公开(公告)号：GB1145539A

公开(公告)日：1969-03-19

申请号：GB3071266

申请日：1966-07-08

Applicant: BASF AG

Inventor： BECK FRITZ ,  LEITNER HANS ,  GUTHKE HARALD ,  WINTERSBERGER KARL

IPC: C25B3/25 ,  C25B3/29 ,  C25B9/17 ,  C25B15/00 ,  C25B15/06

Abstract: 1,145,539. Electrolytic cell for producing organic compounds. BADISCHE ANILIN - & SODA - FABRIK A.G. July 8, 1966 [July 9, 1965; Jan.13, 1966], No.30712/66. Heading C7B. Apparatus for performing electro-chemical reactions of organic compounds in a flowing electrolyte, particularly the hydrodimerization of acrylonitrile to adiponitrile, comprises at least one uniformly liquid-permeable electrode pair 1a, b in which the electrodes are spaced less than 1 mm. apart, preferably separated by a liquid-permeable insulator 22, e.g. porous glass fibre cloth or paper, or porous plastic sheeting or ceramics. Electrolyte may be supplied and withdrawn, preferably recycled through a heat exchanger, to enable it to flow through the electrode pair(s). Pulsations may be imparted to the electrolyte and/or the electrode pair(s), e.g. by securing the electrode support and connection 4 to a vibrator 23. Current may be supplied through metal sleeves 2 pressed coaxially into plastic spoked-wheel shaped members 3. The electrodes may be made of metal or wire cloth, screens, expanded metal or sintered articles. Cathodes may be composed of Cu, brass or iron wire coated with Pb, Cd, Hg, Hg-Pb, Pb-Th, Hg-Ag, or Zn, Cu, Pt, Pd, Ni or graphite activated with Pt; anodes may be composed of metal or wire cloth or expanded metal support of Pt, Ni, Ti, or Ta coated with Ni or Pt with a coating of PbO 2 or Tl 2 O 3 , Pt, Pt-Ir, Pt-Rh, Ni, Fe, alloy steel or graphite. For producing adiponitrile with some propionitrile, examples are given of electrolytes composed of 66-81À5% acrylonitrile, 5-15% methanol or 20 or 22À5% isopropanol or 20% dioxane or dimethyl formamide, 7 or 8% water, and 0À5 or 1% tetramethyl ammonium methyl (or p-totuene) sulphate; the pH is regulated by adding acetic acid and triethylamine through a dropping funnel 27, and the off gas pipe passes through a reflux condenser 28. A solution of monomethyl adipate in methanol, electrochemically reacted with sodium methylate, is condensed to dimethyl sebacate. The apparatus may be used for other organic electro-chemical reactions.

公开(公告)号：FR1476162A

公开(公告)日：1967-04-07

申请号：FR57694

申请日：1966-04-14

Applicant: BASF AG

Inventor： GUTHKE HARALD ,  WINTERSBERGER KARL ,  BECK FRITZ ,  FLOSS JOSEF GEORG ,  HABERMANN WOLFGANG

IPC: C25B3/29

公开(公告)号：GB1059386A

公开(公告)日：1967-02-22

申请号：GB1854564

申请日：1964-05-05

Applicant: BASF AG

Inventor： BECK FRITZ ,  SCHUSTER LUDWIG

IPC: C07C5/05 ,  C07C5/08 ,  G01N27/416 ,  G01N31/00

Abstract: Unsaturated hydrocarbons are selectively hydrogenated in a liquid containing hydrogen ions and in the presence of a finely-divided metallic catalyst, the electrochemical hydrogen reference potential being measured during hydrogenation and the hydrogenation being stopped when the change in the reference potential with respect to time reaches or approximates to a maximum value at the prevailing pH value. Hydrogenation is carried out either by saturating the catalyst with hydrogen in a shaker prior to the addition of the organic compound, or the organic compound/catalyst mixture is put into an autoclave and the hydrogen forced in. For suitable catalysts, solvents, electrolytes and buffers (see Division B1). Examples of suitable unsaturated compounds are cyclic, mono- or polyunsaturated hydrocarbons, particularly cycloolefins and cyclo-diolefins with 5-12 C atoms, phenylacetylene; 1,3,5-triethinyl benzene, cyclohexene, cyclooctadiene. The following hydrogenations are exemplified. Example 3, one double bond in cyclooctadiene, and cyclohexene; Example 10, phenylacetylene to phenylethylene (i.e. styrene).ALSO:The electrochemical hydrogen reference potential is measured during the hydrogenation of C-C multiple bonds in organic compounds in a liquid containing hydrogen ions and in the presence of a finely divided metallic catalyst, and selective hydrogenation is effected by stopping the hydrogenation when the change in the reference potential with respect to time reaches or approximates to a maximum value at the prevailing pH value. Hydrogenation is carried out either by saturating the catalyst with hydrogen in a shaker prior to the addition of the organic compound, or the organic compound/catalyst mixture is put into an autoclave and the hydrogen forced in. For suitable catalysts, solvents, electrolytes and buffers (see Division B1). Compounds that may be hydro-genated are aralkyl compounds having acetylenic side chains, particularly those having a benzene radical and one to three side chains each having a triple bond, the side chains containing from 2-6 C atoms; acetylene alcohols, particularly acetylene alcohols with 3-16 C atoms, 1-2 triple bonds and 1-2 hydroxy groups; olefine alcohols with 3-16 C atoms, 2-3 double bond and 1-2 hydroxy groups; esters of these acetylene or olefine alcohols with lower fatty acids with 1-4 C atoms; vinyl esters; olefinically and acetylenically unsaturated carboxylic acids, particularly acetylene carboxylic acids with one to two acid groups and 3-10 C atoms; olefine carboxylic acids with 1-3 double bonds, 1-2 carboxylic groups and 3-12 C atoms; derivatives of these acids, e.g. esters of lower alcohols with 1-4 C atoms in each alkyl; unsaturated ketones, e.g. alkylalkenyl ketones and alkylalkinyl ketones with 1-6 C atoms in the alkyl and 2-6 C atoms in the unsaturated radical. Preferred compounds are named. The following hydrogenations are exemplified Ex. 1 the triple bond in 2-butinediol-(1,4) to a double bond; Ex. 2 the terminal double bond in linalool; Ex. 4 the triple bond in 1,1,4,4 - tetramethyl - 2 - butinediol - (1,4) to a double bond; Ex. 5 dimethyl ethinyl carbinol to dimethylvinyl carbinol; Ex. 6-9 (1,4)-butinediol to butenediol; Ex. 12 one double bond in farnesylacetone; Ex. 13 acetylene dicarboxylic acid to ethylene dicarboxylic acid.