WO2000044698A1 - Separation of methanol and acetone from mixtures thereof by extractive distillation - Google Patents

Separation of methanol and acetone from mixtures thereof by extractive distillation Download PDF

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Publication number
WO2000044698A1
WO2000044698A1 PCT/IB2000/000077 IB0000077W WO0044698A1 WO 2000044698 A1 WO2000044698 A1 WO 2000044698A1 IB 0000077 W IB0000077 W IB 0000077W WO 0044698 A1 WO0044698 A1 WO 0044698A1
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Prior art keywords
methanol
acetone
extractive distillation
mixture
liquid
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PCT/IB2000/000077
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French (fr)
Inventor
Izak Nieuwoudt
Braam Van Dyk
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Izak Nieuwoudt
Braam Van Dyk
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Application filed by Izak Nieuwoudt, Braam Van Dyk filed Critical Izak Nieuwoudt
Priority to AU30700/00A priority Critical patent/AU3070000A/en
Publication of WO2000044698A1 publication Critical patent/WO2000044698A1/en
Priority to US09/671,334 priority patent/US6383343B1/en

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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
    • C07C29/84—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by distillation by extractive distillation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/78—Separation; Purification; Stabilisation; Use of additives
    • C07C45/81—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
    • C07C45/82—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
    • C07C45/83—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation by extractive distillation

Definitions

  • the present invention relates to the separation of methanol and acetone from mixtures thereof by extractive distillation.
  • Extractive distillation is a process to separate close-boiling compounds from each other by introducing a selectively-acting third component, the extractive distillation solvent, with the result that the relative volatility of the mixture to be separated is increased and azeotropes, if present, are overcome.
  • the extractive distillation solvent is to be selected such that it does not form an undesired azeotrope with any of the compounds in the mixture.
  • extractive distillation is the method of separating close boiling compounds from each other by carrying out the distillation in a multiplate rectification column in the presence of an added liquid or liquid mixture, said liquid(s) having a boiling point higher than the compounds being separated.
  • the extractive distillation solvent is introduced near the top of the column and flows downward until it reaches the stillpot or reboiler. Its presence on each plate of the rectification column alters the relative volatility of the close boiling compounds in a direction to make the separation on each plate greater and thus require either fewer plates to effect the same separation or make possible a greater degree of separation with the same number of plates.
  • the extractive distillation solvent should boil l higher than any of the close boiling liquids being separated and not form minimum azeotropes with them.
  • the extractive distillation solvent is introduced a few plates from the top of the column to ensure that none of the extractive distillation solvent is carried over with the lowest boiling component.
  • a method of separation of methanol and acetone includes the step of distilling a mixture of methanol / acetone containing at least methanol and acetone by way of an extractive distillation process in the presence of an extractive distillation solvent selected from the group consisting of a secondary amine, a chlorinated hydrocarbon, a brominated hydrocarbon and a paraffin.
  • the methanol / acetone mixture may contain only methanol and acetone.
  • the secondary amine may be N,N'-dimethyl-1 ,3-propanediamine.
  • the secondary amine may be N,N'-dimethylethylenediamine.
  • the secondary amine may be dibutylamine.
  • the chlorinated hydrocarbon may be hexachlorobutadiene.
  • the chlorinated hydrocarbon may be tetrachloroethylene.
  • the brominated hydrocarbon may be 1 ,4-dibromo-butane.
  • the paraffin may be at least one of the components selected from the group consisting of undecane, dodecane, tridecane and tetradecane.
  • vapour-liquid equilibrium still 10 including a bulb flask 12 having a tube 14 leading to a condenser 16 and terminating in an outlet 18.
  • the outlet 18 has an electromagnetic closure mechanism 20.
  • a liquid phase sample conduit 22 leads into the flask 12.
  • a further liquid phase sample conduit 24 leads into the tube 14.
  • a first thermometer 26 is adapted to read the temperature of the liquid contained in the flask 12, and a second thermometer 28 is adapted to read the temperature of the vapour in the tube 14.
  • the flask 12 can be heated by a heating mantle 30.
  • the extractive distillation procedure is as follows:
  • a liquid mixture is prepared consisting of methanol, acetone and an extractive distillation solvent.
  • the liquid is introduced into the bulb flask 12 via conduit 22.
  • the mixture in the bulb flask 12 is then heated by the heating mantle 30 and kept at boiling point.
  • the mixture separates into a liquid phase remaining in the bulb flask 12 and a vapour phase in the tube 14.
  • the vapour phase is cooled by the condenser 16, whereafter it condenses and returns as liquid to the bulb flask 12.
  • the mixture is boiled and condensed for several hours, normally 5 to 6 hours. The process of evaporation and condensation is repeated until equilibrium is reached between the vapour and liquid phases. Thereafter, a liquid sample of the liquid phase in the bulb flask 12 is extracted through conduit 22 and a liquid sample of the condensed vapour phase in the tube 14 is extracted through conduit 24.
  • thermometer 26 The temperature of the liquid phase in the bulb flask 12 is continuously monitored by the thermometer 26, and the temperature of the vapour phase in the tube 14 is continuously monitored by the thermometer 28.
  • a methanol/acetone liquid mixture with a molar ratio of 1.55:1 has a relative volatility of 0.63.
  • the separation was effected by using a suitable secondary amine as an extractive distillation solvent.
  • An acetone/methanol mixture with a molar ratio of 1 :1 has a relative volatility of 1.4.
  • the separation was effected by a suitable secondary amine as an extractive distillation solvent.
  • a methanol/acetone mixture with a molar ratio of 0.85:1 has a relative volatility of 0.75.
  • the separation was effected by using a suitable chlorinated hydrocarbon as an extractive distillation solvent.
  • a methanol/acetone mixture with a molar ratio of 0.63:1 has a relative volatility of 0.81.
  • the separation was effected by using a suitable chlorinated hydrocarbon as an extractive distillation solvent. After sampling in experiment 3, the mixture left in the apparatus was boiled up again (for 5 to 6 hours) and liquid and vapour samples drawn. The liquid and vapour phases were analysed. The liquid and vapour molar fractions were determined to be as follows:
  • a methanol/acetone mixture with a molar ratio of 1.1 :1 has a relative volatility of 0.70.
  • the separation was effected by using a suitable brominated hydrocarbon as an extractive distillation solvent.
  • a methanol/acetone mixture with a molar ratio of 1.13:1 has a relative volatility of 0.69.
  • the separation was effected by using a suitable paraffin as an extractive distillation solvent.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

Extractive distillation is a process to separate close-boiling compounds from each other by introducing a selectively-acting third component, the extractive distillation solvent, with the result that the relative volatility of the mixture to be separated is increased and azeotropes, if present, are overcome. The extractive distillation solvent is to be selected such that it does not form an undesired azeotrope with any of the compounds in the mixture. The invention suggests a method of separation of methanol and acetone by distilling a mixture of methanol/acetone by way of an extractive distillation process in the presence of an extractive distillation solvent selected from the group consisting of a secondary amine, a chlorinated hydrocarbon, a brominated hydrocarbon and a paraffin.

Description

Separation of methanol and acetone from mixtures thereof by extractive distillation.
FIELD OF INVENTION
The present invention relates to the separation of methanol and acetone from mixtures thereof by extractive distillation.
BACKGROUND TO INVENTION
Extractive distillation is a process to separate close-boiling compounds from each other by introducing a selectively-acting third component, the extractive distillation solvent, with the result that the relative volatility of the mixture to be separated is increased and azeotropes, if present, are overcome. The extractive distillation solvent is to be selected such that it does not form an undesired azeotrope with any of the compounds in the mixture.
The separation of methanol and acetone is complicated due to the existence of an azeotrope. Water or ethylene glycol have been proposed in the literature as extractive distillation solvents to produce methanol as distillate.
As has been stated in US Patent 5,800,681 (Berg) extractive distillation is the method of separating close boiling compounds from each other by carrying out the distillation in a multiplate rectification column in the presence of an added liquid or liquid mixture, said liquid(s) having a boiling point higher than the compounds being separated. The extractive distillation solvent is introduced near the top of the column and flows downward until it reaches the stillpot or reboiler. Its presence on each plate of the rectification column alters the relative volatility of the close boiling compounds in a direction to make the separation on each plate greater and thus require either fewer plates to effect the same separation or make possible a greater degree of separation with the same number of plates. The extractive distillation solvent should boil l higher than any of the close boiling liquids being separated and not form minimum azeotropes with them. Usually the extractive distillation solvent is introduced a few plates from the top of the column to ensure that none of the extractive distillation solvent is carried over with the lowest boiling component.
It is an object of this invention to suggest at least one further extractive distillation solvent for the separation of methanol and acetone from mixtures thereof.
SUMMARY OF INVENTION
According to the invention, a method of separation of methanol and acetone includes the step of distilling a mixture of methanol / acetone containing at least methanol and acetone by way of an extractive distillation process in the presence of an extractive distillation solvent selected from the group consisting of a secondary amine, a chlorinated hydrocarbon, a brominated hydrocarbon and a paraffin.
The methanol / acetone mixture may contain only methanol and acetone.
The secondary amine may be N,N'-dimethyl-1 ,3-propanediamine.
The secondary amine may be N,N'-dimethylethylenediamine.
The secondary amine may be dibutylamine.
The chlorinated hydrocarbon may be hexachlorobutadiene.
The chlorinated hydrocarbon may be tetrachloroethylene.
The brominated hydrocarbon may be 1 ,4-dibromo-butane.
The paraffin may be at least one of the components selected from the group consisting of undecane, dodecane, tridecane and tetradecane. BRIEF DESCRIPTION OF DRAWING
The invention will now be described by way of example with reference to the accompanying schematic drawing.
In the drawing there is shown a schematic view of an experimental apparatus for testing an extractive distillation solvent for separating methanol and acetone from mixtures thereof in accordance with the invention.
DETAILED DESCRIPTION OF DRAWING AND EXPERIMENTS
In the drawing there is shown a vapour-liquid equilibrium still 10 including a bulb flask 12 having a tube 14 leading to a condenser 16 and terminating in an outlet 18. The outlet 18 has an electromagnetic closure mechanism 20.
A liquid phase sample conduit 22 leads into the flask 12.
A further liquid phase sample conduit 24 leads into the tube 14.
A first thermometer 26 is adapted to read the temperature of the liquid contained in the flask 12, and a second thermometer 28 is adapted to read the temperature of the vapour in the tube 14.
The flask 12 can be heated by a heating mantle 30.
The extractive distillation procedure is as follows:
A liquid mixture is prepared consisting of methanol, acetone and an extractive distillation solvent. The liquid is introduced into the bulb flask 12 via conduit 22.
The mixture in the bulb flask 12 is then heated by the heating mantle 30 and kept at boiling point.
During boiling the mixture separates into a liquid phase remaining in the bulb flask 12 and a vapour phase in the tube 14. In the tube 14 the vapour phase is cooled by the condenser 16, whereafter it condenses and returns as liquid to the bulb flask 12.
The mixture is boiled and condensed for several hours, normally 5 to 6 hours. The process of evaporation and condensation is repeated until equilibrium is reached between the vapour and liquid phases. Thereafter, a liquid sample of the liquid phase in the bulb flask 12 is extracted through conduit 22 and a liquid sample of the condensed vapour phase in the tube 14 is extracted through conduit 24.
The temperature of the liquid phase in the bulb flask 12 is continuously monitored by the thermometer 26, and the temperature of the vapour phase in the tube 14 is continuously monitored by the thermometer 28.
Experiment 1
A methanol/acetone liquid mixture with a molar ratio of 1.55:1 has a relative volatility of 0.63.
The separation was effected by using a suitable secondary amine as an extractive distillation solvent.
A mixture of methanol (8.1g), acetone (9.4g) and N,N'-dimethylethylene diamine (39.5g) was charged into the flask 12 of the vapour-liquid equilibrium still 10 and the above procedure was applied. The liquid and vapour phases were analysed. The liquid and vapour molar fractions were determined to be as follows:
Table 1
Figure imgf000007_0001
This translates to a relative volatility of 7.73 for the system methanol/acetone in the ternary system shown above, the methanol being the distillate.
Experiment 2
An acetone/methanol mixture with a molar ratio of 1 :1 has a relative volatility of 1.4.
The separation was effected by a suitable secondary amine as an extractive distillation solvent.
A mixture of methanol (7.9g), acetone (14.4g) and di-butylamine (245.3g) was charged into the flask 12 of the vapour-liquid equilibrium still 10 and the above procedure was applied. The liquid and vapour phases were analysed. The liquid and vapour molar fractions were determined to be as follows:
Table 2
Figure imgf000007_0002
This translates to a relative volatility of 1.88 for the system acetone/methanol in the ternary system shown above, the acetone being the distillate.
Experiment 3
A methanol/acetone mixture with a molar ratio of 0.85:1 has a relative volatility of 0.75.
The separation was effected by using a suitable chlorinated hydrocarbon as an extractive distillation solvent.
A mixture of methanol (11.7g), acetone (24.9g) and tetrachloroethylene (491. Og) was charged into the flask 12 of the vapour-liquid equilibrium 10 and the above procedures was applied. The liquid and vapour phases were analysed. The liquid and vapour molar fractions were determined to be as follows:
Table 3
Figure imgf000008_0001
This translates to a relative volatility of 1.87 for the system methanol/ acetone in the ternary system shown above, the methanol being the distillate.
Experiment 4
A methanol/acetone mixture with a molar ratio of 0.63:1 has a relative volatility of 0.81.
The separation was effected by using a suitable chlorinated hydrocarbon as an extractive distillation solvent. After sampling in experiment 3, the mixture left in the apparatus was boiled up again (for 5 to 6 hours) and liquid and vapour samples drawn. The liquid and vapour phases were analysed. The liquid and vapour molar fractions were determined to be as follows:
Table 4:
Figure imgf000009_0001
This translates to a relative volatility of 2.57 for the system methanol/acetone in the ternary system shown above, the methanol being the distillate.
Experiment 5
A methanol/acetone mixture with a molar ratio of 1.1 :1 has a relative volatility of 0.70.
The separation was effected by using a suitable brominated hydrocarbon as an extractive distillation solvent.
A mixture of methanol (11.6g), acetone (6.9g) and 1 ,4-dibromobutane (173.1g) was charged into the flask 12 of the vapour-liquid equilibrium still 10 and the above procedure was applied. The liquid and vapour phases were analysed. The liquid and vapour molar fractions were determined to be as follows: Table 5:
Figure imgf000010_0001
This translates to a relative volatility of 6.12 for the system methanol/acetone in the ternary system shown above, the methanol being the distillate.
Experiment 6
A methanol/acetone mixture with a molar ratio of 1.13:1 has a relative volatility of 0.69.
The separation was effected by using a suitable paraffin as an extractive distillation solvent.
A mixture of methanol (6.3g), acetone (10.2g) and dodecane (207.3g) was charged into the flask 12 of the vapour-liquid equilibrium still 10 and the above procedure was applied. The liquid and vapour phases were analysed. The liquid and vapour molar fractions were determined to be as follows:
Table 6:
Figure imgf000011_0001
This translates to a relative volatility of 1.56 for the system methanol/acetone in the ternary system shown above, the methanol being the distillate.

Claims

PATENT CLAIMS
1. A method of separation of methanol and acetone, which includes the step of distilling a mixture of methanol / acetone containing at least methanol and acetone by way of an extractive distillation process in the presence of an extractive distillation solvent selected from the group consisting of a secondary amine, a chlorinated hydrocarbon, a brominated hydrocarbon and a paraffin.
2. A method as claimed in claim 1 , in which the methanol / acetone mixture contains only methanol and acetone.
3. A method as claimed in claim 1 or claim 2, in which the secondary amine is N,N'-dimethyl-1 ,3-propanediamine.
4. A method as claimed in claim 1 or claim 2, in which the secondary amine is N.N'-dimethylethylenediamine.
5. A method as claimed in claim 1 or claim 2, in which the secondary amine is dibutylamine.
6. A method as claimed in claim 1 or claim 2, in which the chlorinated hydrocarbon is hexachlorobutadiene.
7. A method as claimed in claim 1 or claim 2, in which the chlorinated hydrocarbon is tetrachloroethylene.
8. A method as claimed in claim 1 or claim 2, in which the brominated hydrocarbon is 1 ,4-dibromo-butane.
9. A method as claimed in claim 1 or claim 2, in which the paraffin is at least one of the components selected from the group consisting of undecane, dodecane, tridecane and tetradecane.
PCT/IB2000/000077 1999-01-28 2000-01-26 Separation of methanol and acetone from mixtures thereof by extractive distillation WO2000044698A1 (en)

Priority Applications (2)

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AU30700/00A AU3070000A (en) 1999-01-28 2000-01-26 Separation of methanol and acetone from mixtures thereof by extractive distillation
US09/671,334 US6383343B1 (en) 1999-01-28 2000-09-28 Separation of components from methanol mixtures by extractive distillation

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ZA99637 1999-01-28
ZA99638 1999-01-28
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ZA99/0635 1999-01-28
ZA99/0640 1999-01-28
ZA99/0636 1999-01-28
ZA99635 1999-01-28
ZA99636 1999-01-28
ZA99/0638 1999-01-28

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2369125A (en) * 2000-10-17 2002-05-22 Instrumentation Scient De Labo Process and apparatus for determining the distillation characteristics of liquid petroleum products
CN114956961A (en) * 2022-04-21 2022-08-30 科富恺工艺设备(上海)有限公司 Separation method of methanol acetone azeotrope

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4584063A (en) * 1982-06-28 1986-04-22 Lloyd Berg Separation of acetone from methanol by extractive distillation
US4620901A (en) * 1985-11-04 1986-11-04 Lloyd Berg Separation of acetone from methanol by extractive distillation
US5453166A (en) * 1994-11-07 1995-09-26 Lloyd Berg Separation of ethanol from 2-butanone by extractive distillation
US5897750A (en) * 1997-08-28 1999-04-27 Berg; Lloyd Separation of acetone from isopropanol-water mixtures by extractive distillation

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4584063A (en) * 1982-06-28 1986-04-22 Lloyd Berg Separation of acetone from methanol by extractive distillation
US4620901A (en) * 1985-11-04 1986-11-04 Lloyd Berg Separation of acetone from methanol by extractive distillation
US5453166A (en) * 1994-11-07 1995-09-26 Lloyd Berg Separation of ethanol from 2-butanone by extractive distillation
US5897750A (en) * 1997-08-28 1999-04-27 Berg; Lloyd Separation of acetone from isopropanol-water mixtures by extractive distillation

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2369125A (en) * 2000-10-17 2002-05-22 Instrumentation Scient De Labo Process and apparatus for determining the distillation characteristics of liquid petroleum products
GB2369125B (en) * 2000-10-17 2002-09-18 Instrumentation Scient De Labo Process for determining the distillation characteristics of liquid petroleum products by express mini-distillation and apparatus permitting implementation
CN114956961A (en) * 2022-04-21 2022-08-30 科富恺工艺设备(上海)有限公司 Separation method of methanol acetone azeotrope

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