US2404163A - Method of refining crude olefinic nitriles - Google Patents

Method of refining crude olefinic nitriles Download PDF

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Publication number
US2404163A
US2404163A US302072A US30207239A US2404163A US 2404163 A US2404163 A US 2404163A US 302072 A US302072 A US 302072A US 30207239 A US30207239 A US 30207239A US 2404163 A US2404163 A US 2404163A
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Prior art keywords
water
nitrile
acrylonitrile
layer
crude
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Expired - Lifetime
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US302072A
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English (en)
Inventor
Erwin L Carpenter
Harold S Davis
Oscar F Wiedeman
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Wyeth Holdings LLC
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American Cyanamid Co
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Priority to US302072A priority Critical patent/US2404163A/en
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Publication of US2404163A publication Critical patent/US2404163A/en
Priority to BE474492A priority patent/BE474492A/fr
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C253/00—Preparation of carboxylic acid nitriles
    • C07C253/32—Separation; Purification; Stabilisation; Use of additives
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C253/00—Preparation of carboxylic acid nitriles
    • C07C253/32—Separation; Purification; Stabilisation; Use of additives
    • C07C253/34—Separation; Purification
    • 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
    • Y10S203/03—Acrylonitrile

Definitions

  • afquantity of 'a crude oleflnic nitrile such as, for example, a crude product of acrylonitrile and water produced, for instance,
  • the present invention relates to the refining of crude oletlnic nitriles, that is, those nitriles which may be hydrolyzed to olenlc acids.
  • the upper nitrile layer of the product is found to contain from4 to 5% of water whereas the lower or water layer may contain from 5-8% of nitrile.
  • Fig. 1 is a diagrammatic ilow sheetvof a preferred method of carrying out theinvention
  • ll'lg. 2 shows a modied method
  • Fig. 3 illustrates still another alternative sysby the dehydration of ethylene cyanohydrin, is permitted to separate into two layers.
  • the lower layer of water containingfrom 5 'to 8% of acrylonitrile is withdrawn and shaken with about twice its volume of xylene.
  • the mixture separates into two layers upon standing.
  • the lower layer being principally water, isj withdrawn and discarded.
  • the upper xylene layer containing the acrylonitrile is united with the initial acrylonitrile layer containing from 4 to 5% water.
  • the xylene displaces a small amount of water from the mixture.
  • This water layer is withdrawn and returned to an initial water layer containing some acrylonitrile.-
  • the remaining layer of acrylonitrile, xylene and dissolved water is fractionated in a fractionating still operating with substantially total reflux of the nitrile. 'I'he Water and nitrile form an azeotropic mixture in the reflux column.
  • this reux mixture is condensed at the retlux head and allowed to' stratify into two layers.
  • the upper nitrile layer flows -back into the still while the lowerfwater layer is-Withdrawn and returned to an initial water layer containing some acrylonitrile.
  • a small amount of nitrilepolymer forms As illustrated by the flow sheet of Fig.2, a nuan-v tity of a crude olefinic nitrile such as. for examv ple, a crude product of acrylonitrile and water, f producedasv above, is permitted to separate into vtwo layers.
  • the lower layer of ⁇ waterfcontaining lfrom 5 to 8% of acrylonitrile is withdrawnzand ol vThe mixture upon standing separates into two layers.
  • the lower layer being principally water shaken with .about twice its volume of xylene.
  • the .crude product is allowed to separate into two layers.
  • the lower layer of 'water containing some nitrile is withdrawn and discarded.
  • the upper acrylonitrile layer containing some ,water is fractionated in a fractionating still operating with substantiallyy total reux of the nitrile.
  • the water and acrylonitrile form an azeotropic mixture in the reflux column. Over a temperature range of from 70 to'75 C. this mixture is condensed at the reflux head and allowed to stratify into two layers.
  • the upper nitrile layer flows back into the still while the lower water layer is withdrawn and discarded.
  • a fraction of wet acrylonitrile is then removed at a temperature of from 75 to 77C. and returned to an initial acrylonitrile layer containing water.
  • the dry acrylonitrile is distilled from the polymer residue at a temperaturev of from '77 to 78 C.
  • a crude crotonic nitrile-water mixture produced for instance by the dehydration of propylene cyanohydrin, is ⁇ permitted to separate into two layers.
  • the lower layer of water containing some crotonic nitrile is withdrawn and discarded.
  • the upper layer which is predominantly crotonic nitrile containing some water is dried by azeotropic distillation from a fractionating still.
  • the water and crotonic nitrile form an azeotropic mixture boiling ata temperature yof about 85 C. which is condensed at the reflux head of the still and permitted'to stratify into two layers.
  • the upper crotonic nitrile layer is returned to the still while the lower water layer is removed and discarded.
  • the cisand trans-crotonic nitrile isomers are thereafter fractionally distilled from the stillcontent at the temperatures of 107.5-108.5 C. and 119.0120.5 C. respectively.
  • Olenic nitrile solvents which'are immiscible with water, such as benzene, toluene, xylene and the like are suitable for the extraction of the oleiinic nitrile from the water layer.
  • yl. 'Avmethod of refining a crude olenic nitrile containing' water which comprises separating the product into two layers, the upper of which is predominantly nitrile containing some water while the lower layer is predominantly water containing some nitrile, extracting the nitrile from said lower layer by means of a hydrocarbon solvent, combining the solvent extract and upper nitrile layer, permitting the mix to stratify, re-
  • a method of refining crude acrylonitrile containing water which comprises separating the product into two layers, the upper of which is prei dominantly acrylonitrile containing some water while the lower layer is predominantly water containing same acrylonitrile, extracting the acrylonitrile from the said lower layer by means of xylene, combining the xylene extract and upper acrylonitrile layer, permitting the mix to stratify.
  • a method ⁇ of reilning a crude oleflnic nitrile containing water which comprises separating the product into two layers, the upper of which is predominantly nitrile containing some water while the lower la'yer is predominantly water containing some nitrile, extracting the nitrile from said lower layer by means of a hydrocarbon solvent, distilling the nitrile from the hydrocarbon solvent, separating the still residuev of polymer and hydrocarbon solvent and returning the latter to the cycle, distilling the major portion of "the water from tlieinitially produced upper nitrile layer and returning said ⁇ water distillate to a subsequently produced initial water layer containing nitrile, adding to the nitrile layer remaining from the major water removal step, the nitrile from the hydrocarbon solvent extract to form a-nitrile mixture, subsequently fractionally distilling a wet nitrile fraction from the said nitrile mixture and returningsaid nitrile fraction to an initial nitrile layer containing water, thereafter fractionally distilling
  • a method of refining crude acrylonitrile containing water which comprises separating the ⁇ product into two layers, the upper of which is predominantly acrylonitrile containing some water while the lower layer is predominantly water containing some acrylonitrile, extracting the acrylonitrile from the said lower layer by means of xylene, distilling the acrylonitrile from the xylene, separating the still residue of polymer and xylene and returning the latter to the cycle, distilling the major portion of the water from the upper acrylonitrile layer at a temperature of from 'I0 to 75 C.
  • a method of refining a crude olenic nitrile containing water which comprises separating the product into two layers, the upper of which is predominantly nitrile containing some water while the lower layer is predominantly water containing some nitrile, distilling from the upper nitrile layer an azeotropic mixture of nitrile and water, subsequently fractionally distilling a wet nitrile fraction therefrom and returning the same to a subsequently produced initial nitrile layer containing water, thereafter 4distilling the dry olenic nitrile from the polymer residue.
  • a method of refining crude acrylonitrile containing water which comprises separating the product into two layers, the upper of which is predominantly acrylonitrile containing some water while the lower layer is predominantly water containing some acrylonitrile, distilling from the upper acrylonitrile layer an azeotropic mixture of acrylonitrile and water until the distillate temperature has risen from 70 C. to '75 C., subsequently fractionally distilling a wet acrylonitrile fraction therefrom at a temperature of from 'l5-77 C. and returning the same to a subsequently produced initial acrylonitrile layer containing water, thereafter distilling the dry acrylonitrile from the polymer residue at a temperature of from 77 to '78 C.
  • a method of refining crude crotonic nitrile containing water which comprises separating the product into two layers, the upper of which is predominantly crotonic nitrile containing some water while the lower layer is predominantly water containing some crotonic nitrile, distilling from the upper crotonic nitrile layer an azeotropic mixture of crotonic nitrile and Water until the crude crotonic nitrile is substantially dehydrated, subsequently distilling a wet crotonic nitrile fraction therefrom to remov.
  • a method of refining a crude olenic nitrile containing water to remove water therefrom which comprises distilling therefrom an azeotropic mixture of the nitrile and water, condensing the distillate, permitting the condensed distillate to stratify into an upper wet nitrile layer and a lower water layer. separating et! the water layer, returning the wet nitrile layer to the distilland for recycling and finally collecting the substantially dehydrated nitrile.
  • a method of refining a crude acrylonitrile containing water to remove water therefrom which comprises distilling therefrom an azeotropic mixture of the acrylonitrile and water, condensing the distillate, permitting the condensed distillate to stratify into an upper wet acrylonitrile layer and a lower water layer, separating off the water layer, returning the wet acrylonitrile layer to the distillandv for recycling and nally collecting the substantially dehydrated acrylonitrile.
  • a method of refining a crude crotonic nitrile containing water to substantially dehydrate the same which comprises distilling therefrom an azeotropic mixture of the crotonic nitrile and water, condensing the distillate, permitting the condensed distillate to stratify into an upper wet crotonic nitrile layer and a lower water layer, separating olf the waterlayer, returning the wet crotonic nitrile layer to the distilland for recycling and finally collecting the substantially dehydrated crotonic nitrile.
  • the process which comprises placing the crude nitrile in a still provided with a fractionating column and a condenser, distilling an azeotropic mixture of nitrile and water from the crude nitrile, passing the vapor distillate through the fractionating column and into the condenser, condensing the distillate,' allowing the distillate t0 stratify into an upper nitrile layer substantially saturated with water,A and a lower water layer, drawing oif the water layer, and returning the wet nitrile to the fractionating column, and finally collecting the substantially dehydrated nitrile.
  • the process which comprises placing the crude acrylonitrile in a still provided with a fractionating column and a. condenser, distilling an azeotropic mixture of acrylonitrile and water from the crude acrylonitrile, passing the vapor distillate through the fractionating column and into the condenser, condensing the distillate, allowing the distillate to stratify into an upper acrylonitrile layer substantially saturated with water, and a lower water layer, drawing ofi ⁇ the water layer, and returning the wet acrylonitrile to the fractionating column, and finally collecting the substantially dehydrated acrylonitrile.
  • the yprocess which comprises placing the crude crotonic nitrile in a still provided with a fractionating column and a condenser, distillng an azeotropic mixture of crotonic nitrile and water from the crude crotonic nitrile, passing the vapor distillate through the fractionating column and into the condenser, condensing the distillate, allowing the distillate to stratify into an upper crotonic nitrile layer substantially saturated with water, and a lower water layer, drawing olf the water layer, and returning the wet crotonic nitrile to the fractionating column, and iinally collecting the substantially dehydrated crotonic nitrile.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US302072A 1939-10-31 1939-10-31 Method of refining crude olefinic nitriles Expired - Lifetime US2404163A (en)

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Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2453472A (en) * 1944-10-12 1948-11-09 Sinclair Refining Co Dehydration of saturated nitriles
US2527660A (en) * 1949-07-12 1950-10-31 Allied Chem & Dye Corp Methacrylonitrile purification
US2542752A (en) * 1949-05-27 1951-02-20 Shell Dev Dehydration of acrolein by stratification and distillation
US2582214A (en) * 1946-03-20 1952-01-08 Distillers Co Yeast Ltd Process for drying alcohols and ketones
US2621204A (en) * 1950-01-26 1952-12-09 Celanese Corp Production of acrylonitrile
US2681306A (en) * 1952-02-06 1954-06-15 Du Pont Purification of acrylonitrile by extractive distillation
US2719169A (en) * 1951-06-30 1955-09-27 Eastman Kodak Co Method of refining crude acrylonitrile
US2836614A (en) * 1952-08-13 1958-05-27 Distillers Co Yeast Ltd Process for producing unsaturated nitriles
US3074968A (en) * 1960-06-03 1963-01-22 American Viscose Corp Method of separating a mixture of tetrahydrofuran, toluene and water
US3133957A (en) * 1960-04-07 1964-05-19 Distillers Co Yeast Ltd Purification of acrylonitrile
US3149055A (en) * 1962-08-22 1964-09-15 Standard Oil Co Purification of olefinically unsaturated nitriles
US3155599A (en) * 1962-08-22 1964-11-03 Standard Oil Co Removal of saturated carbonyl compounds from unsaturated nitriles

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2453472A (en) * 1944-10-12 1948-11-09 Sinclair Refining Co Dehydration of saturated nitriles
US2582214A (en) * 1946-03-20 1952-01-08 Distillers Co Yeast Ltd Process for drying alcohols and ketones
US2542752A (en) * 1949-05-27 1951-02-20 Shell Dev Dehydration of acrolein by stratification and distillation
US2527660A (en) * 1949-07-12 1950-10-31 Allied Chem & Dye Corp Methacrylonitrile purification
US2621204A (en) * 1950-01-26 1952-12-09 Celanese Corp Production of acrylonitrile
US2719169A (en) * 1951-06-30 1955-09-27 Eastman Kodak Co Method of refining crude acrylonitrile
US2681306A (en) * 1952-02-06 1954-06-15 Du Pont Purification of acrylonitrile by extractive distillation
US2836614A (en) * 1952-08-13 1958-05-27 Distillers Co Yeast Ltd Process for producing unsaturated nitriles
US3133957A (en) * 1960-04-07 1964-05-19 Distillers Co Yeast Ltd Purification of acrylonitrile
US3074968A (en) * 1960-06-03 1963-01-22 American Viscose Corp Method of separating a mixture of tetrahydrofuran, toluene and water
US3149055A (en) * 1962-08-22 1964-09-15 Standard Oil Co Purification of olefinically unsaturated nitriles
US3155599A (en) * 1962-08-22 1964-11-03 Standard Oil Co Removal of saturated carbonyl compounds from unsaturated nitriles

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BE474492A (enrdf_load_stackoverflow) 1947-08-30

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