US3616321A - Process for the production of adiponitrile - Google Patents
Process for the production of adiponitrile Download PDFInfo
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- US3616321A US3616321A US830521A US3616321DA US3616321A US 3616321 A US3616321 A US 3616321A US 830521 A US830521 A US 830521A US 3616321D A US3616321D A US 3616321DA US 3616321 A US3616321 A US 3616321A
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- United States
- Prior art keywords
- comprised
- salts
- electrolysis
- percent
- acrylonitrile
- Prior art date
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- 238000000034 method Methods 0.000 title claims abstract description 73
- BTGRAWJCKBQKAO-UHFFFAOYSA-N adiponitrile Chemical compound N#CCCCCC#N BTGRAWJCKBQKAO-UHFFFAOYSA-N 0.000 title abstract description 17
- 238000004519 manufacturing process Methods 0.000 title description 5
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 40
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims abstract description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229920000137 polyphosphoric acid Polymers 0.000 claims abstract description 9
- 239000002253 acid Substances 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 21
- 150000003839 salts Chemical class 0.000 claims description 19
- 229910052783 alkali metal Inorganic materials 0.000 claims description 18
- 150000001340 alkali metals Chemical class 0.000 claims description 17
- 239000008151 electrolyte solution Substances 0.000 claims description 15
- 150000007513 acids Chemical class 0.000 claims description 14
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 13
- 150000008043 acidic salts Chemical class 0.000 claims description 13
- 230000002378 acidificating effect Effects 0.000 claims description 13
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 11
- 239000011734 sodium Substances 0.000 claims description 11
- 239000004094 surface-active agent Substances 0.000 claims description 11
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 9
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 9
- 229910052700 potassium Inorganic materials 0.000 claims description 9
- 239000011591 potassium Substances 0.000 claims description 9
- 229910052708 sodium Inorganic materials 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- 239000010439 graphite Substances 0.000 claims description 8
- 229910002804 graphite Inorganic materials 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 7
- 235000019832 sodium triphosphate Nutrition 0.000 claims description 7
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 claims description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 6
- 229910052744 lithium Inorganic materials 0.000 claims description 6
- 125000004437 phosphorous atom Chemical group 0.000 claims description 6
- 239000002585 base Substances 0.000 claims description 5
- -1 bis-methylpyridinium phosphate Chemical compound 0.000 claims description 5
- 235000011007 phosphoric acid Nutrition 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical class C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 3
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical group [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- 150000003016 phosphoric acids Chemical class 0.000 claims description 3
- JMTCDHVHZSGGJA-UHFFFAOYSA-M potassium hydrogenoxalate Chemical compound [K+].OC(=O)C([O-])=O JMTCDHVHZSGGJA-UHFFFAOYSA-M 0.000 claims description 3
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 claims description 3
- 229910000342 sodium bisulfate Inorganic materials 0.000 claims description 3
- 150000002913 oxalic acids Chemical class 0.000 claims description 2
- 235000019858 potassium salts of orthophosphoric acid Nutrition 0.000 claims description 2
- 239000011644 potassium salts of orthophosphoric acid Substances 0.000 claims description 2
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 2
- 235000019857 sodium salts of orthophosphoric acid Nutrition 0.000 claims description 2
- KVTGAFMPJKTYNO-UHFFFAOYSA-L hydrogen phosphate;tetraethylazanium Chemical compound OP([O-])([O-])=O.CC[N+](CC)(CC)CC.CC[N+](CC)(CC)CC KVTGAFMPJKTYNO-UHFFFAOYSA-L 0.000 claims 1
- 150000001447 alkali salts Chemical class 0.000 abstract description 15
- 238000002474 experimental method Methods 0.000 description 26
- 238000005260 corrosion Methods 0.000 description 21
- 230000007797 corrosion Effects 0.000 description 21
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 12
- 239000003792 electrolyte Substances 0.000 description 9
- 239000001205 polyphosphate Substances 0.000 description 9
- 235000011176 polyphosphates Nutrition 0.000 description 9
- 229920000388 Polyphosphate Polymers 0.000 description 8
- 239000000839 emulsion Substances 0.000 description 8
- 229910019142 PO4 Inorganic materials 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 5
- 235000021317 phosphate Nutrition 0.000 description 5
- 239000013543 active substance Substances 0.000 description 4
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical class [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 description 4
- 239000010452 phosphate Substances 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 description 4
- 235000019982 sodium hexametaphosphate Nutrition 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- 239000008346 aqueous phase Substances 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000012074 organic phase Substances 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 2
- GIXFALHDORQSOQ-UHFFFAOYSA-N 2,4,6,8-tetrahydroxy-1,3,5,7,2$l^{5},4$l^{5},6$l^{5},8$l^{5}-tetraoxatetraphosphocane 2,4,6,8-tetraoxide Chemical compound OP1(=O)OP(O)(=O)OP(O)(=O)OP(O)(=O)O1 GIXFALHDORQSOQ-UHFFFAOYSA-N 0.000 description 1
- 229910000497 Amalgam Inorganic materials 0.000 description 1
- 239000004254 Ammonium phosphate Substances 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-N Metaphosphoric acid Chemical compound OP(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- YDHWWBZFRZWVHO-UHFFFAOYSA-N [hydroxy(phosphonooxy)phosphoryl] phosphono hydrogen phosphate Chemical compound OP(O)(=O)OP(O)(=O)OP(O)(=O)OP(O)(O)=O YDHWWBZFRZWVHO-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- RXKJFZQQPQGTFL-UHFFFAOYSA-N dihydroxyacetone Chemical compound OCC(=O)CO RXKJFZQQPQGTFL-UHFFFAOYSA-N 0.000 description 1
- 230000003292 diminished effect Effects 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 1
- KCIDZIIHRGYJAE-YGFYJFDDSA-L dipotassium;[(2r,3r,4s,5r,6r)-3,4,5-trihydroxy-6-(hydroxymethyl)oxan-2-yl] phosphate Chemical compound [K+].[K+].OC[C@H]1O[C@H](OP([O-])([O-])=O)[C@H](O)[C@@H](O)[C@H]1O KCIDZIIHRGYJAE-YGFYJFDDSA-L 0.000 description 1
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical class [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- PEYVWSJAZONVQK-UHFFFAOYSA-N hydroperoxy(oxo)borane Chemical compound OOB=O PEYVWSJAZONVQK-UHFFFAOYSA-N 0.000 description 1
- 235000014413 iron hydroxide Nutrition 0.000 description 1
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000002560 nitrile group Chemical group 0.000 description 1
- 150000003891 oxalate salts Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- HIFXHEXRVMWOAG-UHFFFAOYSA-M phenylmethanesulfonate;tetramethylazanium Chemical compound C[N+](C)(C)C.[O-]S(=O)(=O)CC1=CC=CC=C1 HIFXHEXRVMWOAG-UHFFFAOYSA-M 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229940005657 pyrophosphoric acid Drugs 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- UNXRWKVEANCORM-UHFFFAOYSA-N triphosphoric acid Chemical compound OP(O)(=O)OP(O)(=O)OP(O)(O)=O UNXRWKVEANCORM-UHFFFAOYSA-N 0.000 description 1
- 229940048102 triphosphoric acid Drugs 0.000 description 1
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 1
Classifications
-
- 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
Definitions
- the present invention is concerned with a process .for the production of adiponitrile from acrylonitrile.
- Another process consists in hydrodimerizing acrylonitrile by the electrolysis of a inixture of acrylonitrile and of a small quantity of water saturated by an electrolyte, such as lithium bromide, on a platinum electrode (Belgian Pat. specification No. 649,625).
- the electrolyte used according to the process of Belgian Pat. specification No. 684,436 is responsible for the corrosion of the iron oxide anode and that, if the salts of the electrolyte are replaced wholly or partially by the alkali metal salts of polycondensed phosphoric acids, it is possible to maintain substantially all of the advantages of this process, while reducing the corrosion of the iron oxide anode to an amount which is technically acceptable.
- the process according to the present invention for the hydrodimerization of acrylonitrile to adiponitrile by the direct electrolytic route, by passing a direct electrical current through an electrolytic cell having the anode and cathode in contact with the electrolytic medium comprises using an initial electrolysis medium consisting essentially of (a) acrylonitrile, (b) water, (c) at least one alkali salt selected from the group consisting of the alkali salts of condensed polyphosphoric acids of the formula:
- alkali salts of condensed polyphosphoric acids of formula (1) there are intended the sodium, potassium, lithium, ammonium and quaternary ammonium salts of acids, such as pyrophosphoric acid (H,P O,-), triphosphoric acid (H P O tetraphosphoric acid (H -P 0 polyphosphoric acids containing from 5 to 100 phosphorus atoms, and mixtures thereof.
- acids such as pyrophosphoric acid (H,P O,-), triphosphoric acid (H P O tetraphosphoric acid (H -P 0 polyphosphoric acids containing from 5 to 100 phosphorus atoms, and mixtures thereof.
- 'By alkali salts of polymetaphosphoric acids of formula (11) there are intended the sodium, potassium, lithium, ammonium and quaternary ammonium salts of acids, such as dimetaphosphoric acid (H P- O), tn'metaphosphoric acid (11 F 0 tetrametaphosphoric acid (H,P.oa). metaphosphoric acids containing from 5 to 100 phosphorus atoms and mixtures thereof.
- alkali salts of the condensed polyphosphoric acids of formula (1) and of the metaphosphoric acids of formula (11) may also be used in the form of mixtures with one another in any desired proportions; furthermore, there can be used the alkali salts of these acids such as are available commercially, for example, under the names of Graham's salt, Kurrol salt, sodium hexametaphosphate, SQ salt sold by Monsanto (Na,,P 0 and the like.
- acidic salts of alkali metals and of polyacids there are intended the salts of a polyacid, such as sulfuric acid, boric acid, perboric acid, phosphoric acid, oxalic acid or the like, which is incompletely substituted, containing at least one hydrogen cation.
- a polyacid such as sulfuric acid, boric acid, perboric acid, phosphoric acid, oxalic acid or the like, which is incompletely substituted, containing at least one hydrogen cation.
- monoand disodium orthophosphates, monoand dipotassium orthophosphates, sodium hydrogen sulfate, monopotassium oxalate and the like as well as mixtures thereof.
- the salts used according to the present invention may replace wholly the partially substituted salts of alkali metals and of polyacids, especially the acidic alkali metal orthophosphates.
- the salts according to the present invention are more expensive, especially with regard to the alkali orthophosphates, and as, on the other hand, their lower ionization, increases the terminal voltage, it is intended, according to the present invention, to use mixtures, on the one hand, of acidic salts of alkali metal and of polyacid and, on the other hand, of salts of acids according to formulas (l) and (11) in which the amount of polyphosphates according to the present invention is sufficient to maintain the corrosion of the anode at an acceptable level.
- the amount of polyphosphate may be relatively low, without prejudicing the anticorrosive effect.
- the ratio by weight between the acidic salts of alkali metal and of polyacid and of the polyphosphates used according to the present invention may be 99.9/01 to 0/100, advantageously 99/1 to /20, and preferably 95/5 to /15.
- the concentration by weight of the polyphosphates (or of the mixture of polyphosphates and of acidic salts of alkali metal and of polyacid) in the aqueous electrolytic solution may'vary from 0.5 percent up to the concentration corresponding to saturation.
- quaternary ammonium salts or pyridinium salts such as acidic bistetraethyl-amrnonium phosphate, penta-tetraethyl-ammonium tripolyphosphate or acidic bis-methyl-pyridinum phosphate or the like.
- concentration of these surface-active substances in the aqueous electrolytic solution may vary from 0.05 to 5 percent by weight, preferably from 0.2 to 2 percent
- the initial electrolytic solution essentially contains water.
- a small quantity of a base or of an acid in order to maintain a definite pH value, this pH value advantageously being maintained between 5 and 10, preferably between 8 and 9.
- a mixture of emulsified acrylonitrile and of the initial aqueous electrolytic solution is circulated through the electrolysis apparatus, the volumetric ration between the aqueous phase and the acrylonitrile phase being maintained within the limits of 1:1 and 6: l.
- This anode is surrounded by two cathodes made of graphite and of the same dimensions, placed on both sides of the anode at a distance ofl cm.
- the supply of current is made by means of steel threaded rods screwed to the upper part ofeach electrode.
- the assembly of the three electrodes is fixed vertically in the beaker.
- the apparatus is provided with [.8 liters of the electrolytic solution to be tested. A temperature of 20 C. is maintained and there is passed through a continuous current of 14 amperes. The current density is in the region of 7 amperes/dmf". Every 24 hours, the electrolysis is interrupted for the time necessary to remove the anode, rinse it, dry and weigh it. The anode is then replaced and the electrolysis resumed under the same conditions.
- the first experiment is a comparative one carried out with an TABLE I Experiment number KzEPO 5.6 5.6 5.3 4.8 KsPzOnL 0. 06 0.3 1.14 (Et NhllPOt 1 1 1 1 Hexarnetaphosphatc Phosphate SQ NB P207 Rate of corrosion, mmJyear:
- the temperature during the electrolysis is maintained within the limits of 0 C., to 40 C., preferably within the region of room temperature.
- the linear velocity of circulation of the emulsified mixture is between 0.1 and l m./sec.
- an electrolysis apparatus without a diaphragm, having graphite cathodes and magnetite anodes, with or without a metallic support.
- the current density is l20 amperes/dm. and the voltage is comprised between 4 and volts preferably between 4 and 7 volts.
- the process according to the present invention is equally applicable to anodes made of materials other than iron oxide, for example, anodes made of metallic iron or the like.
- the electrolysis is carried out in a manner such that the conversion of the acrylonitrile is -70 percent, preferably -50 percent. Below 20 percent, the economy of the process according to the present invention or the production ratio is too poor for industrial use, while when the conversion is increased beyond 70 percent, the selectivity of adiponitrile is less good.
- the process according to the present invention may be carried out as well discontinuously as continuously.
- the apparatus for measuring the rate of corrosion of the anodes comprises a beaker provided with means for cooling and a mechanical stirrer.
- the magnetite anode subjected to the experiments is a square plate of steel or of Armco iron, the edges of which are 10 cm. long and the thickness of which is l cm., entirely covered with a coating of magnetite with a thickness of about 1 mm., obtained by the superficial oxidation of the metal in water vapor at a temperature of 1,000 C.
- the composition of the electrolyte is of the type used in Belgian Pat. specification No. 684,436; it contains, in particular, acidic dipotassium orthophosphatev
- the second experiment which is according to the present invention, a part of the acidic dipotassium orthophosphate of the first experiment is replaced by potassium tripolyphosphate.
- the whole of the dipotassium orthophosphate is replaced by potassium tripolyphosphate.
- the electrolysis device functions in a continuous manner, with a constant supply of acrylonitrile and of water (to compensate for the electrolytic decomposition of this latter) and a continuous removal, by decantation, of an organic phase containing unchanged acrylonitrile,
- the pH value is permanently controlled and maintained at 8.4.
- AN Acrylonitrile.
- ADN Adiponitrile.
- PN Propionitrile.
- ADNlAN Percent of the number of moles of ADN formed referred to the number of moles of AN supplied.
- PNlAN Percent of the number of moles of PN formed, referred to the number of moles of AN supplied.
- Yield ADN/Elec. Ratio in percent between the number of moles of ADN formed and the number of taradays provided to the cell in the course of the electrol sis.
- the experiment was carried out in a tubular electrolytic cell constituted by a cylindrical anode made of molten magnetite surrounded by a graphite tube which functions both as cathode and as container.
- the anode has a diameter of 6 cm. and an effective length of 61 cm., i.e., a surface of 11.3 dm. dm.?
- the cathode has an interior diameter of7 cm., i.e.. an effective surface of l3.2 dm.?
- the distance between the electrodes is 0.5 cm.
- the cell proper is completed by a tubing system with pumps, hydrocyclone and filter allowing the circulation of the reaction medium between the electrodes and the collection of the solid products resulting from the corrosion of the anode (phosphate+iron hydroxide). Cooling is effected by circulating brine in a double jacket surrounding the graphite tube.
- Process of hydrodimerization of acrylonitrile to adiponitrile by the direct electrolytic route by passing a direct electrical current through an electrolytic cell having the anode and cathode in contact with the electrolytic medium, which comprises using an initial electrolysis medium consisting essentially of (a) acrylonitrile, (b) water, (c) at least one alkali salt selected from the group consisting of the alkali salts of condensed polyphosphoric acids of the formula in which n has a value of from 2 to I00, and the alkali salts of polymetaphosphoric acids of the formula n n fln in which n has a value of from 2 to I00, (d) a surface-active substance, and (e) at least one acidic salt of an alkali metal and ofa polyacid, the ratio by weight of (e) to (c) being comprised between 99.9/0.l and 0/l00.
- Process as claimed in claim I in which the concentration 5.
- Process as c laimed in claim 1, in which the salts of formu la (1) are selected from the group consisting of sodium, potassium, lithium, ammonium and quaternary ammonium salts of pyrophosphoric, triphosphoric, tetraphosphoric and polyphosphoric acids containing from 5 to 100 phosphorous atoms and mixtures thereof.
- salts offormula (II) are selected from the group consisting of sodium, potassium, lithium, ammonium and quaternary ammonium salts of dimetaphosphoric, trimetaphosphoric, tetrametaphosphoric acids and metaphosphoric acids having 5 to 100 phosphorous atoms and mixtures thereof.
- the surface-active substance is selected from the group consisting of acidic bistetraethyl-ammonium phosphate, penta-tetraethyl-ammonium tripolyphosphate and acidic bis-methylpyridinium phosphate.
- the acidic salt of an alkali metal and of a polyacid is selected from the group consisting of acidic salts of sulfuric, boric, perboric, phosphoric and oxalic acids, which are incompletely substituted, containing at least one hydrogen cation.
- the acidic salts of an alkali metal and of a polyacid is selected from the group consisting of acidic sodium and potassium salts of orthophosphoric acid, sodium hydrogen sulfate and 8 monopotassium oxalate.
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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)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB2705168 | 1968-06-06 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3616321A true US3616321A (en) | 1971-10-26 |
Family
ID=10253371
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US830521A Expired - Lifetime US3616321A (en) | 1968-06-06 | 1969-06-04 | Process for the production of adiponitrile |
Country Status (14)
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3897318A (en) * | 1973-08-06 | 1975-07-29 | Monsanto Co | Single-compartment electrolytic hydrodimerization process |
| US3898140A (en) * | 1973-08-06 | 1975-08-05 | Monsanto Co | Electrolytic hydrodimerization process improvement |
| US3966566A (en) * | 1974-08-15 | 1976-06-29 | Monsanto Company | Electrolytic hydrodimerization process improvement |
| US4250001A (en) * | 1979-06-19 | 1981-02-10 | Monsanto Company | Pretreatment of cathodes in electrohydrodimerization of acrylonitrile |
| US4306949A (en) * | 1979-12-19 | 1981-12-22 | Monsanto Company | Electrohydrodimerization process |
| US4462876A (en) * | 1983-03-25 | 1984-07-31 | Ppg Industries, Inc. | Electro organic method and apparatus for carrying out same |
| US4472252A (en) * | 1983-03-25 | 1984-09-18 | Ppg Industries, Inc. | Electrolytic synthesis of organic compounds from gaseous reactants |
| US4472251A (en) * | 1983-03-25 | 1984-09-18 | Ppg Industries, Inc. | Electrolytic synthesis of organic compounds from gaseous reactant |
| US4636286A (en) * | 1983-03-25 | 1987-01-13 | Ppg Industries, Inc. | Electro organic method |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB8308145D0 (en) * | 1983-03-24 | 1983-05-05 | Rylands Whitecross Ltd | Nails |
-
1968
- 1968-06-06 GB GB2705168A patent/GB1233266A/en not_active Expired
-
1969
- 1969-06-02 LU LU58763D patent/LU58763A1/xx unknown
- 1969-06-02 FR FR6918295A patent/FR2010513A1/fr not_active Withdrawn
- 1969-06-02 NL NL6908359.A patent/NL159366B/xx not_active IP Right Cessation
- 1969-06-04 US US830521A patent/US3616321A/en not_active Expired - Lifetime
- 1969-06-04 IL IL32339A patent/IL32339A/en unknown
- 1969-06-04 PL PL1969134011A patent/PL80063B1/pl unknown
- 1969-06-04 BG BG012388A patent/BG16183A3/bg unknown
- 1969-06-04 AT AT532169A patent/AT289056B/de not_active IP Right Cessation
- 1969-06-04 CH CH848569A patent/CH502312A/fr not_active IP Right Cessation
- 1969-06-05 CS CS399669A patent/CS154624B2/cs unknown
- 1969-06-05 BE BE734090D patent/BE734090A/xx not_active IP Right Cessation
- 1969-06-05 NO NO02331/69A patent/NO130430B/no unknown
- 1969-06-05 SE SE08003/69A patent/SE367820B/xx unknown
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3897318A (en) * | 1973-08-06 | 1975-07-29 | Monsanto Co | Single-compartment electrolytic hydrodimerization process |
| US3898140A (en) * | 1973-08-06 | 1975-08-05 | Monsanto Co | Electrolytic hydrodimerization process improvement |
| US3966566A (en) * | 1974-08-15 | 1976-06-29 | Monsanto Company | Electrolytic hydrodimerization process improvement |
| US4250001A (en) * | 1979-06-19 | 1981-02-10 | Monsanto Company | Pretreatment of cathodes in electrohydrodimerization of acrylonitrile |
| US4306949A (en) * | 1979-12-19 | 1981-12-22 | Monsanto Company | Electrohydrodimerization process |
| US4462876A (en) * | 1983-03-25 | 1984-07-31 | Ppg Industries, Inc. | Electro organic method and apparatus for carrying out same |
| US4472252A (en) * | 1983-03-25 | 1984-09-18 | Ppg Industries, Inc. | Electrolytic synthesis of organic compounds from gaseous reactants |
| US4472251A (en) * | 1983-03-25 | 1984-09-18 | Ppg Industries, Inc. | Electrolytic synthesis of organic compounds from gaseous reactant |
| US4636286A (en) * | 1983-03-25 | 1987-01-13 | Ppg Industries, Inc. | Electro organic method |
Also Published As
| Publication number | Publication date |
|---|---|
| DE1928748A1 (de) | 1969-12-11 |
| PL80063B1 (enrdf_load_stackoverflow) | 1975-08-30 |
| NL6908359A (enrdf_load_stackoverflow) | 1969-12-09 |
| BE734090A (enrdf_load_stackoverflow) | 1969-12-05 |
| GB1233266A (enrdf_load_stackoverflow) | 1971-05-26 |
| IL32339A (en) | 1972-08-30 |
| FR2010513A1 (enrdf_load_stackoverflow) | 1970-02-20 |
| CH502312A (fr) | 1971-01-31 |
| NL159366B (nl) | 1979-02-15 |
| IL32339A0 (en) | 1969-08-27 |
| SE367820B (enrdf_load_stackoverflow) | 1974-06-10 |
| BG16183A3 (bg) | 1972-07-20 |
| DE1928748B2 (de) | 1976-08-26 |
| AT289056B (de) | 1971-04-13 |
| LU58763A1 (enrdf_load_stackoverflow) | 1970-01-14 |
| CS154624B2 (enrdf_load_stackoverflow) | 1974-04-30 |
| NO130430B (enrdf_load_stackoverflow) | 1974-09-02 |
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