US3432401A - Process for production of glacial acrylic acid by azeotropic distillation with a water entrainer - Google Patents

Process for production of glacial acrylic acid by azeotropic distillation with a water entrainer Download PDF

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Publication number
US3432401A
US3432401A US352829A US3432401DA US3432401A US 3432401 A US3432401 A US 3432401A US 352829 A US352829 A US 352829A US 3432401D A US3432401D A US 3432401DA US 3432401 A US3432401 A US 3432401A
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acrylic acid
entrainer
water
distillation
glacial
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US352829A
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English (en)
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Claude Tcherkawsky
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Societe dElectro Chimie dElectro Metallurgie et des Acieries Electriques Dugine SA SECEMAU
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Societe dElectro Chimie dElectro Metallurgie et des Acieries Electriques Dugine SA SECEMAU
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/42—Separation; Purification; Stabilisation; Use of additives
    • C07C51/43—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation
    • C07C51/44—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation by distillation
    • C07C51/46—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation by distillation by azeotropic distillation
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S203/00—Distillation: processes, separatory
    • Y10S203/22—Accessories

Definitions

  • This invention relates to a process for production of glacial acrylic acid from dilute aqueous solutions of same by heteroazeotropic entrainment of the water contained in the aqueous solutions.
  • Processes for the obtention of raw acrylic acid comprise treating carbon monoxide with acetylene in the presence of catalysts; treating acrylonitrile with aqueous solutions of sulphuric acid; treating ethylene cyanohydrin with aqueous solutions of sulphuric acid; or treating propylene with oxygen in the presence of a catalyst. All these processes give a raw product in the form of an aqueous solution which generally contains less than 50% by Weight acrylic acid.
  • the acrylic acid is extracted from an aqueous solution by a solvent or a mixture of solvents with or without metallic salts.
  • the resulting organic solution is afterwards distilled to obtain glacial acrylic acid.
  • this process produces no quantitative extraction of the acid and a substantial quantity of the acid remains in the water which effects a decreased yield of glacial acrylic acid.
  • My invention overcomes the foregoing disadvantages and covers a process for obtention of glacial acrylic acid from dilute aqueous solutions. Specifically, it comprises quantitatively eliminating the water contained in the raw acrylic acid Iby heteroazeotropic entrainment by entrainers which form heteroazeotropes with water and do not react with acrylic acid.
  • the process is applicable to any 3,432,401 Patented Mar. 11, 1969 which mixture forms a heterogeneous liquid upon condensation thereof.
  • Azeotropic entrainment of the water may be carried out under various conditions of pressure, depending on the nature of the entrainer. With some entrainers, it is worked under higher pressure than atmospheric pressure; however, operating under vacuum or under less than atmospheric pressure gives better results. I prefer an absolute pressure inferior to 400 mm. Hg.
  • the temperature is limited by polymerization of acrylic acid, and it is advisable not to heat beyond 120 C. and preferably to work at temperature below C.
  • the entrainer have a little solubility in water, form a heteroazeotrope rich in water, be substantially chemically inert towards said acrylic acid, and be easily separated from acrylic acid by distillation.
  • An excessive solubility of the entrainer in Water would lead to losses of the entrainer through water elimination, and the latter then has to be redistilled.
  • the quantity of water captured by it must be at least 3%, and preferably 7% by weight.
  • the difference between the distillation temperatures of the entrainer and of the acrylic acid must be between 5 C. and 100 C., and preferably between 15 C. and 40 C.
  • entrainers examples include: benzene, toluene, esters of acrylic and methacrylic acids, acrylonitrile, monochlorobenzene, carbon tetrachloride, orthodichlorobenzene, etc.
  • This distillation of the heteroazeotrope may be carried out by a continuous or a discontinuous process, but it is preferable to operate continuously to avoid prolonged super beatings which can alter the product.
  • the ulterior separation of the small quantity of entrainer remaining in the glacial acrylic acid is carried out, if desired, by further distillation; but this operation is not necessary.
  • the accompanying. drawing shows one example of continuous industrial installation -for practicing my process.
  • a dilute aqueous solution of acrylonitrile is introduced through pipe a into a distillation column I from which the heteroazeotrope exits through conduit b and is condensed in a vessel II and then decanted in apparatus III.
  • the water is eliminated through pipe c and the entrainer is returned to the column I through conduit d.
  • the acrylic acid practically anhydrous but containing a small amount of the entrainer, leaves column I through pipe e and is introduced into a column IV where the acrylic acid is separated from excess entrainer.
  • the separated entrainer is recycled to column I by conduit f.
  • the anhydrous acrylic acid exits from column IV through pipe g and is introduced into a column V where the pure acrylic acid is removed through pipe h and residues are obtained through line i.
  • EXAMPLE I 500 g. of an aqueous Solution of a 50% acrylic acid and g. of benzene as an entrainer were introduced into a one-liter llask surmounted by a Fenske ring-column to which is connected a condenser. ⁇ 0.5 g. of hydroquinone and 1 g. of copper turnings as polymerization inhibitors were added to the ask.
  • the amount of acrylic acid obtained as glacial acid was 95.8% of the total amount of acrylic acid utilized.
  • the entire distillation was effected under a pressure of 100 mrn. Hg at increasing temperatures and at 38 C. a water-toluene heteroazeotrope was obtained. After separation of this heteroazeotrope into two phases, the toluene was sent back as reux into the ask. When formation of the heteroazeotrope stopped, the temperature rose to 53 C. and a dilute solution of acrylic acid in toluene was obtained. After elimination of the toluene, the ternperature rose to 87 C. and then the glacial acrylic acid desired was recovered.
  • the amount of acrylic acid obtained as glacial acrylic acid reached 94% of the total amount utilized.
  • Percent Acrylic acid 45 Water 45 Entrainer, acrylonitrile 2 kg. of hydroquinone and 5 kg. of copper turnings as polymerization inhibitors were added.
  • the amount of acrylic acid obtained as glacial acid was 98% of the total amount utilized.
  • a process for the production of at least 98% glacial acrylic acid from an aqueous solution containing 10% to 80% acrylic acid comprising:
  • entrainer being selected from the group consisting of benzene, toluene, esters of acrylic and methacrylic acids, acrylonitrile, monochlorobenzene, carbon tetrachloride and orthodichlorobenzene.
  • a process for the production of at least 98% glacial acrylic acid from an aqueous solution containing 10% to 80% acrylic acid comprising:

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US352829A 1963-03-21 1964-03-18 Process for production of glacial acrylic acid by azeotropic distillation with a water entrainer Expired - Lifetime US3432401A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
FR928802A FR1359885A (fr) 1963-03-21 1963-03-21 Procédé de fabrication d'acide acrylique glacial

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US3432401A true US3432401A (en) 1969-03-11

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US (1) US3432401A (en, 2012)
JP (1) JPS4827292B1 (en, 2012)
BE (1) BE643942A (en, 2012)
DE (1) DE1468956A1 (en, 2012)
ES (1) ES296656A1 (en, 2012)
FR (1) FR1359885A (en, 2012)
GB (1) GB1055532A (en, 2012)
LU (1) LU45409A1 (en, 2012)
NL (1) NL6401921A (en, 2012)

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3527677A (en) * 1969-03-06 1970-09-08 Goodrich Co B F Process for dehydration of aqueous acrylic acid solutions by extractive - azeotropic distillation with 2-ethylhexanol or 2-ethylhexylacrylate
US3868417A (en) * 1972-08-24 1975-02-25 Basf Ag Separation of acrylic acid from the reaction gases from propylene or acrolein oxidation
US3932500A (en) * 1971-07-21 1976-01-13 Badische Anilin- & Soda-Fabrik Aktiengesellschaft Recovering anhydrous acrylic acid
US4021310A (en) * 1972-12-22 1977-05-03 Nippon Shokubai Kagaku Kogyo Co., Ltd. Method for inhibiting the polymerization of acrylic acid or its esters
US4219389A (en) * 1977-06-14 1980-08-26 Rhone-Poulenc Industries Separation of acrylic acid from solutions thereof in tri-n-butyl phosphate
US4820385A (en) * 1988-02-18 1989-04-11 Monsanto Company Purification of alkyl glyoxylate in a continuous column by azeotropic distillation
EP0861820A3 (en) * 1997-02-28 1998-10-21 Nippon Shokubai Co., Ltd. Method for recovering acrylic acid
US20030150705A1 (en) * 2002-01-08 2003-08-14 Deshpande Sanjeev D. Acrylic acid recovery utilizing ethyl acrylate and selected co-solvents
US20030205451A1 (en) * 2002-05-01 2003-11-06 Briegel Keith Frederick Process for manufacturing high purity methacrylic acid
US6926810B2 (en) * 2001-03-15 2005-08-09 A. E. Staley Manufacturing Co. Process for obtaining an organic acid from an organic acid ammonium salt, an organic acid amide, or an alkylamine organic acid complex
US6982026B2 (en) * 2001-03-15 2006-01-03 Tate & Lyle Ingredients Americas, Inc. Azeotropic distillation process for producing organic acids or organic acid amides
US6984293B2 (en) * 2001-03-15 2006-01-10 Tate & Lyle Ingredients Azeotropic distillation of cyclic esters of hydroxy organic acids
US11866631B2 (en) 2019-04-29 2024-01-09 Ecolab Usa Inc. Oxygenated aminophenol compounds and methods for preventing monomer polymerization
US12312291B2 (en) 2019-04-29 2025-05-27 Ecolab Usa Inc. Oxygenated aromatic amines and use as antioxidants

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3493471A (en) * 1967-12-01 1970-02-03 Dow Chemical Co Acrylic acid purification
US3666632A (en) * 1968-10-08 1972-05-30 Asahi Chemical Ind Method for the separation of acrylic acid from aqueous solution containing acrylic acid and acetic acid

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1668380A (en) * 1923-12-28 1928-05-01 Distilleries Des Deux Sevres Continuous process for the dehydration of volatile fatty acids
US1915002A (en) * 1929-03-19 1933-06-20 Us Ind Alcohol Co Process of obtaining fatty acids in anhydrous state from aqueous solutions
US2033978A (en) * 1932-04-01 1936-03-17 Dreyfus Henry Concentration of lower aliphatic acids
FR1169740A (fr) * 1956-03-22 1959-01-05 Solvay Werke Gmbh Procédé de concentration d'acide acrylique aqueux
US3337740A (en) * 1962-02-13 1967-08-22 Deering Milliken Res Corp Process for separating acrylic acid from impurities

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1668380A (en) * 1923-12-28 1928-05-01 Distilleries Des Deux Sevres Continuous process for the dehydration of volatile fatty acids
US1915002A (en) * 1929-03-19 1933-06-20 Us Ind Alcohol Co Process of obtaining fatty acids in anhydrous state from aqueous solutions
US2033978A (en) * 1932-04-01 1936-03-17 Dreyfus Henry Concentration of lower aliphatic acids
FR1169740A (fr) * 1956-03-22 1959-01-05 Solvay Werke Gmbh Procédé de concentration d'acide acrylique aqueux
US3337740A (en) * 1962-02-13 1967-08-22 Deering Milliken Res Corp Process for separating acrylic acid from impurities

Cited By (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3527677A (en) * 1969-03-06 1970-09-08 Goodrich Co B F Process for dehydration of aqueous acrylic acid solutions by extractive - azeotropic distillation with 2-ethylhexanol or 2-ethylhexylacrylate
US3932500A (en) * 1971-07-21 1976-01-13 Badische Anilin- & Soda-Fabrik Aktiengesellschaft Recovering anhydrous acrylic acid
US3868417A (en) * 1972-08-24 1975-02-25 Basf Ag Separation of acrylic acid from the reaction gases from propylene or acrolein oxidation
US4021310A (en) * 1972-12-22 1977-05-03 Nippon Shokubai Kagaku Kogyo Co., Ltd. Method for inhibiting the polymerization of acrylic acid or its esters
US4219389A (en) * 1977-06-14 1980-08-26 Rhone-Poulenc Industries Separation of acrylic acid from solutions thereof in tri-n-butyl phosphate
US4820385A (en) * 1988-02-18 1989-04-11 Monsanto Company Purification of alkyl glyoxylate in a continuous column by azeotropic distillation
KR100375780B1 (ko) * 1997-02-28 2003-08-19 니폰 쇼쿠바이 컴파니 리미티드 아크릴산의회수방법
EP0861820A3 (en) * 1997-02-28 1998-10-21 Nippon Shokubai Co., Ltd. Method for recovering acrylic acid
US6084127A (en) * 1997-02-28 2000-07-04 Nippon Shokubai Co Ltd Method for recovering acrylic acid
US6982026B2 (en) * 2001-03-15 2006-01-03 Tate & Lyle Ingredients Americas, Inc. Azeotropic distillation process for producing organic acids or organic acid amides
US6926810B2 (en) * 2001-03-15 2005-08-09 A. E. Staley Manufacturing Co. Process for obtaining an organic acid from an organic acid ammonium salt, an organic acid amide, or an alkylamine organic acid complex
US6984293B2 (en) * 2001-03-15 2006-01-10 Tate & Lyle Ingredients Azeotropic distillation of cyclic esters of hydroxy organic acids
US20030150705A1 (en) * 2002-01-08 2003-08-14 Deshpande Sanjeev D. Acrylic acid recovery utilizing ethyl acrylate and selected co-solvents
US20030205451A1 (en) * 2002-05-01 2003-11-06 Briegel Keith Frederick Process for manufacturing high purity methacrylic acid
US7128813B2 (en) * 2002-05-01 2006-10-31 Rohm And Haas Company Process for manufacturing high purity methacrylic acid
US20070015938A1 (en) * 2002-05-01 2007-01-18 Briegel Keith F Process for manufacturing high purity methacrylic acid
US20090084667A1 (en) * 2002-05-01 2009-04-02 Keith Frederick Briegel Process for manufacturing high purity methacrylic acid
US11866631B2 (en) 2019-04-29 2024-01-09 Ecolab Usa Inc. Oxygenated aminophenol compounds and methods for preventing monomer polymerization
US12312291B2 (en) 2019-04-29 2025-05-27 Ecolab Usa Inc. Oxygenated aromatic amines and use as antioxidants

Also Published As

Publication number Publication date
ES296656A1 (es) 1964-05-01
JPS4827292B1 (en, 2012) 1973-08-21
DE1468956A1 (de) 1969-01-02
LU45409A1 (en, 2012) 1964-04-13
NL6401921A (en, 2012) 1964-09-22
BE643942A (en, 2012) 1964-06-15
GB1055532A (en) 1967-01-18
FR1359885A (fr) 1964-04-30

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