US3280168A - Catalytic acrylonitrile production - Google Patents

Catalytic acrylonitrile production Download PDF

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US3280168A
US3280168A US381434A US38143464A US3280168A US 3280168 A US3280168 A US 3280168A US 381434 A US381434 A US 381434A US 38143464 A US38143464 A US 38143464A US 3280168 A US3280168 A US 3280168A
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acrylonitrile
bis
cyanoethylether
adiponitrile
feed
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US381434A
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Charles R Campbell
Iii Marion J Mathews
Jr John J Hicks
John F Giblin
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Monsanto Co
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Monsanto Co
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Priority to US381434A priority Critical patent/US3280168A/en
Priority to IL23897A priority patent/IL23897A/en
Priority to GB28643/65A priority patent/GB1089054A/en
Priority to SE8993/65A priority patent/SE312135B/xx
Priority to NL6508778A priority patent/NL6508778A/xx
Priority to NO158853A priority patent/NO116078B/no
Priority to FR24071A priority patent/FR1439659A/en
Priority to CH965565A priority patent/CH454119A/en
Priority to DE19651543213 priority patent/DE1543213A1/en
Priority to AT626065A priority patent/AT264492B/en
Priority to BE666700D priority patent/BE666700A/xx
Priority to LU49032D priority patent/LU49032A1/xx
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C253/00—Preparation of carboxylic acid nitriles
    • C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups

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  • This invention relates to the production of acrylonitrile. More particularly, it relates to the catalytic production of acrylonitrile from bis-cyanoethylether.
  • acrylonitrile can be electrohydrodimerized to adiponitrile.
  • the electrohydrodimerization takes place in the cathode compartment of a dually compartmented electrolytic cell.
  • the two compartments, anode and cathode, are separated by an ion exchange membrane.
  • An aqueous mixture comprised of acrylonitrile and a quaternary ammonium salt is continuously fed to the cathode compartment.
  • a solution of a strong mineral acid, usually sulfuric is circulated in the anode compartment.
  • acrylonitrile is converted to adiponitrile and a minor amount of byproducts, among which is bis-cyanoethylether.
  • the adiponitrile, byproducts and acrylonitrile contained in the eflluent from the cathode compartment are separated from the quaternary ammonium salt by an extraction procedure.
  • Acrylonitrile and propionitrile, a byproduct are subsequently separated from the adiponitrile by distillation in an acrylonitrile-propionitrile stripping column.
  • the tails from this distillation procedure comprised of adiponitrile and impurities, such as 3-hydroxypropioni-trile and bis-cyanoethylether, are passed to a distillation train to obtain a product of a least 99 weight percent adiponitrile.
  • Bis-cyanoethylether produced in the electrohydrodimerization procedure represents a yield loss. Furthermore, biscyanoethylether is in part thermally decomposed to 3- hydroxypropionitrile and acrylonitrile in the distillation train, thereby making the purification of adiponitrile more difficult.
  • An object of the invention is to provide a process for catalytically producing acrylonitrile from bis-cyanoethylether.
  • the above objects are achieved in the provision of a procedure for catalytically converting bis-cyanoethylether to acrylonitrile and 3-hydroxypropionitrile.
  • a small quantity of alkaline catalyst preferably a quaternary ammonium hydroxide, is intimately contacted with bis-cyanoethylether.
  • the catalyst and bis-cyanoethylethylether mixture is then heated to decompose the bis-cyanoethylether to acrylonitrile and 3-hydroxypropionitrile.
  • a process for catalytically converting to acrylonitrile and 3-hydroxypropionitrile the bis-cyanoethylether contained in a stream comprised of acrylonitrile, adiponitrile, propionitrile, bis-cyanoethylether, and 3-hydrox"'" nionitrile.
  • the process basically, comprises heating tnc )am in the presence of an alkaline catalyst, preferably a quaternary ammonium hydroxide.
  • any suitable strong base catalyzes the decomposition of bis-cyanoethylether.
  • Quaternary ammonium hydroxide compounds are preferred because they decompose at elevated temperatures to form trialkyl amines and a monohydroxy alcohol or alkene, all of which can be separated from the adiponitrile by distillation.
  • Metallic bases do not decompose as readily as do organic bases; thus, they remain in the crude adiponitrile as it is further purified in the hereinbefore noted distillation train. Distillation in the presence of a metallic base tends to increase the hydrolysis of adiponitrile and the formation of 2-cyanocylopentylideneimine.
  • Alkaline catalyst concentration can vary over a rather wide range.
  • a catalyst concentration of about one (1) percent based on the weight of bis-cyanoethylether substantially decomposes the bis-cyanoethylether contained in the feed to the distillation zone wherein acrylonitrile and propionitrile are separated from said feed.
  • One-tenth (0.10) of one percent alkaline catalyst based on the weight of bis-cyanoethylether contatined in the feed mentioned next above decomposes about Weight percent of the bis-cyanoethylether.
  • As low as one (1) part per million alkaline catalyst based on the weight of the entire feed to the acrylonitrile-propionitrile stripping column, decomposes a substantial portion of the bis-cyanoethylether contained therein.
  • the drawing is a schematic flow diagram illustrating a specific embodiment of the invention.
  • the drawing illustrates a convenient point in the adiponitrile separation and purification procedure where catalytic decomposition of biscyanoethylether can take place.
  • the system represented in the drawing is a distillation column wherein acrylonitrile and propionitrile are stripped from a stripper feed similar to that described in Table I below.
  • This column is preferably operated at about atmospheric pressure. Decomposition of bis-cyanoethylether can be accomplished at below atmospheric pressure; but, condensation and recovery of acrylonitrile is more difficult. This column is a convenient point to decompose biscyanoethylether, for one of its basic functions is to strip away acrylonitrile. It follows that at this point in the acrylonitrile recovery process very little new equipment would be necessary to practice the invention.
  • Stripper feed is fed to stripper 18 through line 10.
  • a small quantity of an alkaline catalyst for descriptive purposes hereinafter restricted to quaternary ammonium hydroxide, is metered from reservoir 12 through line 14 to feed line 10. It is to be noted that catalyst could also be metered into the column itself rather than the feed line.
  • a typical stripper feed is set forth in the following table.
  • Feed is introduced near the top of column 18.
  • This column is operated at substantially atmospheric pressure and customarily has a base temperature from 200 to 220 C.
  • the temperature across the column varies, i.e., the base temperature is greater than at the top.
  • the base temperature of the column can range from 150 to 250 C.
  • Bis-cyanoethylether is catalytically decomposed to acrylonitrile and 3-hydroxypropionitrile.
  • Trialkylamine, monohydroxy alcohol or alkene, catalytically produced acrylonitrile, acrylonitrile already present in the feed, water and propionitrile are distilled overhead through line 20. After condensation the overhead stream separates in decanter 22 to produce an organic and an aqueous layer.
  • the organic layer comprised of acrylonitrile, propionitrile and water
  • the aqueous layer comprised of Water and a minor quantity of acrylonitrile
  • a portion of the aqueous layer is recycled as reflux to column 18 via line 26 while the remainder flows by way of line 28 to an acrylonitrile recovery distillation column.
  • a tails stream of crude adiponitrile treated in accordance with the invention is withdrawn from column 18 via line 32. This tails stream has a typical composition as shown in the following table.
  • High boilers are primarily d cyanosuberonitrile and other higher molecular weight acrylonitrile oligomers.
  • Example II A series of continuous distillations were performed in which feed of a composition shown in Table III was introduced onto the top tray of a lO-tray, 2-inch Oldershaw column. The still was mounted on an electrically heated reboiler having a weir arrangement for continuous withdrawal of still tails. Overhead vapors were condensed in a glass condenser and the condensate flowed to a decanter wherein an upper layer containing acrylonitrile, propionitrile, and water was separated from a lower aqueous layer containing about 7 weight percent acrylonitrile.
  • Feed was pumped to the column at the rate of 1,675 grams per hour.
  • the aqueous, lower layer from the decanter was returned to the top of the column as reflux at 360 grams per hour.
  • the residence time of the tails in the reboiler at a tails withdrawal rate of 360 grams per hour was 2 hours.
  • the reboiler temperature was maintained at 200-210 C. while the head temperature ranged from 80 to 85 C.
  • Composition of Tails Stream Composition Component of Feed Strem With No With 13 p.p.m. With 310 p.p.m. With 130 p.p.m.
  • TMAOH is tetramethylammonium hydroxide.
  • TBAOH is tetrabutylammonium hydroxide.
  • Example I Twenty-five (25) grams of bis-cyanoethylether and one (1) gram of an aqueous solution having a 25 weight perproduced from acrylonitrile. Furthermore, a process is provided for the effective removal of bis-cyanoethylether from the crude adiponitrile prior to its entering the adiponitrile purifying distillation train.
  • a continuous process for producing acrylonitrile from bis-cyanoethylether produced as a by-product in the electrohydrodimerization of acrylonitrile to adiponithe heated zone contains at least 1 part per million alkaline catalyst based on the weight of the stream.

Description

Oct 1966 c. R. CAMPBELL ETAL 3,280,168
CATALYTIC AGRYLONITRILE PRODUCTION Filed July 9, 1964 INVENTORS BY filial 771. TM
ATTORNEY United States Patent O 3,280,168 CATALYTIC ACRYLONETRILE PRODUCTHON Charles R. Campbell, Marion J. Mathews HI, and John J. Hicks, J12, Pensacola, Fla., and John F. Giblnr, Decatur, Ala., assignors to Monsanto Company, St. Louis, Mo., a corporation of Delaware Filed July 9, 1964, Ser. No. 381,434 6 Claims. (Cl. 260-4653) This invention relates to the production of acrylonitrile. More particularly, it relates to the catalytic production of acrylonitrile from bis-cyanoethylether.
It is known that acrylonitrile can be electrohydrodimerized to adiponitrile. Ordinarily, the electrohydrodimerization takes place in the cathode compartment of a dually compartmented electrolytic cell. The two compartments, anode and cathode, are separated by an ion exchange membrane. An aqueous mixture comprised of acrylonitrile and a quaternary ammonium salt is continuously fed to the cathode compartment. A solution of a strong mineral acid, usually sulfuric, is circulated in the anode compartment. As current flows through the cell, acrylonitrile is converted to adiponitrile and a minor amount of byproducts, among which is bis-cyanoethylether.
After electrohydrodimerization, the adiponitrile, byproducts and acrylonitrile contained in the eflluent from the cathode compartment are separated from the quaternary ammonium salt by an extraction procedure. Acrylonitrile and propionitrile, a byproduct, are subsequently separated from the adiponitrile by distillation in an acrylonitrile-propionitrile stripping column. The tails from this distillation procedure, comprised of adiponitrile and impurities, such as 3-hydroxypropioni-trile and bis-cyanoethylether, are passed to a distillation train to obtain a product of a least 99 weight percent adiponitrile.
Bis-cyanoethylether produced in the electrohydrodimerization procedure represents a yield loss. Furthermore, biscyanoethylether is in part thermally decomposed to 3- hydroxypropionitrile and acrylonitrile in the distillation train, thereby making the purification of adiponitrile more difficult.
An object of the invention is to provide a process for catalytically producing acrylonitrile from bis-cyanoethylether.
Further, it is an object of this invention to provide a process for decomposing bis-cyanoethylether obtained as a by-product of the electrohydrodirneric conversion of acrylonitrile to adiponitrile, thus increasing the yield of adiponitrile electrohydrodimerized from acrylonitrile.
Other objects will become apparent from the following descriptive material.
In general, the above objects are achieved in the provision of a procedure for catalytically converting bis-cyanoethylether to acrylonitrile and 3-hydroxypropionitrile. A small quantity of alkaline catalyst, preferably a quaternary ammonium hydroxide, is intimately contacted with bis-cyanoethylether. The catalyst and bis-cyanoethylethylether mixture is then heated to decompose the bis-cyanoethylether to acrylonitrile and 3-hydroxypropionitrile.
To be more specific, a process is provided for catalytically converting to acrylonitrile and 3-hydroxypropionitrile the bis-cyanoethylether contained in a stream comprised of acrylonitrile, adiponitrile, propionitrile, bis-cyanoethylether, and 3-hydrox"'" nionitrile. The process, basically, comprises heating tnc )am in the presence of an alkaline catalyst, preferably a quaternary ammonium hydroxide.
It has been discovered that when the pH of the catholyte from the electrohydrodimerization of acrylonitrile to adiponitrile is alkaline, a portion of the bis-cyanoethylether contained therein decomposes at elevated temperatures to form 3-hydroxypropionitrile and acrylonitrile.
ICC
On evaluation of various alkaline compounds including potassium hydroxide, tetrabutylammoniurn hydroxide and tetramethylammonium hydroxide, one finds that any suitable strong base catalyzes the decomposition of bis-cyanoethylether. Quaternary ammonium hydroxide compounds are preferred because they decompose at elevated temperatures to form trialkyl amines and a monohydroxy alcohol or alkene, all of which can be separated from the adiponitrile by distillation. Metallic bases do not decompose as readily as do organic bases; thus, they remain in the crude adiponitrile as it is further purified in the hereinbefore noted distillation train. Distillation in the presence of a metallic base tends to increase the hydrolysis of adiponitrile and the formation of 2-cyanocylopentylideneimine.
Alkaline catalyst concentration can vary over a rather wide range. A catalyst concentration of about one (1) percent based on the weight of bis-cyanoethylether substantially decomposes the bis-cyanoethylether contained in the feed to the distillation zone wherein acrylonitrile and propionitrile are separated from said feed. One-tenth (0.10) of one percent alkaline catalyst based on the weight of bis-cyanoethylether contatined in the feed mentioned next above decomposes about Weight percent of the bis-cyanoethylether. As low as one (1) part per million alkaline catalyst, based on the weight of the entire feed to the acrylonitrile-propionitrile stripping column, decomposes a substantial portion of the bis-cyanoethylether contained therein.
The drawing is a schematic flow diagram illustrating a specific embodiment of the invention.
To aid in further describing the invention, reference will now be made to the drawing. The drawing illustrates a convenient point in the adiponitrile separation and purification procedure where catalytic decomposition of biscyanoethylether can take place. The system represented in the drawing is a distillation column wherein acrylonitrile and propionitrile are stripped from a stripper feed similar to that described in Table I below.
This column is preferably operated at about atmospheric pressure. Decomposition of bis-cyanoethylether can be accomplished at below atmospheric pressure; but, condensation and recovery of acrylonitrile is more difficult. This column is a convenient point to decompose biscyanoethylether, for one of its basic functions is to strip away acrylonitrile. It follows that at this point in the acrylonitrile recovery process very little new equipment would be necessary to practice the invention.
Decomposition of bis-cyanoethylether could take place at other points in the process for separation and purification of adiponitrile. However, they would not be nearly as convenient as the point or locale illustrated.
Stripper feed is fed to stripper 18 through line 10. Prior to entering the column a small quantity of an alkaline catalyst, for descriptive purposes hereinafter restricted to quaternary ammonium hydroxide, is metered from reservoir 12 through line 14 to feed line 10. It is to be noted that catalyst could also be metered into the column itself rather than the feed line. A typical stripper feed is set forth in the following table.
TABLE I.TYPICAL STRIPPER FEED COMPOSITION 1 Principally 4-cyauo suberonitrlle 2 Principally suecinonltrile, cyanocyelopentylideneimine, cyanovaleramlde, and cyanovalerlc acid.
Feed is introduced near the top of column 18. This column is operated at substantially atmospheric pressure and customarily has a base temperature from 200 to 220 C. The temperature across the column varies, i.e., the base temperature is greater than at the top. The base temperature of the column can range from 150 to 250 C. Bis-cyanoethylether is catalytically decomposed to acrylonitrile and 3-hydroxypropionitrile. Trialkylamine, monohydroxy alcohol or alkene, catalytically produced acrylonitrile, acrylonitrile already present in the feed, water and propionitrile are distilled overhead through line 20. After condensation the overhead stream separates in decanter 22 to produce an organic and an aqueous layer. The organic layer, comprised of acrylonitrile, propionitrile and water, is withdrawn through line 30. The aqueous layer, comprised of Water and a minor quantity of acrylonitrile, is withdrawn from decanter 22 by means of line 24. A portion of the aqueous layer is recycled as reflux to column 18 via line 26 while the remainder flows by way of line 28 to an acrylonitrile recovery distillation column. A tails stream of crude adiponitrile treated in accordance with the invention is withdrawn from column 18 via line 32. This tails stream has a typical composition as shown in the following table.
TABLE IL-TYPICAL STRIPPER TAILS COMPOSITION With 13 ppm. tetramethylamrnonium hydroxide added to feed Component:
Acrylonitrile 0.30 3-iydroxypropionitrile 3 .49 Z-meth-ylglutaronitrile 0.3 2
Adiponitrile 90.75
High boilers 1 3.66 2-cyan0cyclopentylideneirnine 0.3 8 Cyanovaleric acid 0.39 Bis-cyanoethylether 0.17
1 High boilers are primarily d cyanosuberonitrile and other higher molecular weight acrylonitrile oligomers.
cent concentration of tetramethylammonium hydroxide therein were charged to a 100 ml. round-bottom flask equipped with a thermometer well. This flask was fitted with a heating mantle, distilling head, condenser, and receiver. The flask was heated until the temperature reached 124 C. at which point material began to distill overhead. The temperature of the flask was increased over a four-minute period to 150 C. at the end of which it was cooled to room temperature. Condensate distilled overhead weighed 6.24 grams and contained 5.99 grams (96%) acrylonitrile. This experiment demonstrates that bis-cyanoethylether can be decomposed efiectively in the presencee of an alkaline catalyst to produce acrylonitrile.
Example II A series of continuous distillations were performed in which feed of a composition shown in Table III was introduced onto the top tray of a lO-tray, 2-inch Oldershaw column. The still was mounted on an electrically heated reboiler having a weir arrangement for continuous withdrawal of still tails. Overhead vapors were condensed in a glass condenser and the condensate flowed to a decanter wherein an upper layer containing acrylonitrile, propionitrile, and water was separated from a lower aqueous layer containing about 7 weight percent acrylonitrile.
Feed was pumped to the column at the rate of 1,675 grams per hour. The aqueous, lower layer from the decanter was returned to the top of the column as reflux at 360 grams per hour. The residence time of the tails in the reboiler at a tails withdrawal rate of 360 grams per hour was 2 hours. The reboiler temperature was maintained at 200-210 C. while the head temperature ranged from 80 to 85 C.
A series of runs was performed employing the above operating conditions and using various catalysts and catalyst concentrations; in one of the runs no alkaline catalyst was added to the feed. Table HI summarizes the runs. Compositions are given in weight percent.
TABLE III-SUMMARY OF RUNS EMPLOYING ALKALINE CATALYSTS TO DECOMPOSE BIS-CYANOETHYLETHE R.
Composition of Tails Stream Composition Component of Feed Strem With No With 13 p.p.m. With 310 p.p.m. With 130 p.p.m.
Catalyst TMAOI-I 2 TBAOH KOH 4 Added to Feed Added to Feed Added to Feed Acrylonitrilo, percent i, 73. 84 0. 25 30 0.23 0.14 Propionitrile, percent 5. 43 3-Hydroxypr0pionitrile,
percent O. 20 2. 75 3. 49 1. 0. 64 Z-methylglutaronitrile,
percent 0. 11 0. 58 .32 0. 40 0. 53 Adiponitrile, percent 18. 00 86. 83 9 .75 93. 20 92. 57 High Boilers percen 0. 85 3. 29 3. 6 2. 98 3. 95 2 eyauocyclopentyllden imine, percent 0. O1 0. 31 38 0. D6 0. 21 Cyanovalerie Acid,
percent 0. l8 0. 32 39 0. 85 0. 53 B is-cyanoethylether,
percent 1. 30 4. 93 0. l7 0. 00 0. 00
1 High boilers are primarily cyariosuberonitrile and other higher molecular weight aerylonitrile oligomers 2 TMAOH is tetramethylammonium hydroxide. 3 TBAOH is tetrabutylammonium hydroxide.
4 KOH is potassium hydroxide.
The following examples are set forth to illustrate the invention. They are intended to elucidate and are not intended to be limiting in any way.
Example I Twenty-five (25) grams of bis-cyanoethylether and one (1) gram of an aqueous solution having a 25 weight perproduced from acrylonitrile. Furthermore, a process is provided for the effective removal of bis-cyanoethylether from the crude adiponitrile prior to its entering the adiponitrile purifying distillation train.
Although the invention has been described by reference to specific embodiments, it should be broadly construed and should be limited only to the scope of the claims appended hereto.
We claim:
1. A continuous process for producing acrylonitrile from bis-cyanoethylether produced as a by-product in the electrohydrodimerization of acrylonitrile to adiponithe heated zone contains at least 1 part per million alkaline catalyst based on the weight of the stream.
3. The process of claim 1 wherein the highest tem perature in the heated zone is between and 250 C.
4. The process of claim 1 wherein the distillation is performed at substantially atmospheric pressure.
5. The process of claim 1 wherein the alkaline catalyst is a quaternary ammonium hydroxide.
6. The method of claim 1 wherein the quaternary ammonium hydroxide is tetramethylammonium hydroxide.
References Cited by the Examiner UNITED STATES PATENTS 2,382,036 8/1945 Bruson 260465.6 2,448,979 9/1948 Hopff et al 260465.6 2,770,640 11/1956 Journeay 260465.9 X-R 2,790,818 4/1957 Journeay 260465.9 XR 2,816,130 12/1957 Selcer et a1. 260465.6 2,832,798 4/1958 Rapoport 260465.9 3,024,267 3/ 1962 Howsman 260465 .6
CHARLES B. PARKER, Primary Examiner.
JOSEPH P. BRUST, Assistant Examiner.
UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,280,168 October 18, 1966 Charles R. Campbell et ale It is hereby certified that error appears in the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.
Column 1, line 64, the indistinct word should read S-hydroxypropionitrile line 65, the indistinct words should read the stream Signed and sealed this 5th day of September 1967! L) Attest:
ERNEST W. SWIDER Attesting Officer EDWARD J. BRENNER Commissioner of Patents

Claims (1)

1. A CONTINUOUS PROCESS FOR PRODUCING ACRYLONITRILE FROM BIS-CYANOETHYLETHER PRODUCED AS A BY-PRODUCT IN THE ELECTROHYDRODIMERIZATION OF ACRYLONITRILE TO ADIPONITRILE COMPRISING THE STEPS OF: (A) METERING A MINOR QUANTITY OF AN ALKALINE CATALYST SELECTED FROM THE GROUP CONSISTING OF QUATERNARY AMMONIUM HYDROXIDE AND POTASSIUM HYDROXIDE INTO A STREAM COMPRISED OF ACRYLONITRILE, ADIPONITRILE, PROPIONITRILE, BIS-CYANOETHYLETHER, AND 3-HYDROXYPROPIONITRILE; (B) FEEDING SAID STREAM HAVING ALKALINE CATALYST THEREIN INTO A ZONE BETWEEN 70 AND 250*C.; AND (C) DISTILLING SAID STREAM TO REMOVE ACRYLONITRILE AND PROPIONITRILE THEREFROM.
US381434A 1964-07-09 1964-07-09 Catalytic acrylonitrile production Expired - Lifetime US3280168A (en)

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Application Number Priority Date Filing Date Title
US381434A US3280168A (en) 1964-07-09 1964-07-09 Catalytic acrylonitrile production
IL23897A IL23897A (en) 1964-07-09 1965-07-06 Catalytic acrylonitrile production
GB28643/65A GB1089054A (en) 1964-07-09 1965-07-06 Acrylonitrile production from dimerisation by products
SE8993/65A SE312135B (en) 1964-07-09 1965-07-07
NO158853A NO116078B (en) 1964-07-09 1965-07-08
NL6508778A NL6508778A (en) 1964-07-09 1965-07-08
FR24071A FR1439659A (en) 1964-07-09 1965-07-09 Catalytic production of acrylic nitrile
CH965565A CH454119A (en) 1964-07-09 1965-07-09 Catalytic production of acrylonitrile
DE19651543213 DE1543213A1 (en) 1964-07-09 1965-07-09 Process for the catalytic production of acrylonitrile from biscyanoethyl ether
AT626065A AT264492B (en) 1964-07-09 1965-07-09 Process for the catalytic production of acrylonitrile
BE666700D BE666700A (en) 1964-07-09 1965-07-09
LU49032D LU49032A1 (en) 1964-07-09 1965-07-09

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Cited By (5)

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US3429783A (en) * 1965-02-10 1969-02-25 Monsanto Co Process for upgrading an acrylonitrile electrohydrodimerization effluent containing adiponitrile by distillation and alkaline treatment
US3479389A (en) * 1967-03-16 1969-11-18 Monsanto Co Production of olefinic nitriles by catalytic dehydration of monohydroxylated paraffinic nitriles and subsequent flash distillation
US3674653A (en) * 1969-05-01 1972-07-04 Asahi Chemical Ind Method of the purification of catholytes
US4072713A (en) * 1972-07-27 1978-02-07 Phillips Petroleum Company Method for separating tetraalkylammonium salts
US4128571A (en) * 1977-10-27 1978-12-05 Monsanto Company Thermal conversion of 4-cyano-suberonitrile to acrylonitrile

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GB8323961D0 (en) * 1983-09-07 1983-10-12 Bp Chem Int Ltd Chemical process

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US2382036A (en) * 1941-01-10 1945-08-14 Resinous Prod & Chemical Co Bis(2-cyanoethyl) ether and process for making same
US2448979A (en) * 1940-06-19 1948-09-07 Hopff Heinrich Process for the production of beta, beta'-dicyano diethyl ether
US2770640A (en) * 1954-09-23 1956-11-13 Monsanto Chemicals Cyanoethylation of ketones
US2790818A (en) * 1954-09-23 1957-04-30 Monsanto Chemicals Cyanoethylation of organic sulfur compounds
US2816130A (en) * 1955-04-06 1957-12-10 Monsanto Chemicals Preparation of beta, beta'-oxydipropionitrile
US2832798A (en) * 1955-06-30 1958-04-29 American Cyanamid Co Preparation of acrylonitrile from beta, beta'-oxydipropionitrile
US3024267A (en) * 1959-09-03 1962-03-06 Standard Oil Co Preparation of hydracrylonitrile

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2448979A (en) * 1940-06-19 1948-09-07 Hopff Heinrich Process for the production of beta, beta'-dicyano diethyl ether
US2382036A (en) * 1941-01-10 1945-08-14 Resinous Prod & Chemical Co Bis(2-cyanoethyl) ether and process for making same
US2770640A (en) * 1954-09-23 1956-11-13 Monsanto Chemicals Cyanoethylation of ketones
US2790818A (en) * 1954-09-23 1957-04-30 Monsanto Chemicals Cyanoethylation of organic sulfur compounds
US2816130A (en) * 1955-04-06 1957-12-10 Monsanto Chemicals Preparation of beta, beta'-oxydipropionitrile
US2832798A (en) * 1955-06-30 1958-04-29 American Cyanamid Co Preparation of acrylonitrile from beta, beta'-oxydipropionitrile
US3024267A (en) * 1959-09-03 1962-03-06 Standard Oil Co Preparation of hydracrylonitrile

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3429783A (en) * 1965-02-10 1969-02-25 Monsanto Co Process for upgrading an acrylonitrile electrohydrodimerization effluent containing adiponitrile by distillation and alkaline treatment
US3479389A (en) * 1967-03-16 1969-11-18 Monsanto Co Production of olefinic nitriles by catalytic dehydration of monohydroxylated paraffinic nitriles and subsequent flash distillation
US3674653A (en) * 1969-05-01 1972-07-04 Asahi Chemical Ind Method of the purification of catholytes
US4072713A (en) * 1972-07-27 1978-02-07 Phillips Petroleum Company Method for separating tetraalkylammonium salts
US4128571A (en) * 1977-10-27 1978-12-05 Monsanto Company Thermal conversion of 4-cyano-suberonitrile to acrylonitrile

Also Published As

Publication number Publication date
GB1089054A (en) 1967-11-01
BE666700A (en) 1966-01-10
IL23897A (en) 1969-06-25
NO116078B (en) 1969-01-27
AT264492B (en) 1968-09-10
SE312135B (en) 1969-07-07
DE1543213A1 (en) 1969-08-14
LU49032A1 (en) 1966-01-10
NL6508778A (en) 1966-01-10
CH454119A (en) 1968-04-15

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