A1 WO 2020048444 A1 WO2020048444 A1 WO 2020048444A1 CN 2019104167 W CN2019104167 W CN 2019104167W WO 2020048444 A1 WO2020048444 A1 WO 2020048444A1
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ethylene glycol
weight
isomers
azeotrope
stream
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English (en)
French (fr)
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袁一
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Changchun Meihe Science and Technology Development Co Ltd
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Changchun Meihe Science and Technology Development Co Ltd
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Priority to KR1020217009794A priority Critical patent/KR102815867B1/ko
Priority to PE2021000299A priority patent/PE20211216A1/es
Priority to BR112021004157-5A priority patent/BR112021004157B1/pt
Priority to AU2019336424A priority patent/AU2019336424B2/en
Priority to US17/274,033 priority patent/US20210340087A1/en
Priority to CA3112269A priority patent/CA3112269A1/en
Priority to MX2021002638A priority patent/MX2021002638A/es
Priority to NZ774636A priority patent/NZ774636B2/en
Application filed by Changchun Meihe Science and Technology Development Co Ltd filed Critical Changchun Meihe Science and Technology Development Co Ltd
Priority to JP2021512755A priority patent/JP2022503653A/ja
Priority to EP19858584.6A priority patent/EP3848346A4/en
Publication of WO2020048444A1 publication Critical patent/WO2020048444A1/zh
Priority to PH12021550478A priority patent/PH12021550478A1/en
Anticipated expiration legal-status Critical
Priority to JP2024088356A priority patent/JP2024116203A/ja
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
    • C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
    • C07C29/80—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by distillation
    • C07C29/82—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by distillation by azeotropic distillation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
    • C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
    • C07C29/86—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by liquid-liquid treatment
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
    • C07C29/94—Use of additives, e.g. for stabilisation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C31/00—Saturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
    • C07C31/18—Polyhydroxylic acyclic alcohols
    • C07C31/20—Dihydroxylic alcohols
    • C07C31/202—Ethylene glycol
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/04—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
    • C07D307/10—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D307/12—Radicals substituted by oxygen atoms

Definitions

  • the present invention relates to a method for refining ethylene glycol, and particularly to a method comprising butanediol, pentanediol, hexanediol, and optionally A method for purifying non-petroleum-based ethylene glycol, such as impurities close to the boiling point of ethylene glycol, and trace amounts of impurities such as acids, ethers, aldehydes, ketones, and / or alcohols that affect the ultraviolet transmittance of ethylene glycol.
  • non-petroleum routes such as coal-to-ethylene glycol and technologies for producing ethylene glycol using biomass as raw materials have developed rapidly.
  • the non-petroleum route to produce ethylene glycol produces by-products different from the ethylene glycol produced by the petroleum route, such as butanediol, pentanediol, hexanediol, And other alcohol impurities, as well as impurities such as acids, ethers, aldehydes, ketones, and / or alcohols that affect the ultraviolet transmittance of ethylene glycol in a trace amount that is even lower than the detection limit of gas chromatography.
  • the traditional means of purifying liquid-phase compounds is a rectification process that separates substances with different boiling points.
  • these impurities are close to the boiling point of ethylene glycol, such as butanediol, hexanediol, pentanediol,
  • Other alcohol impurities, as well as impurities that affect the ultraviolet transmittance of ethylene glycol, even acid, ether, aldehyde, ketone, and / or alcohol that are less than the detection limit of gas chromatography have similar physical properties to ethylene glycol, and have a boiling point. They are all very close.
  • the separation of ethylene glycol from these alcohol impurities by direct distillation will result in a low ethylene glycol distillation yield and high energy consumption. Impurities, the ultraviolet transmittance of ethylene glycol cannot directly meet the requirements of fiber-grade and bottle-grade polyester.
  • US4935102, US4966658, US5423955, US8906205 all describe techniques for separating ethylene glycol from butanediol using different azeotropic agents.
  • An azeotropic agent has an azeotropic point with ethylene glycol. Generally, the temperature of the azeotropic point is significantly lower than the boiling point of ethylene glycol. In this way, the boiling point of the azeotrope of ethylene glycol and azeotrope and the boiling point of impurities such as butanediol produce a significant temperature difference, and the separation of ethylene glycol and butanediol can be achieved economically by rectification.
  • Processes for the production of ethylene glycol from non-petroleum routes produce other than butanediol such as pentanediol, hexanediol, Such as alcohol impurities that are very close to the boiling point of ethylene glycol, and impurities that affect the ultraviolet transmittance of ethylene glycol are even below the detection limit of gas chromatography, such as acids, ethers, aldehydes, ketones and / or alcohols.
  • CN106946654A describes the use of an adsorbent bed equipped with a porous carbon adsorbent to adsorb impurities in biomass ethylene glycol to achieve the effect of refining ethylene glycol.
  • This technology only describes the enhancement of the ultraviolet transmittance of ethylene glycol. It does not explain the ability to separate butanediol, compounds of the following formula: Alcohol impurities such as pentanediol and hexanediol.
  • the invention provides a method for refining non-petroleum-based ethylene glycol, in which impurities close to the boiling point of ethylene glycol are separated.
  • This method can increase the purity of the ethylene glycol to 99.90% or more, preferably 99.95% or more under high-yield conditions of ethylene glycol recovery of 95% or more, preferably 97% or more, and particularly preferably 98% or more, and
  • the ultraviolet transmittance of the obtained ethylene glycol at the wavelengths of 220 nm, 275 nm, and 350 nm was increased to 75%, 92%, and 99%, respectively.
  • the non-petroleum-based ethylene glycol refers to ethylene glycol produced by a non-petroleum route, especially coal-based ethylene glycol or ethylene glycol made from biomass, which includes but is not limited to ethylene glycol and butanediol. , Pentanediol and hexanediol.
  • the non-petroleum-based ethylene glycol further includes a compound having the following molecular formula:
  • the butanediol is preferably 1,2-butanediol.
  • the pentanediol is preferably 1,2-pentanediol.
  • the hexanediol is preferably 1,2-hexanediol.
  • one or two or more of C 5 -C 20 lipophilic alcohol compounds, C 5 -C 20 alkanes and C 4 -C 20 lipophilic ketone compounds are used as azeotropic agents.
  • Azeotrope with the non-petroleum based ethylene glycol to obtain an azeotrope containing ethylene glycol then add water to dissolve the ethylene glycol in the azeotrope, dissolve the water-insoluble azeotrope and the ethylene glycol aqueous solution After separation, the obtained ethylene glycol aqueous solution was dehydrated and purified to obtain ethylene glycol.
  • the C 5 -C 20 lipophilic alcohol compound is preferably a C 6 -C 15 lipophilic alcohol compound, more preferably a C 7 -C 12 lipophilic alcohol compound, particularly C 7 -C 10 lipophilic alcohols are preferred.
  • the lipophilic alcohol compound may be a fatty alcohol and a heterocyclic-containing alcohol.
  • the lipophilic alcohol compounds are, for example, pentanol and its isomers, hexanol and its isomers, heptanol and its isomers, octanol and its isomers, nonanol and its isomers, decanol and its isomers , Undecanol and its isomers, lauryl alcohol and its isomers, and benzyl alcohol.
  • the lipophilic alcohol compounds are heptanol, isoheptanol, octanol, isooctanol, nonanol, isononanol, decanol and isodecanol.
  • the C 5 -C 20 alkane is preferably a C 5 -C 15 alkane, preferably a C 5 -C 12 alkane, and particularly preferably a C 5 -C 10 alkane.
  • the alkane may be a linear alkane, a branched alkane, a cycloalkane, or a benzene ring-containing alkane.
  • alkanes examples include pentane and its isomers, hexane and its isomers, heptane and its isomers, octane and its isomers, nonane and its isomers, decane and its Isomers, undecane and its isomers, dodecane and its isomers, cyclopentane and cyclohexane, ethylbenzene and its isomers.
  • the alkane is hexane, heptane, octane, nonane, decane, undecane, dodecane, cyclopentane, cyclohexane, ethylbenzene.
  • the C 4 -C 20 lipophilic ketone compound is preferably a C 5 -C 15 lipophilic ketone compound, and more preferably a C 6 -C 12 lipophilic ketone compound. Particularly preferred are C 6 -C 10 lipophilic ketones.
  • the ketone may be a fatty ketone or an alicyclic ketone. Very preferably, the ketone is heptone, diisobutyl ketone, cyclohexanone, 2-nonanone.
  • the biomass in the present invention preferably refers to edible first-generation biomass including corn, sugar cane, and the like, and non-grain second-generation biomass including agricultural, forestry, and waste including straw, wood, bagasse, and the like.
  • the non-petroleum-based ethylene glycol of the present invention includes, but is not limited to, ethylene glycol, butanediol (preferably 1,2-butanediol), pentanediol (preferably 1,2-pentanediol), and hexanediol Alcohol (preferably 1,2-hexanediol) and
  • the non-petroleum based ethylene glycol of the present invention optionally comprises propylene glycol, glycerol and / or sorbitol. More preferably, the non-petroleum-based ethylene glycol includes, but is not limited to:
  • ethylene glycol 1-100% by weight of ethylene glycol (except 100% by weight of the endpoint), preferably 1-99% by weight of ethylene glycol, more preferably 5-99% by weight of ethylene glycol, and particularly preferably 10-95% by weight of ethylene glycol,
  • butanediol preferably 1,2-butanediol; except for endpoint 0
  • pentanediol preferably 1,2-pentanediol; except for endpoint 0
  • hexanediol preferably 1,2-hexanediol; except for endpoint 0
  • the non-petroleum based ethylene glycol optionally further comprises:
  • glycerol 0-20% by weight, preferably 0.01-10% by weight of glycerol, and / or
  • the azeotrope is azeotroped with ethylene glycol to form an azeotrope.
  • the boiling point and impurities of the azeotrope such as butanediol, pentanediol, hexanediol, As well as other trace amounts of acids, ethers, aldehydes, ketones, and / or alcohols that affect ultraviolet transmittance, there are obvious differences in boiling points, so that ethylene glycol can be economically purified by, for example, a distillation process.
  • the azeotrope can be separated from the ethylene glycol-containing aqueous solution by an extraction process after the azeotrope is mixed with water.
  • the ethylene glycol-containing aqueous solution is purified after dehydration to obtain ethylene glycol.
  • FIG. 1 is a flowchart of the azeotropic refining process of non-petroleum-based ethylene glycol according to the present invention.
  • Figure 2 is a flowchart of a conventional distillation process for non-petroleum based glycols.
  • the mixed alcohol feed is mixed with the azeotrope feed and then enters the azeotropic tower, which is a rectification tower.
  • the weight ratio of ethylene glycol in the azeotrope feed and the mixed alcohol feed is 0.1: 1 to 20: 1, preferably 0.2: 1 to 10: 1, and more preferably 0.5: 1 to 10: 1.
  • the operating pressure of the azeotropic column is 1 kPa (absolute) to 101 kPa (absolute), and the weight ratio (ie, reflux ratio) of the reflux material and the recovered material of the azeotropic column is 0.1: 1 to 15: 1.
  • ethylene glycol and a small amount of other impurities in the mixed alcohol feed are extracted from the top of the azeotropic column (ie, stream 1) together with the azeotrope and enter the top phase separator.
  • azeotropic column ie, stream 1
  • the heavy component impurities and a small amount of azeotrope are withdrawn from the tower kettle (ie, stream 8) and enter the evaporator.
  • Stream 1 is mixed with fresh water and optional recycled water (i.e. stream 4) in the overhead phase separator and stratified.
  • the azeotrope layer ie, stream 2) is recycled to the azeotropic column; and the water layer (ie, stream 3) enters the overhead dehydration column.
  • the water in stream 3 is extracted from the top of the tower (ie, stream 4) and recycled to the overhead phase separator.
  • the side line extracts ethylene glycol containing impurities of light components (i.e., stream 5) and enters the ethylene glycol purification column.
  • the heavy component impurities (ie, stream 6) in the tower kettle are discharged from the system.
  • Stream 5 is purified in a glycol refining tower, and the glycol is recovered from the side line of the refining tower.
  • the purity and UV transmittance of the obtained glycol products meet the requirements of fiber-grade and bottle-grade polyester.
  • Other light component impurities are extracted from the top of the ethylene glycol refining tower.
  • Heavy component impurities are recovered from the ethylene glycol refining tower kettle.
  • the azeotrope tower kettle material enters the evaporator where extremely high-boiling heavy component impurities, such as glycerol and sorbitol, are separated from the bottom of the evaporator and discharged from the system (ie, stream 9).
  • Stream 10 enters the tower kettle phase separator and is mixed with fresh water and optional return water (ie, stream 13) and layered.
  • the azeotrope layer ie, stream 11
  • the aqueous layer ie, stream 12
  • aqueous layer containing, but not limited to, water, butanediol, pentanediol, and hexanediol, enters the dehydration tower dehydration tower.
  • the water in the water layer of the tower boiler phase separator (ie, stream 12) is separated in the tower kettle dehydration tower and produced from the top of the tower (ie, stream 13) and recycled to the tower phase separator.
  • impurities including but not limited to butanediol, pentanediol and hexanediol are extracted from the tower dehydration tower and discharged from the system.
  • the technology of the present invention can combine the ethylene glycol in the non-petroleum-based ethylene glycol with including but under the condition of high yield of 95% or more, preferably 97% or more, and particularly preferably 98% or more. Not limited to butanediol, pentanediol, hexanediol, and optional Separation of impurities.
  • the purity of ethylene glycol is purified to more than 99.90%, preferably more than 99.95%, and the ultraviolet transmittance of the obtained ethylene glycol at the wavelengths of 220nm, 275nm, and 350nm is increased to 75%, 92%, and 99%, respectively Solved the current non-petroleum-based glycol purification technology that cannot be achieved simultaneously with butanediol, pentanediol, hexanediol and optional Such as the separation of impurities and the problem of improving UV transmittance.
  • the mixed alcohol feed is a material obtained by dehydrating and removing light components of a mixed product produced using biomass as a raw material.
  • the composition of the material in terms of weight percentage is ethylene glycol 85.1%, 1,2-propanediol 6.6%, 1,2-butanediol 2.2%, 2,3-butanediol 0.4%, 1,4-butanediol 0.7%, 1,2-pentanediol 0.2%, 1,2 -Hexanediol 0.2%, 0.1%, glycerol 0.5%, sorbitol 0.5%, other light and heavy components 3.5%.
  • the mixed alcohol feed was mixed with fresh azeotrope isooctanol into the 45th theoretical plate of the azeotrope.
  • the weight ratio of azeotrope (including fresh azeotrope and recycled azeotrope stream 2 and stream 11) to ethylene glycol in the mixed alcohol feed was 3.39: 1.
  • the azeotrope has a total of 90 theoretical plates.
  • the azeotrope stream 2 for the top of the tower and the azeotrope stream 11 for the return to the tower enter the azeotropic tower on the 40th theoretical plate of the azeotropic tower.
  • This azeotrope has an operating pressure of 50 kPa (absolute) and a reflux ratio of 0.5: 1.
  • Azeotrope ethylene glycol, 1,2-propanediol, 1,2-butanediol, 2,3-butanediol, 1,4 -Butanediol, 1,2-pentanediol, 1,2-hexanediol, And the composition of other light components are: 74.97%, 22.18%, 2.54%, 0.11%, 0.08%, 0%, 0%, 0%, 0%, 0.12%.
  • Stream 8 separates the high boiling point heavy component stream 9 through an evaporator.
  • Stream 10 and tower dehydration tower overhead stream 13 enter the tower kettle phase separator.
  • the layered azeotrope layer i.e. stream 11
  • the water layer i.e. stream 12
  • Stream 13 is recycled to the tower kettle phase separator.
  • the azeotrope overhead stream 1 and the overhead dehydration tower overhead stream 4 enter the overhead phase separator together. After being separated by the phase separator, the water layer stream (ie, stream 3) enters the dehydration tower top to dewater. After dehydration, the side stream 5 enters the 60th theoretical plate of the glycol refining tower.
  • the ethylene glycol refining tower has a total theoretical plate of 90, a reflux ratio of 20: 1, and an operating pressure of 10 kPa (absolute). The glycol product was extracted from the 80th theoretical plate of the glycol refining tower.
  • the purity of the refined ethylene glycol in terms of weight percentage is 99.96%, and the ultraviolet transmittance is 83.2% and 220nm at 220nm 96.0% and 99.0% at a wavelength of 350 nm.
  • the total ethylene glycol distillation yield was 98.2%.
  • the mixed alcohol feed is a material obtained by dehydrating and removing light components of a mixed product produced using biomass as a raw material.
  • the composition of the material in terms of weight percentage is ethylene glycol 23.20%, 1,2-propanediol 55.09%, 1,2-butanediol 4.60%, 2,3-butanediol 1.40%, 1,4-butanediol 0.60%, 1,2-pentanediol 0.31%, 1, 2-hexanediol 0.49%, 0.15%, glycerol 2.10%, sorbitol 1.90%, other light and heavy components 10.16%.
  • the mixed alcohol feed was mixed with fresh azeotrope 2-nonanone into the 30th theoretical plate of the azeotropic column.
  • the weight ratio of azeotrope (including fresh azeotrope and recycled azeotrope stream 2 and stream 11) to ethylene glycol in the mixed alcohol feed is 7.04: 1.
  • the azeotrope has a total of 90 theoretical plates.
  • the azeotrope stream 2 for the top of the tower and the azeotrope stream 11 for the return to the bottom of the tower enter the azeotropic tower on the 25th theoretical plate of the azeotropic tower, respectively.
  • This azeotrope has an operating pressure of 30 kPa (absolute) and a reflux ratio of 2.5: 1.
  • Azeotrope ethylene glycol, 1,2-propanediol, 1,2-butanediol, 2,3-butanediol, 1,4 -Butanediol, 1,2-pentanediol, 1,2-hexanediol, And the composition of other light components are: 64.96%, 9.23%, 24.98%, 0.20%, 0.32%, 0%, 0%, 0%, 0%, 0.31%.
  • Stream 8 separates the high boiling point heavy component stream 9 through an evaporator.
  • Stream 10 and tower dehydration tower overhead stream 13 enter the tower kettle phase separator.
  • the layered azeotrope layer i.e. stream 11
  • the water layer i.e. stream 12
  • Stream 13 is recycled to the tower kettle phase separator.
  • the azeotrope overhead stream 1 and the overhead dehydration tower overhead stream 4 enter the overhead phase separator together. After being separated by the phase separator, the water layer stream (ie, stream 3) enters the dehydration tower top to dewater. After dehydration, the side stream 5 enters the 60th theoretical plate of the glycol refining tower.
  • the total theoretical plate of the ethylene glycol refining tower is 90, the reflux ratio is 20: 1, and the operating pressure is 10 kPa (absolute).
  • the glycol product was extracted from the 80th theoretical plate of the glycol refining tower.
  • the purity of the purified ethylene glycol in terms of weight percentage is 99.95%, and the ultraviolet transmittance is 76.1% and 275nm at 220nm. The value is 95.5%, and the value is 99.0% at a wavelength of 350 nm. The total ethylene glycol distillation yield was 98.8%.
  • the mixed alcohol feed is a material obtained by dehydrating and removing light components of a mixed product produced by using biomass as a raw material.
  • the mixed alcohol feed was mixed with the fresh azeotrope n-decanol into the 30th theoretical plate of the azeotrope.
  • the weight ratio of azeotrope (including fresh azeotrope and recycled azeotrope stream 2 and stream 11) to ethylene glycol in the mixed alcohol feed was 0.60: 1.
  • the azeotrope has a total of 90 theoretical plates.
  • the azeotrope stream 2 for the top of the tower and the azeotrope stream 11 for the return to the bottom of the tower enter the azeotropic tower on the 25th theoretical plate of the azeotropic tower, respectively.
  • This azeotrope has an operating pressure of 20 kPa (absolute) and a reflux ratio of 3: 1.
  • Azeotrope ethylene glycol, 1,2-propanediol, 1,2-butanediol, 2,3-butanediol, 1,4 -Butanediol, 1,2-pentanediol, 1,2-hexanediol, And the composition of other light components are: 35.81%, 60.45%, 3.15%, 0.44%, 0.02%, 0%, 0%, 0%, 0%, 0.13%.
  • Stream 8 separates the high boiling point heavy component stream 9 through an evaporator.
  • Stream 10 and tower dehydration tower overhead stream 13 enter the tower kettle phase separator.
  • the layered azeotrope layer i.e. stream 11
  • the water layer i.e. stream 12
  • Stream 13 is recycled to the tower kettle phase separator.
  • the azeotrope overhead stream 1 and the overhead dehydration tower overhead stream 4 enter the overhead phase separator together. After being separated by the phase separator, the water layer stream (ie, stream 3) enters the dehydration tower top to dewater. After dehydration, the side stream 5 enters the 60th theoretical plate of the glycol refining tower.
  • the total theoretical plate of the ethylene glycol refining tower is 90, the reflux ratio is 40: 1, and the operating pressure is 20kPa (absolute).
  • the glycol product was extracted from the 80th theoretical plate of the glycol refining tower.
  • the purity of the refined ethylene glycol in terms of weight percentage is 99.96%, and the ultraviolet transmittance is 76.0% and 275nm at 220nm 95.4% and 99.0% at 350 nm.
  • the total ethylene glycol distillation yield was 96.5%.
  • the mixed alcohol feed is the same as the mixed alcohol feed in Example 3.
  • the mixed alcohol feed was mixed with fresh azeotrope 2-heptanol into the 30th theoretical plate of the azeotropic column.
  • the weight ratio of azeotrope (including fresh azeotrope and recycled azeotrope stream 2 and stream 11) to ethylene glycol in the mixed alcohol feed was 8.35: 1.
  • the azeotrope has a total of 90 theoretical plates.
  • the azeotrope stream 2 for the top of the tower and the azeotrope stream 11 for the return to the bottom of the tower enter the azeotropic tower on the 25th theoretical plate of the azeotropic tower, respectively.
  • This azeotrope has an operating pressure of 50 kPa (absolute) and a reflux ratio of 3: 1.
  • Azeotrope ethylene glycol, 1,2-propanediol, 1,2-butanediol, 2,3-butanediol, 1,4 -Butanediol, 1,2-pentanediol, 1,2-hexanediol, And the composition of other light components are: 88.15%, 11.21%, 0.55%, 0%, 0%, 0%, 0%, 0%, 0%, 0%, 0.09%.
  • Stream 8 separates the high boiling point heavy component stream 9 through an evaporator.
  • Stream 10 and tower dehydration tower overhead stream 13 enter the tower kettle phase separator.
  • the layered azeotrope layer i.e. stream 11
  • the water layer i.e. stream 12
  • Stream 13 is recycled to the tower kettle phase separator.
  • the azeotrope overhead stream 1 and the overhead dehydration tower overhead stream 4 enter the overhead phase separator together. After being separated by the phase separator, the water layer stream (ie, stream 3) enters the dehydration tower top to dewater. After dehydration, the side stream 5 enters the 60th theoretical plate of the glycol refining tower.
  • the total theoretical plate of the ethylene glycol refining tower is 90, the reflux ratio is 20: 1, and the operating pressure is 20kPa (absolute).
  • the glycol product was extracted from the 80th theoretical plate of the glycol refining tower.
  • the purity of the purified ethylene glycol in terms of weight percentage is 99.96%, and the ultraviolet transmittance is 76.6% and 275nm at 220nm.
  • the wavelength is 92.1%, and the wavelength is 350.95%.
  • the total ethylene glycol distillation yield was 97.0%.
  • the mixed alcohol feed is the same as the mixed alcohol feed in Example 3.
  • the mixed alcohol feed was mixed with fresh azeotrope n-octane into the 30th theoretical plate of the azeotrope.
  • the weight ratio of azeotrope (including fresh azeotrope and recycled azeotrope stream 2 and stream 11) to ethylene glycol in the mixed alcohol feed was 9.1: 1.
  • the azeotrope has a total of 63 theoretical plates.
  • the azeotrope stream 2 for the top of the tower and the azeotrope stream 11 for the return to the bottom of the tower enter the azeotropic tower on the 25th theoretical plate of the azeotropic tower, respectively.
  • This azeotrope has an operating pressure of 101 kPa (absolute) and a reflux ratio of 5: 1.
  • Azeotrope ethylene glycol, 1,2-propanediol, 1,2-butanediol, 2,3-butanediol, 1,4 -Butanediol, 1,2-pentanediol, 1,2-hexanediol, And the composition of other light components are: 89.55%, 9.86%, 0.51%, 0.01%, 0.01%, 0%, 0%, 0%, 0%, 0.06%.
  • Stream 8 separates the high boiling point heavy component stream 9 through an evaporator.
  • Stream 10 and tower dehydration tower overhead stream 13 enter the tower kettle phase separator.
  • the layered azeotrope layer i.e. stream 11
  • the water layer i.e. stream 12
  • Stream 13 is recycled to the tower kettle phase separator.
  • the azeotrope overhead stream 1 and the overhead dehydration tower overhead stream 4 enter the overhead phase separator together. After being separated by the phase separator, the water layer stream (ie, stream 3) enters the dehydration tower top to dewater. After dehydration, the side stream 5 enters the 60th theoretical plate of the glycol refining tower.
  • the total theoretical plate of the ethylene glycol refining tower is 90, the reflux ratio is 40: 1, and the operating pressure is 20kPa (absolute).
  • the glycol product was extracted from the 80th theoretical plate of the glycol refining tower.
  • the purity of the refined ethylene glycol in terms of weight percentage is 99.96%, and the ultraviolet transmittance is 75.3% and 275nm at 220nm. 93.0% and 99.2% at a wavelength of 350 nm.
  • the total glycol distillation yield was 97.1%.
  • the mixed alcohol feed is a mixed product produced by using coal as a raw material, and the composition of the material in terms of weight percentage is ethylene glycol 77.94%, 1,2-propanediol 0.86%, 1,2- Butylene glycol 17.15%, 2,3-butanediol 0.60%, 1,4-butanediol 0.01%, 1,2-pentanediol 0.02%, 1,2-hexanediol 0.01%, others light, reconstituted Points 3.41%.
  • the mixed alcohol feed was mixed with fresh azeotrope isooctanol into the 30th theoretical plate of the azeotropic column.
  • the weight ratio of azeotrope (including fresh azeotrope and recycled azeotrope stream 2 and stream 11) to ethylene glycol in the mixed alcohol feed was 3.26: 1.
  • the azeotrope has a total of 90 theoretical plates.
  • the azeotrope stream 2 for the top of the tower and the azeotrope stream 11 for the return to the bottom of the tower enter the azeotropic tower on the 25th theoretical plate of the azeotropic tower, respectively.
  • This azeotrope has an operating pressure of 77 kPa (absolute) and a reflux ratio of 2: 1.
  • Azeotrope ethylene glycol, 1,2-propanediol, 1,2-butanediol, 2,3-butanediol, 1,4 -
  • the composition of butanediol, 1,2-pentanediol, 1,2-hexanediol and other light components are: 76.07%, 23.35%, 0.15%, 0.03%, 0.23%, 0%, 0%, 0%, 0.17%.
  • Stream 8 separates the high boiling point heavy component stream 9 through an evaporator.
  • Stream 10 and tower dehydration tower overhead stream 13 enter the tower kettle phase separator.
  • the layered azeotrope layer i.e. stream 11
  • the water layer i.e. stream 12
  • Stream 13 is recycled to the tower kettle phase separator.
  • the azeotrope overhead stream 1 and the overhead dehydration tower overhead stream 4 enter the overhead phase separator together. After being separated by the phase separator, the water layer stream (ie, stream 3) enters the dehydration tower top to dewater. After dehydration, the side stream 5 enters the 60th theoretical plate of the glycol refining tower.
  • the total theoretical plate of the ethylene glycol refining tower is 90, the reflux ratio is 20: 1, and the operating pressure is 20kPa (absolute).
  • the glycol product was extracted from the 80th theoretical plate of the glycol refining tower.
  • the purity of the purified ethylene glycol in terms of weight percentage is 99.98%, and the ultraviolet transmittance is 77.1% and 275nm at 220nm 95.0% and 99.2% at a wavelength of 350 nm.
  • the total ethylene glycol distillation yield was 98.5%.
  • Example 1 The material obtained by using the biomass as the raw material in Example 1 as the raw material of the mixed product produced after dehydration and dehydration as the mixed alcohol raw material was separated by the conventional distillation method shown in FIG. 2. Since the traditional distillation process does not add an azeotrope and does not require an extraction stage, there is no need for a column top phase separator, a tower kettle phase separator, a tower dehydration tower, a tower kettle dehydration tower and an evaporator. Compared with Example 1: The total theoretical plate and operating conditions of the ethylene glycol deweighting tower and azeotropic column are the same; the total theoretical plate and operating conditions of the ethylene glycol delighting tower in this comparative example are the same as those of Example 1 The refinement tower is the same.
  • Ethylene glycol in ethylene glycol products by weight percentage 1,2-propanediol, 1,2-butanediol, 2,3-butanediol, 1,4-butanediol, 1,2-pentanediol Alcohol, 1,2-hexanediol, and
  • the composition is: 99.45%, 0%, 0.25%, 0%, 0%, 0.02%, 0.21%, 0.07%.
  • the ultraviolet transmittance was 56.1% at a wavelength of 220 nm, 87.2% at a wavelength of 275 nm, and 96.8% at a wavelength of 350 nm.
  • the total low-purity glycol distillation yield was 93.0%.

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Abstract

本发明提供了一种精制非石油基乙二醇的方法，其中分离了与乙二醇沸点接近的杂质。在该方法中，将C 5-C 20亲油醇类化合物，C 5-C 20烷烃和/或C 4-C 20亲油酮类化合物作为共沸剂与非石油基乙二醇进行共沸得到包含乙二醇的共沸物，然后将该共沸物中的共沸剂分离除去获得乙二醇粗品，该乙二醇粗品进一步纯化后获得乙二醇。

Description

一种非石油基乙二醇的精制方法 技术领域
本发明涉及一种乙二醇的精制方法，特别是涉及包含丁二醇、戊二醇、己二醇和任选的
Figure PCTCN2019104167-appb-000001
等与乙二醇沸点接近的杂质以及影响乙二醇紫外透过率的微量酸、醚、醛、酮和/或醇等杂质的非石油基乙二醇的精制方法。
背景技术
近年来，由于油价的不确定性和人们对可持续性发展的重视，非石油路线如煤制乙二醇以及以生物质为原料生产乙二醇的技术发展迅速。然而由于合成路线的不同导致非石油路线生产乙二醇过程产生了不同于石油路线生产的乙二醇的副产物，诸如丁二醇、戊二醇、己二醇、
Figure PCTCN2019104167-appb-000002
等醇类杂质，以及影响乙二醇紫外透过率的微量甚至低于气相色谱检测限的酸、醚、醛、酮和/或醇等的杂质。传统的液相化合物的提纯手段为利用物质沸点不同进行分离的精馏工艺。然而，由于这些杂质与乙二醇沸点接近，例如丁二醇、己二醇、戊二醇、
Figure PCTCN2019104167-appb-000003
等醇类杂质，以及影响乙二醇紫外透过率的微量甚至低于气相色谱检测限的酸、醚、醛、酮和/或醇等的杂质，与乙二醇的物理性质比较相似，沸点均非常接近，采用直接精馏的方法将乙二醇与这些醇类杂质的分离会导致乙二醇蒸馏收率低，能耗高，而且通过精馏得到的乙二醇由于还含有部分微量的杂质，乙二醇的紫外透过率无法 直接达到纤维级和瓶级聚酯的要求。
US4935102，US4966658，US5423955，US8906205均描述了使用不同的共沸剂分离乙二醇与丁二醇的技术。共沸剂与乙二醇有共沸点。一般共沸点的温度均要明显低于乙二醇的沸点。这样乙二醇和共沸剂的共沸物的沸点与丁二醇等杂质的沸点产生了明显的温度差，通过精馏的方式可以经济地达到乙二醇与丁二醇的分离。
由非石油路线生产乙二醇的工艺会产生除丁二醇外的其他诸如戊二醇、己二醇、
Figure PCTCN2019104167-appb-000004
等与乙二醇沸点非常接近的醇类杂质以及影响乙二醇紫外透过率的微量甚至低于气相色谱检测限的酸、醚、醛、酮和/或醇等杂质。而这上述几篇文献中仅描述了使用共沸剂达到乙二醇和丁二醇的分离效果，并没有提及使用共沸剂后，乙二醇和戊二醇、己二醇、
Figure PCTCN2019104167-appb-000005
等的分离效果，也没有提及乙二醇与影响乙二醇紫外透过率的微量甚至低于气相色谱检测限的酸、醚、醛、酮和/或醇杂质的分离效果，因而这些专利没有提及可以提升乙二醇的紫外透过率。
CN106946654A描述了一种使用装有多孔碳吸附剂的吸附床吸附生物质乙二醇中的杂质以达到精制乙二醇的效果。此技术仅描述了提升乙二醇的紫外透过率，未说明能够分离丁二醇，如下分子式的化合物：
Figure PCTCN2019104167-appb-000006
戊二醇、己二醇等醇类杂质。
发明内容
本发明提供了一种精制非石油基乙二醇的方法，其中分离了与乙二醇沸点接近的杂质。该方法可以在乙二醇回收率在95％以上，优选97％以上，特别优选98％以上的高收率条件下将所述乙二醇的纯度提高 至99.90％以上，优选99.95％以上，并且所得乙二醇在220nm、275nm、350nm波长下的紫外透过率分别提升至75％、92％、99％以上。
所述的非石油基乙二醇是指非石油路线生产的乙二醇，特别是煤制乙二醇或由生物质制得的乙二醇，其包含但不限于乙二醇，丁二醇，戊二醇和己二醇。优选地，该非石油基乙二醇还包含具有以下分子式的化合物：
Figure PCTCN2019104167-appb-000007
所述的丁二醇优选是1，2-丁二醇。所述的戊二醇优选是1，2-戊二醇。所述的己二醇优选是1，2-己二醇。
在本发明的方法中，将C 5-C 20亲油醇类化合物，C 5-C 20烷烃和C 4-C 20亲油酮类化合物中的一种，二种或多种作为共沸剂与所述非石油基乙二醇进行共沸得到包含乙二醇的共沸物，然后加入水将该共沸物中的乙二醇溶解，将不溶于水的共沸剂和乙二醇水溶液分离，所得乙二醇水溶液脱水精制后获得乙二醇。
在本发明的一种实施方案中，所述C 5-C 20亲油醇类化合物优选是C 6-C 15亲油醇类化合物，更优选是C 7-C 12亲油醇类化合物，特别优选是C 7-C 10亲油醇类化合物。该亲油醇类化合物可以是脂肪醇和含有杂环的醇。该亲油醇类化合物的例子例如是戊醇和其异构体，己醇和其异构体，庚醇和其异构体，辛醇和其异构体，壬醇和其异构体，癸醇和其异构体，十一醇和其异构体，月桂醇和其异构体以及苄醇。非常优选地，所述亲油醇类化合物是庚醇、异庚醇、辛醇、异辛醇、壬醇、异壬醇、癸醇和异癸醇。
在本发明的另一种实施方案中，所述的C 5-C 20烷烃优选是C 5-C 15烷烃，优选是C 5-C 12烷烃，特别优选是C 5-C 10烷烃。该烷烃可以是直链烷烃，支链烷烃、环烷烃或含苯环的烷烃。该烷烃的例子例如是戊烷和其异构体，己烷和其异构体，庚烷和其异构体，辛烷和其异构体，壬烷和其异构体，癸烷和其异构体，十一烷和其异构体，十二烷和其异构体，环戊烷和环己烷，乙苯和其异构体。非常优选地，所述烷烃是己烷、庚烷、辛烷、壬烷、癸烷、十一烷、十二烷、环戊烷、环己烷、乙苯。
在本发明的另一种实施方案中，所述的C 4-C 20亲油酮类化合物优 选是C 5-C 15亲油酮类化合物，更优选是C 6-C 12亲油酮类化合物，特别优选是C 6-C 10亲油酮类化合物。该酮可以是脂肪酮或者脂环酮。非常优选地，所述酮是庚酮，二异丁基酮，环己酮，2-壬酮。
本发明中所述的生物质优选是指包括玉米、甘蔗等可以食用的第-代生物质以及包括秸秆、木材、蔗渣等在内的农林业废弃物的非粮食的第二代生物质。优选地，本发明的非石油基乙二醇包含但不限于乙二醇、丁二醇(优选1，2-丁二醇)、戊二醇(优选1，2-戊二醇)、己二醇(优选1，2-己二醇)和
Figure PCTCN2019104167-appb-000008
本发明的非石油基乙二醇任选地包含丙二醇，丙三醇和/或山梨醇。更优选地，所述的非石油基乙二醇包含但不限于：
1-100重量％乙二醇(端点100重量％除外)，优选1-99重量％乙二醇，更有选5-99重量％乙二醇，特别优选10-95重量％乙二醇，
0-95重量％，优选0-50重量％，更优选0-30重量％，特别优选0-10重量％的丁二醇(优选1，2-丁二醇；端点0除外)，
0-95重量％，优选0-50重量％，更优选0-10重量％，特别优选0-1重量％的戊二醇(优选1，2-戊二醇；端点0除外)，
0-95重量％，优选0-50重量％，更优选0-10重量％，特别优选0-1重量％的己二醇(优选1，2-己二醇；端点0除外)，和
任选的0-95重量％，优选0-50重量％，更优选0-10重量％，特别优选0-1重量％的
Figure PCTCN2019104167-appb-000009
所述的非石油基乙二醇还任选地包含：
0-95重量％，优选0.1-50重量％的1，2-丙二醇，
0-50重量％，优选0.01-10重量％的2，3-丁二醇，
0-20重量％，优选0.01-10重量％的丙三醇，和/或
0-20重量％，优选0.01-10重量％的山梨醇。
在本发明的方法中，所述共沸剂与乙二醇共沸，形成共沸物。该 共沸物的沸点与杂质例如丁二醇、戊二醇、己二醇、
Figure PCTCN2019104167-appb-000010
以及其它影响紫外透过率的微量的酸、醚、醛、酮和/或醇等有明显的沸点差，从而可以通过例如精馏工艺经济地提纯乙二醇。
可以通过共沸物与水混合后的萃取工艺将共沸剂与含乙二醇的水溶液分离。所述的含乙二醇的水溶液在脱水后进行精制获得乙二醇。
附图说明
附图1是本发明的非石油基乙二醇共沸精制过程的流程图。
附图2是非石油基乙二醇传统精馏过程的流程图。
具体实施方式
结合附图1，本发明的精制过程描述如下：
混合醇进料与共沸剂进料混合后进入共沸塔，这里的共沸塔是精馏塔。共沸剂进料和混合醇进料中的乙二醇的重量比为0.1∶1～20∶1，优选0.2∶1～10∶1，更优选0.5∶1～10∶1。该共沸塔的操作压力为1kPa(绝对)-101kPa(绝对)，并且该共沸塔的回流物料和采出物料的重量比(即，回流比)为0.1∶1～15∶1。其中，所述混合醇进料中的绝大部分乙二醇以及少量其他杂质与共沸剂一同从共沸塔塔顶采出(即，物流1)并进入塔顶分相器。包括但不限于丁二醇、戊二醇、己二醇和任选的
Figure PCTCN2019104167-appb-000011
的重组分杂质与少量共沸剂从塔釜采出(即，物流8)并进入蒸发器。
物流1与新鲜水和任选的回用水(即，物流4)在塔顶分相器中混合并分层。共沸剂层(即，物流2)回用至共沸塔；而水层(即，物流3)进入塔顶脱水塔。
在塔顶脱水塔中，将物流3中的水从塔顶采出(即，物流4)并回用至塔顶分相器。侧线采出含有轻组分杂质的乙二醇(即，物流5)并 进入乙二醇精制塔。塔釜中的重组分杂质(即，物流6)排出系统。
物流5在乙二醇精制塔中精制提纯乙二醇，该乙二醇从精制塔侧线采出。所获得的乙二醇产品的纯度和紫外透过率均达到纤维级和瓶级聚酯的要求。其他轻组分杂质从乙二醇精制塔塔顶采出。重组分杂质从乙二醇精制塔塔釜采出。
共沸塔塔釜物料(即，物流8)进入蒸发器，其中将沸点极高的重组分杂质，例如丙三醇和山梨醇，从蒸发器底部分离并排出系统(即，物流9)。
包含但不限于共沸剂、丁二醇、戊二醇、己二醇和任选的
Figure PCTCN2019104167-appb-000012
的物流10进入塔釜分相器，并且与新鲜水和任选的回用水(即，物流13)混合分层。其中的共沸剂层(即，物流11)回用至共沸塔。而包含但不限于水、丁二醇、戊二醇和己二醇的水层(即，物流12)进入塔釜脱水塔脱水。
塔釜分相器的水层(即，物流12)中的水在塔釜脱水塔中分离并从塔顶采出(即，物流13)并回用至塔釜分相器。而包含但不限于丁二醇、戊二醇和己二醇的杂质从塔釜脱水塔塔釜采出并排出系统。
本发明的技术可以在乙二醇回收率在95％以上，优选97％以上，特别优选98％以上的高收率条件下将所述的非石油基乙二醇中的乙二醇与包括但不限于丁二醇、戊二醇、己二醇和任选的
Figure PCTCN2019104167-appb-000013
的杂质分离。同时将乙二醇的纯度提纯至99.90％以上，优选99.95％以上，并且所得乙二醇在220nm、275nm、350nm波长下的紫外透过率分别提升至75％、92％、99％以上，从而解决了目前的非石油基乙二醇提纯技术中无法同时实现与丁二醇，戊二醇，己二醇和任选的
Figure PCTCN2019104167-appb-000014
等杂质的分离和提升紫外透过率的问题。
实施例
本发明通过下面的实施例进行进一步说明，但本发明并不限于下面的实施例。
实施例1
采用附图1中所示的流程，混合醇进料为以生物质为原料生产的混合产物在脱水脱轻组分后得到的物料，该物料以重量百分比计的组成为乙二醇85.1％、1，2-丙二醇6.6％、1，2-丁二醇2.2％、2，3-丁二醇0.4％、1，4-丁二醇0.7％、1，2戊二醇0.2％、1，2-己二醇0.2％、
Figure PCTCN2019104167-appb-000015
0.1％、丙三醇0.5％、山梨醇0.5％、其他轻、重组分3.5％。
混合醇进料与新鲜共沸剂异辛醇混合进入共沸塔的第45块理论板。共沸剂(包括新鲜共沸剂和回用共沸剂物流2和物流11)与混合醇进料中乙二醇的重量比例为3.39∶1。共沸塔共有90块理论板。塔顶回用共沸剂物流2和塔釜回用共沸剂物流11分别在共沸塔的第40块理论板进入共沸塔。该共沸塔操作压力为50kPa(绝对)，回流比为0.5∶1。经共沸塔分离后的塔顶物流1中以重量百分比计的共沸剂、乙二醇、1，2-丙二醇、1，2-丁二醇、2，3-丁二醇、1，4-丁二醇、1，2-戊二醇、1，2-己二醇、
Figure PCTCN2019104167-appb-000016
和其他轻组分的组成分别为：74.97％、22.18％、2.54％、0.11％、0.08％、0％、0％、0％、0％、0.12％。
物流8通过蒸发器将高沸点重组分物流9分离。
物流10与塔釜脱水塔塔顶物流13进入塔釜分相器。分层后的共沸剂层(即物流11)为回收共沸剂，回用至共沸塔；水层(即物流12)为醇和水的混合物，进入塔釜脱水塔脱水并将水(即物流13)回用至塔釜分相器。
共沸塔塔顶物流1与塔顶脱水塔塔顶物流4共同进入塔顶分相器。经过分相器分离后，水层物流(即物流3)进入塔顶脱水塔脱水。经过脱水后，侧线物流5进入乙二醇精制塔的第60块理论板。乙二醇精制 塔的总理论板为90块，回流比为20∶1，操作压力为10kPa(绝对)。乙二醇产品从乙二醇精制塔第80块理论板采出。分别使用国标GB/T4649-2008中的方法与美国ASTM E2409和ASTM E2139分析，精制后的乙二醇以重量百分比计的纯度为99.96％，紫外透过率在220nm波长下为83.2％、275nm波长下为96.0％、350nm波长下为99.0％。总的乙二醇精馏收率为98.2％。
实施例2
采用附图1中所示的流程，混合醇进料为以生物质为原料生产的混合产物在脱水脱轻组分后得到的物料，该物料以重量百分比计的组成为乙二醇23.20％、1，2-丙二醇55.09％、1，2-丁二醇4.60％、2，3-丁二醇1.40％、1，4-丁二醇0.60％、1，2-戊二醇0.31％、1，2-己二醇0.49％、
Figure PCTCN2019104167-appb-000017
0.15％、丙三醇2.10％、山梨醇1.90％、其他轻、重组分10.16％。
混合醇进料与新鲜共沸剂2-壬酮混合进入共沸塔的第30块理论板。共沸剂(包括新鲜共沸剂和回用共沸剂物流2和物流11)与混合醇进料中乙二醇的重量比例为7.04∶1。共沸塔共有90块理论板。塔顶回用共沸剂物流2和塔釜回用共沸剂物流11分别在共沸塔的第25块理论板进入共沸塔。该共沸塔操作压力为30kPa(绝对)，回流比为2.5∶1。经共沸塔分离后的塔顶物流1中以重量百分比计的共沸剂、乙二醇、1，2-丙二醇、1，2-丁二醇、2，3-丁二醇、1，4-丁二醇、1，2-戊二醇、1，2-己二醇、
Figure PCTCN2019104167-appb-000018
和其他轻组分的组成分别为：64.96％、9.23％、24.98％、0.20％、0.32％、0％、0％、0％、0％、0.31％。
物流8通过蒸发器将高沸点重组分物流9分离。
物流10与塔釜脱水塔塔顶物流13进入塔釜分相器。分层后的共沸剂层(即物流11)为回收共沸剂，回用至共沸塔；水层(即物流12)为醇和水的混合物，进入塔釜脱水塔脱水并将水(即物流13)回用至塔釜分相器。
共沸塔塔顶物流1与塔顶脱水塔塔顶物流4共同进入塔顶分相器。经过分相器分离后，水层物流(即物流3)进入塔顶脱水塔脱水。经过脱水后，侧线物流5进入乙二醇精制塔的第60块理论板。乙二醇精制塔的总理论板为90块，回流比为20∶1，操作压力为10kPa(绝对)。乙二醇产品从乙二醇精制塔第80块理论板采出。分别使用国标GB/T4649-2008中的方法与美国ASTM E2409和ASTM E2139分析，精制后的乙二醇以重量百分比计的纯度为99.95％，紫外透过率在220nm波长下为76.1％、275nm波长下为95.5％、350nm波长下为99.0％。总的乙二醇精馏收率为98.8％。
实施例3
采用附图1中所示的流程，混合醇进料为以生物质为原料生产的混合产物在脱水脱轻组分后得到的物料，该物料以重量百分比计的组成为乙二醇92.50％、1，2-丙二醇4.89％、1，2-丁二醇1.42％、2，3-丁二醇0.17％、1，4-丁二醇0.12％、1，2-戊二醇0.06％、1，2-己二醇0.24％、
Figure PCTCN2019104167-appb-000019
0.07％、其他轻、重组分0.53％。
混合醇进料与新鲜共沸剂正癸醇混合进入共沸塔的第30块理论板。共沸剂(包括新鲜共沸剂和回用共沸剂物流2和物流11)与混合醇进料中乙二醇的重量比例为0.60∶1。共沸塔共有90块理论板。塔顶回用共沸剂物流2和塔釜回用共沸剂物流11分别在共沸塔的第25块理论板进入共沸塔。该共沸塔操作压力为20kPa(绝对)，回流比为3∶1。经共沸塔分离后的塔顶物流1中以重量百分比计的共沸剂、乙二醇、1，2-丙二醇、1，2-丁二醇、2，3-丁二醇、1，4-丁二醇、1，2-戊二醇、1，2-己二醇、
Figure PCTCN2019104167-appb-000020
和其他轻组分的组成分别为：35.81％、60.45％、3.15％、0.44％、0.02％、0％、0％、0％、0％、0.13％。
物流8通过蒸发器将高沸点重组分物流9分离。
物流10与塔釜脱水塔塔顶物流13进入塔釜分相器。分层后的共 沸剂层(即物流11)为回收共沸剂，回用至共沸塔；水层(即物流12)为醇和水的混合物，进入塔釜脱水塔脱水并将水(即物流13)回用至塔釜分相器。
共沸塔塔顶物流1与塔顶脱水塔塔顶物流4共同进入塔顶分相器。经过分相器分离后，水层物流(即物流3)进入塔顶脱水塔脱水。经过脱水后，侧线物流5进入乙二醇精制塔的第60块理论板。乙二醇精制塔的总理论板为90块，回流比为40∶1，操作压力为20kPa(绝对)。乙二醇产品从乙二醇精制塔第80块理论板采出。分别使用国标GB/T4649-2008中的方法与美国ASTM E2409和ASTM E2139分析，精制后的乙二醇以重量百分比计的纯度为99.96％，紫外透过率在220nm波长下为76.0％、275nm波长下为95.4％、350nm波长下为99.0％。总的乙二醇精馏收率为96.5％。
实施例4
采用附图1中所示的流程，混合醇进料与实施例3中的混合醇进料相同。
混合醇进料与新鲜共沸剂2-庚醇混合进入共沸塔的第30块理论板。共沸剂(包括新鲜共沸剂和回用共沸剂物流2和物流11)与混合醇进料中乙二醇的重量比例为8.35∶1。共沸塔共有90块理论板。塔顶回用共沸剂物流2和塔釜回用共沸剂物流11分别在共沸塔的第25块理论板进入共沸塔。该共沸塔操作压力为50kPa(绝对)，回流比为3∶1。经共沸塔分离后的塔顶物流1中以重量百分比计的共沸剂、乙二醇、1，2-丙二醇、1，2-丁二醇、2，3-丁二醇、1，4-丁二醇、1，2-戊二醇、1，2-己二醇、
Figure PCTCN2019104167-appb-000021
和其他轻组分的组成分别为：88.15％、11.21％、0.55％、0％、0％、0％、0％、0％、0％、0.09％。
物流8通过蒸发器将高沸点重组分物流9分离。
物流10与塔釜脱水塔塔顶物流13进入塔釜分相器。分层后的共沸剂层(即物流11)为回收共沸剂，回用至共沸塔；水层(即物流12)为醇和水的混合物，进入塔釜脱水塔脱水并将水(即物流13)回用至 塔釜分相器。
共沸塔塔顶物流1与塔顶脱水塔塔顶物流4共同进入塔顶分相器。经过分相器分离后，水层物流(即物流3)进入塔顶脱水塔脱水。经过脱水后，侧线物流5进入乙二醇精制塔的第60块理论板。乙二醇精制塔的总理论板为90块，回流比为20∶1，操作压力为20kPa(绝对)。乙二醇产品从乙二醇精制塔第80块理论板采出。分别使用国标GB/T4649-2008中的方法与美国ASTM E2409和ASTM E2139分析，精制后的乙二醇以重量百分比计的纯度为99.96％，紫外透过率在220nm波长下为76.6％、275nm波长下为92.1％、350nm波长下为99.5％。总的乙二醇精馏收率为97.0％。
实施例5
采用附图1中所示的流程，混合醇进料与实施例3中的混合醇进料相同。
混合醇进料与新鲜共沸剂正辛烷混合进入共沸塔的第30块理论板。共沸剂(包括新鲜共沸剂和回用共沸剂物流2和物流11)与混合醇进料中乙二醇的重量比例为9.1∶1。共沸塔共有63块理论板。塔顶回用共沸剂物流2和塔釜回用共沸剂物流11分别在共沸塔的第25块理论板进入共沸塔。该共沸塔操作压力为101kPa(绝对)，回流比为5∶1。经共沸塔分离后的塔顶物流1中以重量百分比计的共沸剂、乙二醇、1，2-丙二醇、1，2-丁二醇、2，3-丁二醇、1，4-丁二醇、1，2-戊二醇、1，2-己二醇、
Figure PCTCN2019104167-appb-000022
和其他轻组分的组成分别为：89.55％、9.86％、0.51％、0.01％、0.01％、0％、0％、0％、0％、0.06％。
物流8通过蒸发器将高沸点重组分物流9分离。
物流10与塔釜脱水塔塔顶物流13进入塔釜分相器。分层后的共沸剂层(即物流11)为回收共沸剂，回用至共沸塔；水层(即物流12)为醇和水的混合物，进入塔釜脱水塔脱水并将水(即物流13)回用至塔釜分相器。
共沸塔塔顶物流1与塔顶脱水塔塔顶物流4共同进入塔顶分相器。 经过分相器分离后，水层物流(即物流3)进入塔顶脱水塔脱水。经过脱水后，侧线物流5进入乙二醇精制塔的第60块理论板。乙二醇精制塔的总理论板为90块，回流比为40∶1，操作压力为20kPa(绝对)。乙二醇产品从乙二醇精制塔第80块理论板采出。分别使用国标GB/T4649-2008中的方法与美国ASTM E2409和ASTM E2139分析，精制后的乙二醇以重量百分比计的纯度为99.96％，紫外透过率在220nm波长下为75.3％、275nm波长下为93.0％、350nm波长下为99.2％。总的乙二醇精馏收率为97.1％。
实施例6
采用附图1中所示的流程，混合醇进料为煤为原料生产的混合产物，该物料以重量百分比计的组成为乙二醇77.94％、1，2-丙二醇0.86％、1，2-丁二醇17.15％、2，3-丁二醇0.60％、1，4-丁二醇0.01％、1，2-戊二醇0.02％、1，2-己二醇0.01％、其他轻、重组分3.41％。
混合醇进料与新鲜共沸剂异辛醇混合进入共沸塔的第30块理论板。共沸剂(包括新鲜共沸剂和回用共沸剂物流2和物流11)与混合醇进料中乙二醇的重量比例为3.26∶1。共沸塔共有90块理论板。塔顶回用共沸剂物流2和塔釜回用共沸剂物流11分别在共沸塔的第25块理论板进入共沸塔。该共沸塔操作压力为77kPa(绝对)，回流比为2∶1。经共沸塔分离后的塔顶物流1中以重量百分比计的共沸剂、乙二醇、1，2-丙二醇、1，2-丁二醇、2，3-丁二醇、1，4-丁二醇、1，2-戊二醇、1，2-己二醇和其他轻组分的组成分别为：76.07％、23.35％、0.15％、0.03％、0.23％、0％、0％、0％、0.17％。
物流8通过蒸发器将高沸点重组分物流9分离。
物流10与塔釜脱水塔塔顶物流13进入塔釜分相器。分层后的共沸剂层(即物流11)为回收共沸剂，回用至共沸塔；水层(即物流12)为醇和水的混合物，进入塔釜脱水塔脱水并将水(即物流13)回用至塔釜分相器。
共沸塔塔顶物流1与塔顶脱水塔塔顶物流4共同进入塔顶分相器。经过分相器分离后，水层物流(即物流3)进入塔顶脱水塔脱水。经过脱水后，侧线物流5进入乙二醇精制塔的第60块理论板。乙二醇精制塔的总理论板为90块，回流比为20∶1，操作压力为20kPa(绝对)。乙二醇产品从乙二醇精制塔第80块理论板采出。分别使用国标 GB/T4649-2008中的方法与美国ASTM E2409和ASTM E2139分析，精制后的乙二醇以重量百分比计的纯度为99.98％，紫外透过率在220nm波长下为77.1％、275nm波长下为95.0％、350nm波长下为99.2％。总的乙二醇精馏收率为98.5％。
比较例1
以实施例1中的生物质为原料生产的混合产物在脱水脱轻组分后得到的物料作为混合醇原料，采用图2所示的传统精馏方法进行分离。由于传统精馏工艺不加共沸剂，不需要萃取工段，因此不需要塔顶分相器、塔釜分相器、塔顶脱水塔、塔釜脱水塔和蒸发器。与实施例1对比：乙二醇脱重塔与共沸塔的总理论板和操作条件相同；本比较例中的乙二醇脱轻塔的总理论板和操作条件与实施例1的乙二醇精制塔相同。乙二醇产品中以重量百分比计的乙二醇、1，2-丙二醇、1，2-丁二醇、2，3-丁二醇、1，4-丁二醇、1，2-戊二醇、1，2-己二醇和
Figure PCTCN2019104167-appb-000023
的组成分别为：99.45％、0％、0.25％、0％、0％、0.02％、0.21％、0.07％。紫外透过率在220nm波长下为56.1％、275nm波长下为87.2％、350nm波长下为96.8％。总的低纯度乙二醇精馏收率为93.0％。
实验结果表明：不使用共沸剂的传统精馏无法有效分离乙二醇中的1，2-丁二醇、1，2-戊二醇，1，2-己二醇和任选的
Figure PCTCN2019104167-appb-000024
等杂质，如果达到99.9％的纯度，需要增加回流比和能耗，并且无法有效提升紫外透过率，而本发明的方法可以在乙二醇的高收率条件下将所述乙二醇的纯度提高至99.90％以上，并且所得乙二醇在220nm、275nm、350nm波长下的紫外透过率分别提升至75％、92％、99％以上。

Claims (11)

  1. 一种精制非石油基乙二醇的方法，其中将C 5-C 20亲油醇类化合物，C 5-C 20烷烃和C 4-C 20亲油酮类化合物中的一种，二种或多种作为共沸剂与所述非石油基乙二醇进行共沸得到包含乙二醇的共沸物，然后加入水将该共沸物中的乙二醇溶解，将不溶于水的共沸剂和乙二醇水溶液分离，所得乙二醇水溶液脱水精制后获得乙二醇。
  2. 根据权利要求1的方法，其中所述C 5-C 20亲油醇类化合物是C 6-C 15亲油醇类化合物，优选是C 7-C 12亲油醇类化合物，特别优选是C 7-C 10亲油醇类化合物，并且该亲油醇类化合物可以是脂肪醇和含有杂环的醇，例如戊醇和其异构体，己醇和其异构体，庚醇和其异构体，辛醇和其异构体，壬醇和其异构体，癸醇和其异构体，十一醇和其异构体，月桂醇和其异构体以及苄醇。
  3. 根据权利要求2的方法，其中所述C 5-C 20亲油醇类化合物是己醇、异己醇、庚醇、异庚醇、辛醇、异辛醇、壬醇、异壬醇、癸醇和异癸醇。
  4. 根据权利要求1-3任一项的方法，其中所述的C 5-C 20烷烃是C 5-C 15烷烃，优选是C 5-C 12烷烃，特别优选是C 5-C 10烷烃，并且该烷烃可以是直链烷烃，支链烷烃、环烷烃或含苯环的烷烃，例如戊烷和其异构体，己烷和其异构体，庚烷和其异构体，辛烷和其异构体，壬烷和其异构体，癸烷和其异构体，十一烷和其异构体，十二烷和其异构体，环戊烷，环己烷，乙苯和其异构体，优选是己烷、庚烷、辛烷、壬烷、癸烷、十一烷、十二烷、环戊烷、环己烷、乙苯。
  5. 根据权利要求1-4任一项的方法，其中所述的C 4-C 20亲油酮类化合物是C 5-C 15亲油酮类化合物，优选是C 6-C 12亲油酮类化合物，特别优选是C 6-C 10亲油酮类化合物，并且该酮可以是脂肪酮或者脂环酮，优选庚酮，二异丁基酮，环己酮，2-壬酮。
  6. 根据权利要求1-5任一项的方法，其中所述非石油基乙二醇是煤制乙二醇或由生物质制得的乙二醇，其中所述的生物质优选是指包括玉米、甘蔗等可以食用的第一代生物质以及包括秸秆、木材、蔗渣等在内的农林业废弃物的非粮食的第二代生物质。
  7. 根据权利要求1-6任一项的方法，其中所述非石油基乙二醇包 含但不限于乙二醇、丁二醇(优选1，2-丁二醇)、戊二醇(优选1，2-戊二醇)和己二醇(优选1，2-己二醇)，优选地还包含
    Figure PCTCN2019104167-appb-100001
  8. 根据权利要求1-7任一项的方法，其中所述非石油基乙二醇包含丙二醇，丙三醇和/或山梨醇。
  9. 根据权利要求1-8任一项的方法，其中所述非石油基乙二醇包含
    1-100重量％乙二醇，端点100重量％除外，优选1-99重量％乙二醇，更有选5-99重量％乙二醇，特别优选10-95重量％乙二醇，
    0-95重量％，优选0-50重量％，更优选0-30重量％，特别优选0-10重量％的丁二醇，优选1，2-丁二醇，端点0除外，
    0-95重量％，优选0-50重量％，更优选0-10重量％，特别优选0-1重量％的戊二醇，优选1，2-戊二醇，端点0除外，
    0-95重量％，优选0-50重量％，更优选0-10重量％，特别优选0-1重量％的己二醇，优选1，2-己二醇，端点0除外，和
    任选的0-95重量％，优选0-50重量％，更优选0-10重量％，特别优选0-1重量％的
    Figure PCTCN2019104167-appb-100002
  10. 根据权利要求1-9任一项的方法，其中所述非石油基乙二醇包含
    0-95重量％，优选0.1-50重量％的1，2-丙二醇，
    0-50重量％，优选0.01-10重量％的2，3-丁二醇，
    0-20重量％，优选0.01-10重量％的丙三醇，和/或
    0-20重量％，优选0.01-10重量％的山梨醇。
  11. 根据权利要求1-10任一项的方法，其中所述非石油基乙二醇包含影响乙二醇紫外透过率的微量甚至低于气相色谱检测限的酸、醚、醛、酮和/或醇等杂质。
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