WO2012024751A1 - Procédé d'estérification et de purification d'acétate d'éthyle et d'éthanol anhydre - Google Patents

Procédé d'estérification et de purification d'acétate d'éthyle et d'éthanol anhydre Download PDF

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Publication number
WO2012024751A1
WO2012024751A1 PCT/BR2011/000203 BR2011000203W WO2012024751A1 WO 2012024751 A1 WO2012024751 A1 WO 2012024751A1 BR 2011000203 W BR2011000203 W BR 2011000203W WO 2012024751 A1 WO2012024751 A1 WO 2012024751A1
Authority
WO
WIPO (PCT)
Prior art keywords
column
water
separation
ethyl acetate
ethylene glycol
Prior art date
Application number
PCT/BR2011/000203
Other languages
English (en)
Portuguese (pt)
Inventor
Rubens Maciel Filhom
Maria Cristina DE ARAÚJO
Original Assignee
Universidade Estadual De Campinas-Unicamp
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 Universidade Estadual De Campinas-Unicamp filed Critical Universidade Estadual De Campinas-Unicamp
Publication of WO2012024751A1 publication Critical patent/WO2012024751A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/20—Vanadium, niobium or tantalum
    • 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
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/48—Separation; Purification; Stabilisation; Use of additives
    • C07C67/52—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
    • C07C67/54—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation

Definitions

  • the conversion of acetic acid using the catalysts of the invention is at least 20% and may be up to 70%, with ethyl acetate selectivity of at least 60%, preferably 80% and more preferably 95%.
  • the proposed invention differs from that disclosed in WO2010014145-A2 in that it comprises an integrated system and process for obtaining ethyl acetate and anhydrous ethanol and / or hydrous ethanol, and is used as a reaction, washing or separating solvent for those generated by the process itself.
  • the present invention makes use of solvents which advantageously promote the separation of compounds even those having azeotropy when in binary mixing.
  • the proposed system ensures thermal energy utilization by promoting energy savings, as well as milder operating conditions when compared to technology deposited in 2009, and advantageously utilizing residual solvent in subsequent unit operations, reducing both waste treatment and amount of replacement solvent .
  • the present invention provides an alternative system and integrated process for obtaining ethyl acetate and anhydrous ethanol with emphasis on minimizing energy expenditure and reusing the solvents used therein.
  • Said separation means are preferably distillation columns.
  • a further object of the present invention is an integrated system for producing ethyl acetate and anhydrous ethanol in a configuration comprising:
  • the process may or may not comprise nitrogen feed in the reaction step at a temperature ranging from 120 to 170 ° C, preferably from 127 to 131 ° C and a volumetric flow rate of nitrogen to reactor length preferably from 680 to 1530 L / h for each meter of reactor length.
  • Table 2 An example embodiment of the present invention is shown in Table 2 wherein the conversion obtained for the ethanol / acetic acid ratio of 1.85 and the operating conditions for the reactor were the same as for the previous ratio, 1.85.
  • the reactor inlet temperature was 131 ° C and the largest volumetric flow rate was 428.95 l / h corresponding to a ratio of 1530 L / h per meter of reactor. For these conditions, the conversion reached 100% for acetic acid.
  • the separation step aims to purify the obtained product which is in mixtures formed in earlier stages of the ethyl acetate obtaining process.
  • Column 1 is a typical azeotropic distillation column, ethyl acetate and water having minimum boiling azeotropy are at the top of the column in the TOP01 stream and at the bottom of the column in the FUND01 stream are acetic acid and water. .
  • An interesting factor is the amount of water that can be removed at the bottom of the column along with acetic acid.
  • Column 4 is a conventional distillation column for solvent rectification having 22 stages; the preferred feeding plate being 12 ° and operating at a reflux ratio of 0.44.
  • the AGUA2 top stream features pure water.
  • Column 6 is, in the present example, a conventional distillation column for solvent rectification preferably having 21 stages with the feed plate being 12 °.
  • the reflux ratio is 0.426.
  • the AGUA3 top stream features pure water. Column 6 shows no pressure variation.
  • the novelty is the use of water to separate the ethyl acetate azeotrope and water from ethanol and water.
  • the predominant factor is the excess water used in this separation.
  • Columns 1 and 2 are the same as those already discussed in configuration ⁇ , so they will not be parsed again.
  • Column 8 in this example, is a conventional distillation column for the rectification of the solvent preferably having 21 stages and the feed plate is preferably 7, with a reflux ratio of 6.22.
  • the AGUA3 top stream has high purity water (about 99.9%), the solvent remains at the bottom of the column in the high purity SOLVENTE2 stream (up to 100%).

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne un procédé intégré de production d'acétate d'éthyle et d'éthanol anhydre, comprenant deux étapes d'estérification en phase gazeuse d'acide acétique avec éthanol anhydre, ou avec éthanol hydraté, en parallèle, en présence d'un catalyseur de pentoxyde de niobium, et une étape suivante de séparation des produits, réalisée selon deux modes de procédé distincts, l'un basé sur la séparation du mélange azéotropique provenant de la réaction par distillation extractive faisant intervenir l'excès d'eau (système intégré ∑), l'autre faisant appel au solvant éthylèneglycol (système intégré Ω), ce qui permet une réutilisation de solvants dans les étapes suivantes, avec obtention d'acétate d'éthyle de haute pureté et d'éthanol anhydre.
PCT/BR2011/000203 2010-08-27 2011-07-04 Procédé d'estérification et de purification d'acétate d'éthyle et d'éthanol anhydre WO2012024751A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
BRPI1004480-9 2010-08-27
BRPI1004480-9A BRPI1004480B1 (pt) 2010-08-27 2010-08-27 Sistema integrado para produção de acetato de etila e etanol anidro, processo integrado de obtenção de acetato de etila e etanol anidro e, produto obtido pelo mesmo

Publications (1)

Publication Number Publication Date
WO2012024751A1 true WO2012024751A1 (fr) 2012-03-01

Family

ID=45722764

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/BR2011/000203 WO2012024751A1 (fr) 2010-08-27 2011-07-04 Procédé d'estérification et de purification d'acétate d'éthyle et d'éthanol anhydre

Country Status (2)

Country Link
BR (1) BRPI1004480B1 (fr)
WO (1) WO2012024751A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114524742A (zh) * 2022-02-28 2022-05-24 山东大学 一种高纯度月桂酰胺丙基甜菜碱的制备方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3384656A (en) * 1965-12-29 1968-05-21 Commercial Solvents Corp Vapor phase esterification of aliphatic alcohols with lower aliphatic acids in the presence of niobium oxide
US4379028A (en) * 1982-03-30 1983-04-05 Lloyd Berg Separation of ethyl acetate from ethanol and water by extractive distillation
JPH06336455A (ja) * 1993-05-28 1994-12-06 Showa Denko Kk 酢酸エチルの精製方法
US6809217B1 (en) * 1998-10-01 2004-10-26 Davy Process Technology Limited Process for the preparation of ethyl acetate
US20090014313A1 (en) * 2007-07-13 2009-01-15 Fu-Ming Lee Low-energy extractive distillation process for dehydration of aqueous ethanol

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3384656A (en) * 1965-12-29 1968-05-21 Commercial Solvents Corp Vapor phase esterification of aliphatic alcohols with lower aliphatic acids in the presence of niobium oxide
US4379028A (en) * 1982-03-30 1983-04-05 Lloyd Berg Separation of ethyl acetate from ethanol and water by extractive distillation
JPH06336455A (ja) * 1993-05-28 1994-12-06 Showa Denko Kk 酢酸エチルの精製方法
US6809217B1 (en) * 1998-10-01 2004-10-26 Davy Process Technology Limited Process for the preparation of ethyl acetate
US20090014313A1 (en) * 2007-07-13 2009-01-15 Fu-Ming Lee Low-energy extractive distillation process for dehydration of aqueous ethanol

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114524742A (zh) * 2022-02-28 2022-05-24 山东大学 一种高纯度月桂酰胺丙基甜菜碱的制备方法

Also Published As

Publication number Publication date
BRPI1004480B1 (pt) 2019-05-28
BRPI1004480A2 (pt) 2012-05-29

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