US3732276A - Hydrodimerization process of acrylic compounds - Google Patents

Hydrodimerization process of acrylic compounds Download PDF

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Publication number
US3732276A
US3732276A US00562475A US3732276DA US3732276A US 3732276 A US3732276 A US 3732276A US 00562475 A US00562475 A US 00562475A US 3732276D A US3732276D A US 3732276DA US 3732276 A US3732276 A US 3732276A
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acrylonitrile
percent
potassium
yield
adiponitrile
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Eygen C Van
A Hendrickx
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UCB SA
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UCB SA
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C255/00—Carboxylic acid nitriles
    • 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/582—Recycling of unreacted starting or intermediate materials

Definitions

  • the present invention is related to a new process for the hydrodimerization of acrylic compounds, more particularly to the production of adiponitrile from acrylonitrile.
  • Knunyants method namely, the use of at least 0.5 mol of alkali metal or alkaline earth metal per mol of acrylonitrile (Canadian patent specification No. 649,789, the yield being at least 85%, based on the amount of acrylonitrile consumed), the use of a polymerization inhibitor of a salt of a transition metal and of acetone (French patent specification No. 1,289,071, the yield reaching as much as 75% based on the acrylonitrile used), and the addition of various metallic salts to increase the adiponitrile/propionitrile ratio (Belgian patent specification No. 644,877).
  • the first of these reactions is so important that, under the most favorable reaction conditions, a maximum of 30% of the reducing metal employed is used in the actual hydrodimerization of acrylonitrile to adiponitrile, i.e. more than 70% of it is consumed to form hydrogen.
  • the alkali metal or alkaline earth metal amalgam is produced by electrolysis, the cost of the electric power required must be taken into account as well as the increase in investment necessary to cover the low yield based on reducing metal.
  • the adiponitrile yield based on the amount of electric power consumed in preparing the amalgam, is at most 30%.
  • the expression power efiiciency is used to represent this concept.
  • the process of the present invention improves the power efliciency of the acrylonitrile hydrodimerization to adiponitrile and, at the same time, gives excellent yields of adiponitrile based on acrylonitrile as well as a high adiponitrile/propionitrile ratio.
  • the process of hydrodimerization of acrylic compounds by the action of an alkali or alkaline earth metal amalgam in the presence of an organic or inorganic acid is characterized by the fact that it is carried out using a reaction medium of liquid consistency containing the acrylic compound, at least one amide and optionally water, the acid concentration being low enough to avoid the formation of hydrogen and to limit that of the hydrogenated product of said acrylic compound.
  • acrylic compound is to be understood acrylonitrile, methacrylonitrile, acrylic and methacrylic esters, acrylamide and methacrylamide as Well as their mixtures.
  • the present invention is related to a process of hydrodimerization of acrylonitrile to adiponitrile by the action of an amalgam of an alkali metal or alkaline earth metal in the presence of an inorganic or organic acid characterized by the fact that it is carried out using a reaction medium of liquid consistency containing acrylonitrile, at least one amide and optionally water, the acid concentration being low enough to avoid the formation of hydrogen and to limit that of propionitrile.
  • the adiponitrile yield is at least 65% and may reach more than while the adiponitrile yield in relation to the amount of alkali metal or alkaline earth metal consumed (power efliciency) is at least 60% and may exceed 90%.
  • the amount of metal consumed in the formation of gaseous hydrogen is always less than 10% and often nil.
  • power efficiencies have not been previously attained in hydrodimerization processes where the source of adiponitrile is exclusively acrylonitrile, which indicates the technical advance and economic interest of the process of the present invention.
  • the adiponitrile/propionitrile ratio is very favorable and lies between 20/1 and 50/1 and may even reach and exceed /1.
  • reaction mixture or mixture means the reaction medium, excluding the alkali metal or alkaline earth metal amalgam.
  • alkali metal or alkaline earth metal amalgam there is meant a mercury amalgam of a metal of Groups Ia and 11a of the Periodic System, the preferred metal being potassium.
  • concentration of alkali metal or alkaline earth metal in the amalgam is not critical and may range from 0.01 to 0.5% by weight but it is, in principle, possible to work outside these limits. However, below a concentration of 0.01%, extremely large quantities of mercury have to be used, while it is at present difficult to produce industrially amalgams containing more than 0.5% by weight of amalgamated metal.
  • the molar potassium/acrylonitrile ratio is determined by the desired acrylonitrile conversion rate. Since the formation of propionitrile requires, per mole of converted acrylonitrile, twice as much potassium as that of adiponitrile, it may be necessary, for high conversions, for example of the order of 90% and over and in cases where the formation of a small quantity of ropionitrile is accepted, to use a molar potassium/acrylonitrile ratio of efficiency, it is desirable not to exceed a ratio of 1.5 and more than one. However, in order to maintain good power preferably not even 1.1.
  • At least one amide is used so that, under the reaction conditions, the reaction mixture is of liquid consistency.
  • amides of carboxylic acids which may be unsubstituted or substituted on the nitrogen, for example, formamide, N,N- dimethyl formamide, acetamide, N,N-dimethyl-acetamide, propionamide and the like.
  • Sulfonamides such as p-toluene-sulfonamide and amides of inorganic acids, for example, hexamethyl phosphoramide and the like, may also be used.
  • the preferred amide is formamide, a product of low cost which is readily available.
  • the amount of amide used represents, by weight, 10 to 95%, preferably 20 to 90%, of the reaction mixture.
  • a mixture of two or more amides may be used.
  • the solubility of the amides in the mixture may be improved by the addition of auxiliary solvents, such as dioxane.
  • the inorganic or organic acid may be used either pure or in solution.
  • the quantity used is frequently stoichiometrically equivalent to the quantity of alkali metal or alkaline earth metal consumed in the reaction.
  • the acid concentration in the reaction mixture should be between 0.1 and 100 meq. (meq.:milliequivalent) per liter.
  • the acid content is less than 0.1 meq./liter, there is an increased risk of secondary reactions, such as polymerization of the acrylonitrile and various cyanoethylation reactions, whereas, when it exceeds the upper limit, the amount of hydrogen liberated becomes quite large.
  • an inorganic acid such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, hydrofluoric acid, hydrobromic acid, and the like, or a monoor polycarboxylic organic acid, such as formic acid, acetic acid, propionic acid, oxalic acid, tartaric acid and the like.
  • the acrylonitrile concentration in the reaction mixture is between 1 and 80% by weight, preferably between 5 and 60% by weight. In the continuous process, the concentration of acrylonitrile may be kept as low as 5% during the whole course of the reaction.
  • a certain amount of water may be present in the reaction mixture, its concentration may vary from 0 to 50% by weight and is preferably between 0 and by weight.
  • the technical acrylonitrile used in the hydrodimerization reaction according to the present invention is a product containing a polymerization inhibitor to ensure its stability during storage.
  • the amount of inhibitor added to the product is sufiicient to prevent the formation of polymers under the operational conditions.
  • a further amount of polymerization inhibitor may be added to the acrylonitrile, for example, hydroquinone or its methyl ether, p-tert.-butyl-catechol, alpha-amino-anthraquinone, phenothiazine and the like.
  • Such further amount of inhibitor may vary from 0.01 to 1% by weight, based on the acrylonitrile.
  • the acrylonitrile used may be a commercial product, or it may contain acetonitrile as often does the product directly withdrawn from the purification cycle of an acrylonitrile synthesis from propylene, air and ammonia.
  • the temperature is betwen 0 and 50 0., preferably between 10 and 30 C.
  • the process of the present invention may be carried out discontinuously, semi-continuously or entirely continu ously; it offers the advantage that the hydrodimerization products can be easily isolated and recovered by the usual methods, such as distillation and extraction.
  • the process of the present invention is not limited to any particular apparatus. Any apparatus may be used which maintains an intimate contact between the amalgam of the reducing metal and the reaction mixture.
  • the reactor used consists of a vertical tube filled with Raschig rings and surrounded by a sleeve serving for the thermostatic control of the reaction mixture, the latter being continuously recycled by a pump.
  • the mercury amalgam is introduced into the top of the tube and dispensed in droplets, the used mercury running out through the bottom of the reactor.
  • the filling may be eliminated if one of the reaction products precipitates in solid form during the reaction (e.g. potassium chloride, potassium sulfate or potassium acetate).
  • the neutralizing acid is introduced into the circulating reaction mixture by means of a metering pump.
  • the acid concentration is checked by measurement of the difference of potential existing between a glass electrode immersed in the reaction medium and a saturated calomel electrode. The millivolts are converted into acid concentrations (milliequivalents of acid per liter of reaction mixture) by means of a calibration curve.
  • conversion means the proportion of reagent consumed in relation to the quantity used and yield means the proportion of product formed in relation to the reagent actually consumed. All parts and proportions are by weight unless otherwise indicated.
  • EXAMPLE 1 11.84 kg. potassium amalgam containing 17.08 g. potassium (0.144% potassium/amalgam) is passed through the above-described apparatus, which contains a solution consisting initially of 27.5 g. acrylonitrile (9.8% by weight), 5.5 g. acetic acid, 27.5 g. water, 0.275 g. hydroquinone and 220 g. formamide. The temperature is maintained at 20 C. At the same time as the amalgam, a stoichiometrically equivalent quantity of glacial acetic acid is added in such a manner that the acid concentration is maintained at 7 meq./liter during the reaction. The experiment last minutes. The results obtained are as follows:
  • Adiponitrile yield in relation to potassium percent 68.0 Propionitrile yield in relation to acrylonitrile, percent 12.4 Propionitrile yield in relation to potassium, percent 26.0 Adiponitrile/propionitrile weight ratio 5.5 Gaseous hydrogen produced, percent 2.05
  • Adiponitrile yield in relation to potassium percent 60.2 Propionitrile yield in relation to acrylonitrile, percent 20.3 Propionitrile yield in relation to potassium, percent 32.0 Adiponitrile/propionitrile weight ratio 3.7 Gaseous hydrogen produced, percent 3.3
  • EXAMPLE 3 In this example, the experiment is performed in the absence of water and the proportion of acrylonitrile in the reaction mixture is increased.
  • the mixture treated initially contains 96.0 g. acrylonitrile (34.3% by weight), 5.5 g. glacial acetic acid and 179.0 g. formamide. No extra inhibitor is added. Hydrodimerization is effected with 12.34 kg. potassium amalgam containing 17.25 g. potassium (0.1395 potassium/ amalgam). As in the preceding examples, the temperature is maintained constant at 20 C. and a stoichiometrically equivalent quantity of glacial acetic acid is added at the same time as the amalgam so that the acid concentration of the mixture is maintained at 1 meq./liter. The experiment lasts 90 minutes. The following results are obtained:
  • EXAMPLE 4 In this example, the acetic acid is replaced by gaseous hydrogen chloride (1.5 meq./liter).
  • the quantities present initially are 27.5 g. acrylonitrile (10% by weight), 27.5 g. water and 220 g. formamide. No extra inhibitor 'is added. 12.15 kg. potassium amalgam containing 18.85 g. potassium (0.147% potassium/amalgam) is used. A stoichiometrically equivalent quantity of hydrogen chloride is added at the same time as the amalgam so that the acid concentration is maintained at 1.5 meq./liter.
  • the working temperature is C. and the experiment lasts 90 minutes.
  • the results obtained are as follows:
  • the mixture treated initially contains 199 g. acrylonitrile (73% by weight), 5.5 g. glacial acetic acid, 68 g.
  • EXAMPLE 6 In this example, the acetic acid is replaced by sulfuric acid and various initial concentrations of acrylonitrile are used.
  • a solution initially containing 40% commercial acrylonitrile, 55% formamide and 5% Water is introduced into the reactor.”
  • a sodium amalgam containing 0.12% sodium is passed through it in such an amount that the sodium/acrylonitrile molar ratio is 0.63 and concentrated sulfuric acid is added at the same time as the amalgam so that the concentration of the acid is maintained at 10 meq./liter.
  • the temperature is kept at 20 C.
  • a solution initially containing 10% commercial acrylonitrile, 80% dimethylformamide and 10% water is introduced into the reactor.
  • a potassium amalgam containing 0.2% potassium is passed through it in such an amount that the potassium/acrylonitrile molar ratio is 1.23 and concentrated sulfuric acid is added at the same time as the amalgam so that the concentration of the acid is maintained at 1 to 2 meq./liter.
  • the experiment is carried out at 20 C.
  • the amide is acetamide.
  • a solution initially containing 24.4% acrylonitrile, 59.5% acetamide and 16.6% water is introduced into the reactor.
  • a potassium amalgam containing 0.2% potassium is then passed through it in such an amount that the potassium/acrylonitrile molar ratio is 0.66 and concentrated sulfuric acid is added at the same time as the amalgam so that the concentration of the acid is maintained at 3 to 5 meq./liter.
  • the experiment is carried out at 20 C.
  • the amide is p-toluene-sulfonamide mixed with dioxane.
  • a solution initially containing 23% acrylonitrile, 36.7% p-toluene-sulfonamide, 33.9% dioxane and 6.4% water is introduced into the reactor.
  • a potassium amalgam containing 0.2% potassium is then passed through it in such an amount that the potassium/acrylonitrile molar ratio is 0.66 and concentrated sulfuric acid is added at the same time as the amalgam so that the concentration of the acid is maintained at 10 meq./liter.
  • the experiment is carried out at 20 C.
  • a feed solution (constituted by 59% formamide, 40% acrylonitrile and 1% normal aqueous solution of sulfuric acid), the amalgam containing 0.2% potassium and the sulfuric acid meant to neutralize the consumed potassium are continuously introduced into the above described reactor.
  • the exhausted mercury and the reaction suspension containing 10% potassium sulfate are continuously withdrawn.
  • the suspension is filtered in a continuous manner and a determined portion of the filtrate is recycled with the above described reagents in such a way that a 10% concentration of potassium sulfate is maintained in the reactor and that the desired conversion of acrylonitrile is reached.
  • the filtrate contains 57.5% formamide, 12.5% acrylonitrile, 25% adiponitrile, 0.7% propionitrile and 1% water, the balance being constituted by high boiling compounds.
  • the acid concentration is automatically maintained at 10 meq./ liter by means of a pH-meter controlled valve. Temperature is kept at 1820 C.
  • EXAMPLE 12 In this example, acrylonitrile is replaced by ethyl acrylate.
  • a solution initially containing 20% ethyl acrylate, 79% formamide and 1% water is introduced into the reactor.
  • a potassium amalgam containing 0.2% potassium is then passed through it in such an amount that the potassium/ ethyl acrylate molar ratio is 0.945 and concentrated sulfuric acid is added at the same time as the amalgam so that the concentration of the acid is maintained at 10 meq./ liter. Temperature is kept at 20 C.
  • EXAMPLE 13 Acrylo- Ethyl Potasmtrile acrylate sium Conversion, percent 55 65. 5 100 Adiponitrile yield, percent 22. 0 11.5 Diethyl adipate yield, percent 31 18. 5 Ethyl eyanopentanoate yield, percent- 57. 3 48. 1 57 Propionitrile yield, percent 6.7 6. 7 Ethyl propionate yield, percent 0 0 EXAMPLE 14 The example describes the hydrodimerization of an acrylonitrile-methacrylonitrile mixture.
  • a solution initially containing 59% formamide, 40% equimolecular mixture of acrylonitrile and methacrylonitrile and 1% water is introduced into the reactor.
  • a potassium amalgam containing 0.2% of potassium is then passed through it in such an amount that the potassium/ total amount of two monomers molar ratio is 0.68 and concentrated sulfuric acid is added at the same time as the amalgam so that the concentration of the acid is maintained at 10 meq./liter. Temperature is kept at 20 C.
  • EXAMPLE 16 This example is a variation of Example 15.
  • a solution initially containing 83% dimethylformamide, 15% methacrylonitrile and 2% water is introduced into the reactor.
  • a potassium amalgam containing 0.2% potassium is then passed through it in such an amount that the consumed potassium/methacrylonitrile molar ratio is 0.3 and concentrated sulfuric acid is added at the same time as the amalgam so that the concentration of the acid is maintained below meq./liter. Temperature is kept at 40 C.
  • Methacrylonitrile conversion percent 33 Dimethyladiponitrile yield in relation to methacrylonitrile, percent 33.5 Dimethyladiponitrile yield in relation to potassium,
  • a process for the reductive dimerization of acrylonitrile to produce adiponitrile which comprises contacting said acrylonitrile with an alkali metal amalgam and an acid in a liquid dimerization medium which contains therein hexamethylphosphoramide.
  • a process for the reductive dimerization of a compound selected from the group consisting of acrylonitrile, methacrylonitrile and ethyl acrylate to produce adiponitrile, dimethyl-adiponitrile and diethyl adipate respectively which comprises contacting said compound with an alkali metal or alkaline earth metal amalgam and an acid in a liquid dimerization medium which contains therein hexamethylphosphoramide.
  • a process according to claim 2, wherein said acid is selected from the group consisting of acetic acid, hydrochloric acid and sulfuric acid.
  • liquid medium consists essentially of from 5 to by weight of acrylonitrile, from 20 to by weight of said amide and from 0 to 10%, inclusive, by weight of water.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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US00562475A 1965-07-07 1966-07-05 Hydrodimerization process of acrylic compounds Expired - Lifetime US3732276A (en)

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GB28801/65A GB1098726A (en) 1965-07-07 1965-07-07 Process for the hydrodymerisation of acrylic compounds

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AT (1) AT266070B (enrdf_load_stackoverflow)
BE (1) BE683650A (enrdf_load_stackoverflow)
CH (1) CH448046A (enrdf_load_stackoverflow)
ES (1) ES328783A1 (enrdf_load_stackoverflow)
GB (1) GB1098726A (enrdf_load_stackoverflow)
LU (1) LU51483A1 (enrdf_load_stackoverflow)
NL (1) NL6609241A (enrdf_load_stackoverflow)
NO (1) NO123031B (enrdf_load_stackoverflow)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3890365A (en) * 1965-06-30 1975-06-17 Ici Ltd Organic reduction process
US9776479B2 (en) 2014-12-20 2017-10-03 GM Global Technology Operations LLC Vehicle door having a glass channel with separate bracket

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5332844A (en) * 1992-03-06 1994-07-26 Ube Industries, Ltd. Method of producing straight-chain acrylonitrile dimers
US5466858A (en) * 1993-09-03 1995-11-14 Ube Industries, Ltd. Method of producing straight-chain acrylonitrile dimers

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3890365A (en) * 1965-06-30 1975-06-17 Ici Ltd Organic reduction process
US9776479B2 (en) 2014-12-20 2017-10-03 GM Global Technology Operations LLC Vehicle door having a glass channel with separate bracket

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LU51483A1 (enrdf_load_stackoverflow) 1967-01-05
GB1098726A (en) 1968-01-10
AT266070B (de) 1968-11-11
CH448046A (fr) 1967-12-15
BE683650A (enrdf_load_stackoverflow) 1967-01-05
NL6609241A (enrdf_load_stackoverflow) 1967-01-09
ES328783A1 (es) 1967-04-16
NO123031B (enrdf_load_stackoverflow) 1971-09-20

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