US3844911A - Method for producing adiponitrile - Google Patents

Method for producing adiponitrile Download PDF

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Publication number
US3844911A
US3844911A US00275556A US27555672A US3844911A US 3844911 A US3844911 A US 3844911A US 00275556 A US00275556 A US 00275556A US 27555672 A US27555672 A US 27555672A US 3844911 A US3844911 A US 3844911A
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US
United States
Prior art keywords
cell
stream
wash
acrylonitrile
wash stream
Prior art date
Legal status (The legal status 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 status listed.)
Expired - Lifetime
Application number
US00275556A
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English (en)
Inventor
F Ruehlen
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Phillips Petroleum Co
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Phillips Petroleum Co
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Filing date
Publication date
Application filed by Phillips Petroleum Co filed Critical Phillips Petroleum Co
Priority to US00275556A priority Critical patent/US3844911A/en
Priority to CA169,070A priority patent/CA1014102A/en
Priority to JP4713473A priority patent/JPS5310578B2/ja
Priority to IT26409/73A priority patent/IT994932B/it
Priority to GB3566773A priority patent/GB1417285A/en
Priority to BE133875A priority patent/BE802806A/xx
Priority to DE19732338341 priority patent/DE2338341C3/de
Priority to FR7327720A priority patent/FR2194671B1/fr
Application granted granted Critical
Publication of US3844911A publication Critical patent/US3844911A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B3/00—Electrolytic production of organic compounds
    • C25B3/20—Processes
    • C25B3/29—Coupling reactions
    • C25B3/295—Coupling reactions hydrodimerisation
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B3/00—Electrolytic production of organic compounds
    • C25B3/01—Products
    • C25B3/09—Nitrogen containing compounds

Definitions

  • the wash stream is passed through the cell in contact with the cathode and anode for a period of time in the range of about 1-60 minutes and thereafter the passage of the wash stream through the cell is terminated and the acrylonitrile composite stream is passed to the electrolytic cell for electrolysis.
  • This invention resides in an improved method for producing adiponitrile by electrolysis of an acrylonitrile stream passing through an undivided electrolytic cell having a cathode and an anode by periodically washing the cathode and anode of the cell with a basic aqueous wash stream having a concentration in the range of about lweight percent basic compound in the solution.
  • EHD Electrohydrodimerization
  • an aqueous electrolyte comprising a relatively large amount of a conducting inorganic salt such as a potassium phosphate, and a small amount of a directing (catalytic) organic salt such as tetrabutylammonium phosphate is continuously circulated between two suitable electrodes under electrolysis conditions.
  • a conducting inorganic salt such as a potassium phosphate
  • a directing (catalytic) organic salt such as tetrabutylammonium phosphate
  • a feature of the abovedescribed process is that it operates with an undivided cell, that is, there is no membrane orother form of divider which divides the space between the electrodes into a cathode compartment and an anode compartment.
  • Such undivided cell operation has the advantage of simple cell construction and relatively low internal resistance within the cell.
  • anode corrosion is a frequent problem with undivided cells.
  • the conditions under which high conversions and selectivities to desired products are obtained at the lead cathode are generally the same conditions which provide for significant corrosion of and deposits formation on the lead anode.
  • the corrosion of the anode is related to the oxidation losses in that it appears to cause even more oxidation of organic materials which are in the vicinity of the corroding anode. The products of the corrosion and/or oxidation sometimes tend to increase the internal resistance of the cell thereby requiring wasteful high levels of cell voltage.
  • This invention therefore, resides in an improved method for producing adiponitrile by electrolysis of acrylonitrile stream passing through an undivided electrolytic cell having a cathode and an anode by periodically washing the cathode andanode of the cell with a basic aqueous wash stream having a concentration in the range ofabout 1-20 weight percent basic compound in the solution.
  • the drawing is a diagrammatic view of the inventive process with apparatus for practicing the method of this invention.
  • acrylonitrile feed and make-up water and salt pass into line 12 by means of lines 10 and 11, respectively.
  • Line 12 carries a recirculating emulsionstream which passes into and through cell zone 1.
  • the electrodesin the cell are generally positioned such that thegap between them is vertical. The emulsion can pass through this gap either from top to bottom or vice versa.
  • Cell zone 1 comprises one or more cells operating under conditions suitable for the electrolytic conversion of acrylonitrile to adiponitrile.
  • Line 12 carries an aqueous solution of conducting inorganic salts, such as alkali metal phosphate salts and a minor amount of a directing tetraalkylammonium (TAA) salt, such as tetrabutylammonium phosphate.
  • conducting inorganic salts such as alkali metal phosphate salts
  • TAA directing tetraalkylammonium
  • Organic products and by-products are also present.
  • the stream passing through line 12 will hereafter be referred to as an acrylonitrile composite stream.
  • An emulsified mixture is removed from cell zone I through line 13, then passes through filter 2 andthenpasses into gasdisengager unit 3. In this unit, gases, primarily oxygen, are removed from the system through line 14.
  • the positions of the filter, gas disengager, pump, heater, feed entries, etc., need not necessarily be located in the order shown in the circulation loop but can be arranged in other sequences.
  • Cell zone I operates under conditions which include: a temperature of l50F; an atmospheric or near atmospheric pressure; an emulsion linear velocity of 005-6 ft/sec; an emulsion having an organic content of 2-12 weight percent based on the entire liquid stream; suitable electrodes having a composition such aslead, lead alloy, graphite, nickel, mercury, platinum, and the. like; a current density of 50-400 amp/ft an emulsion pH of 6-l2; a normality of 0.1-3 N with respect to inorganic conducting salts; a normality of 0001-03 N with respect to TAA salts, an acrylonitrile per. pass conversion of up to 10 percent; and an overall acrylonitrile conversion of up to 90 percent.
  • a minor part, corresponding to the desired acrylonitrile conversion, of the stream passing through line 19 is diverted and passed through line 15 into cooling zone 4 wherein that portion of the emulsion is cooled, using any conventional cooling means to a temperature suitable for the separation of the emulsioninto separate liquid phases.
  • the chilled emulsion leaves cooling zone 4 through line 16 and passes into separation column 5. Any suitable apparatus or combination of apparatus for settling an emulsified stream into an organic and an inorganic layer can be used in this separation column.
  • the lower aqueous phase leaves the separation zoneS through line 18 and rejoins the recirculating emulsion stream in line 19.
  • the organic phase is drawn off from separation column through line 20 and proceeds to separation zone 6.
  • Separation zone 6 can and generally will comprise cled water and salts, both organic and inorganic, leave separation zone 6, pass through line 24 and also rejoin the recirculating emulsion in stream 19.
  • the recombined materials in line 19 are blended with fresh acrylonitrile through line 10 and make-up water and salt through line ill to-form a mixture passing through line 12, through heater 7, wherein the mixture is adjusted to the desired cell temperature, and thence into cell zone 1.
  • the circulation of emulsion through cell zone 1 is halted, the cell can be drained, and valves 25 and 26 are closed. Valves 27 and 28 are then opened and a wash solution contained in zone 8 is recirculated through cell zone 1 by means of pump 29.
  • the wash solution stream circulates from storage zone 8 through line 30 through cell zone 1 and returned through line 31 to storage zone 8.
  • the recirculating washing solution accumulates solid particulate matter from cell zone 1. This solid particulate is removed from zone 8, either continuously or intermittently, through line 32. Make-up aqueous base solution is added to solution storage zone 8 through line 33.
  • the cell can be fabricated from any suitable material which is compatible with the electrolyte, and which is not attacked or corroded or only slowly corroded, under the operating conditions normally employed in the cell.
  • Preferred materials for the cathode are those having a fairly high hydrogen over-voltage, that is, a hydrogen over-voltage greater than that of copper.
  • Examples of such materials include, among others, lead, graphite, nickel, silver, gold, lead alloys, and the like.
  • Examples of materials suitable for use as the anode include lead, lead alloys, platinum, gold, nickel, iron, and the like.
  • Lead-containing materials such as metallic lead, lead alloys. or lead dioxide are presently preferred as materials of construction for the anode.
  • lead or lead alloys are presently preferred for use in forming the cathode.
  • the cell and electrodes are subjected to the washing with aqueous base according to the process of the present invention.
  • the EHD process is interrupted at intervals of only 10 to hours, ordinarily, 20-50 hours.
  • the washing or flushing operation is carried out very simply by temporarily halting the flow of emulsion through the cell and replacing it with a flow of aqueous base.
  • the circulation of the aqueous base wash stream through the cell is carried out for a sufficient time to restore the surface of the anode to again provide efficient low voltage operation. Ordinarily, this can be accomplished by circulating the aqueous base for 1-60, preferably 5-30 minutes.
  • the temperature at which the electrodes are contacted with the aqueous base can vary widely, ranging from the freezing point to the boiling point of the solution. Room temperature operation is generally satisfactory. With lead dioxide anodes, however, temperatures in excess of F are generally required.
  • the circulation rate can alsovary widely. A linear velocity through the cell in the range of 005-6 ft/second is desirable with operation toward the lower end of this range being preferred.
  • the base wash solution which is applicable for use in the inventive process is a strong base which has substantial solubility in water.
  • preferred bases are alkali metal hydroxides although strong organic bases such as tetramethylammonium hydroxide can also be used if desired.
  • the preferred base is one whose cation is already present'in the process.
  • a solution of potassium hydroxide is the preferred aqueous base.
  • the base can be present in the aqueous wash solution in any concentration which is effective for renewing the surface of the anode. Generally, the concentration will be 1-20, preferably 5-15, weight percent basic compound in the solution.
  • the benefits of the present invention are obtained by the regular removal of the deposit that forms on the anode.
  • lead is a particularly active materialin the EHD process.
  • a deposit is formed on the anode which contains combined lead, phosphorus, and organic material.
  • the present invention does not eliminate the corrosion of the electrodes such as lead anode corrosion, but it provides management of this type of corrosion so that it interferes little with the overall EHD process.
  • the flushing operation is halted and the circulation of emulsion mixture through the cell and over the electrodes is resumed. if desired, the flushing operation can be carried out without interrupting the current flow. Thus, some hydrogen will be generated during the flushing operation but there would be no necessity for the cumbersome off-and-on switching of high flows of current.
  • acrylonitrile was continuously converted to adiponitrile over a period of 202.7 hours at which time the run was terminated voluntarily.
  • the aqueous portion of the recirculating emulsion was a solution of potassium phosphates, being 1.5 N in potassium ion and being neutralized to a pH of 7.5-7.7 with orthophosphoric acid.
  • this aqueous stream is in the form of an emulsion with acrylonitrile and other organic products.
  • The'total organics amount to 4-5 weight percent based on the total emulsion.
  • About 0.1 weight percent of tetrabutylammonium ion was also present in the emulsion.
  • the system was operated continuously in a manner similar to that of FIG. 1 except that neither acrylonitrile nor water nor salts were recycled back into the process from separation zone 6.
  • the voltage across the cell was found to increase from the nominal 4.2 volts to a value of about 4.7 volts.
  • the current and the circulation of emulsion through cell were halted and a weight percent aqueous solution of potassium hydroxide was circulated through the cell at room temperature for 10-15 minutes.
  • the cell was drained of flushing solution and the current and circulation of reaction emulsion were resumed through the cell at the normal operating temperature of l-l 22F.
  • wash stream periodically terminating flow of the acrylonitrile composite stream to the cell; passing a wash stream through the cell in contact with the cathode and the anode, said wash stream 'being a strong base aqueous solution having a concentration in the range of about l weight percent base compound in the solution;
  • wash stream is passed through the cell at a linear velocity in the range of about 0.05 to about 6.0 feet per second.
  • wash stream comprises tetramethylammonium hydroxide.
  • cations of the wash stream are of the same type as cations of material discharging from the cell during electrolysis of the adiponitrile stream.
  • wash stream comprises cations of the same type as cations of material discharging from the cell during electrolysis of the composite stream.
  • wash stream comprises cations of the same type as cations of material discharging from the cell during electrolysis of the composite stream.
  • a potassium hydroxide solution wash stream through the cell in contact with the electrodes for a period of time in the range of about 1-60 minutes, said wash stream having a potassium hydroxide concentration in the range of about 1 to about 20 weight percent, said wash stream also comprising cations of the same type as cations of material discharging from the cell during electrolysis of the composite stream, and said wash stream being maintained at a temperature greater than about 150 F.;

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
US00275556A 1972-07-27 1972-07-27 Method for producing adiponitrile Expired - Lifetime US3844911A (en)

Priority Applications (8)

Application Number Priority Date Filing Date Title
US00275556A US3844911A (en) 1972-07-27 1972-07-27 Method for producing adiponitrile
CA169,070A CA1014102A (en) 1972-07-27 1973-04-18 Method for producing adiponitrile
JP4713473A JPS5310578B2 (it) 1972-07-27 1973-04-25
IT26409/73A IT994932B (it) 1972-07-27 1973-07-10 Metodo per la produzione di adiponitrile
GB3566773A GB1417285A (en) 1972-07-27 1973-07-26 Process for the electrolytic preparation of adiponitrile
BE133875A BE802806A (fr) 1972-07-27 1973-07-26 Procede perfectionne de production d'adiponitrile
DE19732338341 DE2338341C3 (de) 1972-07-27 1973-07-27 Verfahren zur Herstellung von Adipinsäuredinitril
FR7327720A FR2194671B1 (it) 1972-07-27 1973-07-27

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US00275556A US3844911A (en) 1972-07-27 1972-07-27 Method for producing adiponitrile

Publications (1)

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US3844911A true US3844911A (en) 1974-10-29

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US00275556A Expired - Lifetime US3844911A (en) 1972-07-27 1972-07-27 Method for producing adiponitrile

Country Status (7)

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US (1) US3844911A (it)
JP (1) JPS5310578B2 (it)
BE (1) BE802806A (it)
CA (1) CA1014102A (it)
FR (1) FR2194671B1 (it)
GB (1) GB1417285A (it)
IT (1) IT994932B (it)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4155818A (en) * 1978-07-17 1979-05-22 Monsanto Company Semi-continuous electro-hydrodimerization of acrylonitrile to adiponitrile with replating of cathode
US5593557A (en) * 1993-06-16 1997-01-14 Basf Aktiengesellschaft Electrode consisting of an iron-containing core and a lead-containing coating
US20050006252A1 (en) * 2001-10-12 2005-01-13 Fred Korpel Process for improving the purity of quaternary ammonium hydroxides by electrolysis in a two-compartment cell
WO2020242931A1 (en) 2019-05-24 2020-12-03 Ascend Performance Materials Operations Llc Tricyanohexane purification methods
WO2021138497A1 (en) 2019-12-30 2021-07-08 Ascend Performance Materials Operations Llc Process for separating tricyanohexane
WO2021138491A1 (en) 2019-12-30 2021-07-08 Ascend Performance Materials Operations Llc Tricyanohexane purification methods
WO2021138486A1 (en) 2019-12-30 2021-07-08 Ascend Performance Materials Operations Llc Process for recovering adiponitrile
WO2025043163A1 (en) 2023-08-24 2025-02-27 Ascend Performance Materials Operations Llc Process for dewatering and decoloring tricyanohexane

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2530077A (en) 2014-09-12 2016-03-16 Peli Biothermal Ltd Thermally insulated containers

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3511765A (en) * 1965-07-09 1970-05-12 Basf Ag Carrying out electrochemical reactions
US3616392A (en) * 1968-12-04 1971-10-26 Armco Steel Corp Method for coating conductive articles
US3689382A (en) * 1970-11-23 1972-09-05 Huyck Corp Electrochemical reductive coupling

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3511765A (en) * 1965-07-09 1970-05-12 Basf Ag Carrying out electrochemical reactions
US3616392A (en) * 1968-12-04 1971-10-26 Armco Steel Corp Method for coating conductive articles
US3689382A (en) * 1970-11-23 1972-09-05 Huyck Corp Electrochemical reductive coupling

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4155818A (en) * 1978-07-17 1979-05-22 Monsanto Company Semi-continuous electro-hydrodimerization of acrylonitrile to adiponitrile with replating of cathode
US5593557A (en) * 1993-06-16 1997-01-14 Basf Aktiengesellschaft Electrode consisting of an iron-containing core and a lead-containing coating
US20050006252A1 (en) * 2001-10-12 2005-01-13 Fred Korpel Process for improving the purity of quaternary ammonium hydroxides by electrolysis in a two-compartment cell
US7824538B2 (en) * 2001-10-12 2010-11-02 Flexsys B.V. Process for improving the purity of quaternary ammonium hydroxides by electrolysis in a two-compartment cell
WO2020242931A1 (en) 2019-05-24 2020-12-03 Ascend Performance Materials Operations Llc Tricyanohexane purification methods
US11780804B2 (en) 2019-05-24 2023-10-10 Ascend Performance Materials Operations Llc Tricyanohexane purification methods
US12404235B2 (en) 2019-05-24 2025-09-02 Ascend Performance Materials Operations Llc Tricyanohexane purification methods
WO2021138497A1 (en) 2019-12-30 2021-07-08 Ascend Performance Materials Operations Llc Process for separating tricyanohexane
WO2021138491A1 (en) 2019-12-30 2021-07-08 Ascend Performance Materials Operations Llc Tricyanohexane purification methods
WO2021138486A1 (en) 2019-12-30 2021-07-08 Ascend Performance Materials Operations Llc Process for recovering adiponitrile
US11560353B2 (en) 2019-12-30 2023-01-24 Ascend Performance Materials Operations Llc Tricyanohexane purification methods
WO2025043163A1 (en) 2023-08-24 2025-02-27 Ascend Performance Materials Operations Llc Process for dewatering and decoloring tricyanohexane

Also Published As

Publication number Publication date
DE2338341A1 (de) 1974-02-14
IT994932B (it) 1975-10-20
GB1417285A (en) 1975-12-10
BE802806A (fr) 1974-01-28
JPS4955620A (it) 1974-05-30
DE2338341B2 (de) 1975-07-31
FR2194671B1 (it) 1975-08-22
CA1014102A (en) 1977-07-19
JPS5310578B2 (it) 1978-04-14
FR2194671A1 (it) 1974-03-01

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