公开(公告)号：JPH1067790A

公开(公告)日：1998-03-10

申请号：JP21776297

申请日：1997-08-12

Applicant: HOECHST AG

Inventor： BAHRMANN HELMUT DR ,  MUELLER THOMAS DIPL ING

IPC: C07B63/00 ,  B01J31/40 ,  C07C45/50 ,  C07F9/02 ,  C07F9/50 ,  C07F9/53

Abstract: PROBLEM TO BE SOLVED: To efficiently separate the subject catalytically inert compounds by extracting a homogeneous hydroformylation reaction mixture containing a catalyst and an excessive ligand with a solution of an alkali metal hydroxide and separating an aqueous phase. SOLUTION: An organic reaction mixture of a homogeneous hydroformylation carried out by the use of a catalyst containing an organometallic complex compound and an aromatic phosphine ammonium salt of the formula (X is a sulfonate group or a carboxylate group; (a), (b) and (c) are each 0 or 1 and at least one of these parameters (a), (b) and (c) is 1; (n) is 1, 2 or 3; R and R are each a 4-30C alkyl, a 6-10C aryl or cycloalkyl; R' may be H) is extracted with 0.001-0.5wt.% solution of an alkali metal hydroxide or an alkaline earth metal hydroxide. Then an aqueous phase containing phosphine oxide and an alkylarylphosphine is separated to separate the objective compound from the homogeneous hydroformylation reaction mixture.

公开(公告)号：JPH1053551A

公开(公告)日：1998-02-24

申请号：JP11154397

申请日：1997-04-28

Applicant: HOECHST AG

Inventor： BAHRMANN HELMUT DR ,  FROHNING DIETER DR ,  GICK WILHELM DR ,  HOEFS WOLFGANG DIPL ING ,  KALBFELL HEINZ DIPL ING ,  KAPPESSER HARALD ,  LAPPE PETER DR ,  SCHALAPSKI KURT ,  WIEBUS ERNST ,  ZGORZELSKI WOLFGANG DIPL ING

IPC: B01J31/24 ,  C07B61/00 ,  C07C45/50 ,  C07C47/02

Abstract: PROBLEM TO BE SOLVED: To convert an olefinic compound existing in an exhaust gas of hydroformylation carried out by using an aqueous catalyst solution under an economically proper condition into a carbonyl compound. SOLUTION: This hydroformylation for an olefinic unsaturated compound comprises a first reaction stage in which the reaction is carried out in a heterogeneous reaction system by using an aqueous solution containing a rhodium compound containing a water-soluble organic phosphorus (III) compound in the form of complex under 0.4-10MPa to give an exhaust gas. The exhaust gas produced in the first reaction stage is introduced to a second reaction stage, in which the residue of the olefinic unsaturated compound still existing in the exhaust gas is reacted in a heterogeneous reaction system in the presence of the rhodium complex of the organic phosphorus (III) compound as the catalyst under 15-40MPa.

公开(公告)号：JPH1066877A

公开(公告)日：1998-03-10

申请号：JP12450297

申请日：1997-05-14

Applicant: HOECHST AG

Inventor： BAHRMANN HELMUT DR ,  LAPPE PETER DR ,  MUELLER THOMAS DIPL ING

IPC: B01J31/02 ,  B01J31/24 ,  B01J31/40 ,  B01J38/00 ,  C07B61/00 ,  C07C45/49 ,  C07C45/50 ,  C07C45/78 ,  C07C47/02 ,  C07F9/50

Abstract: PROBLEM TO BE SOLVED: To obtain the catalyst system based on rhodium complex containing organophosphorus ligand which can be separated from a hydroformylation reaction mixture by a simple method by using a compound expressed by a specified formula as diphosphine in a catalyst system with a substrate of a rhodium complex containing a diphosphine ligand. SOLUTION: A catalyst used in the production of aldehyde by hydroformylating an olefinic unsaturated compound in a homogeneous phase is made a catalyst system with a substrate of a rhodium complex containing a diphosphine ligand, and a compound expressed by the formula I is used as the existing diphosphine ligand. In the formula, R is carboxylate, sulfonate, or 2-aminoethane bis-phosphonate group, R is alkylene group, oxygen-containing alkylene group, cycloalkylene group, a to d are 0 or 1 and at least one of them is 1, R and R are alkyl, aryl, or cycloalkyl group or benzyl group, and R can be hydrogen.

公开(公告)号：JPH1059890A

公开(公告)日：1998-03-03

申请号：JP12450397

申请日：1997-05-14

Applicant: HOECHST AG

Inventor： BAHRMANN HELMUT DR

IPC: B01D61/02 ,  B01J31/02 ,  B01J31/22 ,  B01J31/24 ,  B01J31/28 ,  B01J31/40 ,  B01J38/00 ,  C07B61/00 ,  C07C45/50 ,  C07C45/78 ,  C07C47/02 ,  C07C47/34 ,  C07F9/50

Abstract: PROBLEM TO BE SOLVED: To provide a method for producing an aldehyde, capable of hydroformylating an olefinic unsaturated compound in high activity and selectivity by reacting an olefinic unsaturated compound with hydrogen and CO in the presence of a specific catalyst system in a uniform phase and subsequently separating the catalyst system from the reaction product. SOLUTION: This method for producing an aldehyde comprises hydroformylating (B) an olefinic unsaturated compound with (C) hydrogen and (D) CO in the presence of (A) a catalyst system containing (i) an organic metal complex compound and (ii) a ligand for the complex compound in an excessive amount in a uniform phase, and subsequently press-filtering off the component A from the hydrofromylation product mixture with an aromatic polyamide semi-permeable membrane. The molar ratio of the component (ii) to the obtained aldehyde is 9-30, preferably 10-25, especially 10-15. The component (ii) excludes the alkyl or arylammonium slat of a sulfonated, carboxylated or phosphonated aromatic diphosphine.

公开(公告)号：JPH1045780A

公开(公告)日：1998-02-17

申请号：JP12450197

申请日：1997-05-14

Applicant: HOECHST AG

Inventor： BAHRMANN HELMUT DR ,  LAPPE PETER DR ,  MUELLER THOMAS DIPL ING

IPC: C07C45/50 ,  C07F9/50

Abstract: PROBLEM TO BE SOLVED: To obtain a novel substituted diphosphine which can be used in a rhodium complex-based catalyst for hydroformylation to give the catalyst a high activity and selectivity and enables the catalyst system to be readily separated from the reaction product. SOLUTION: This novel substituted diphosphine is represented by formula I [R is carboxylate, sulfonate, phosphonate, 2-aminoethanebis-phosphonate; R is a 1-8C straight chain alkylene, an oxygen-containing 2-6C alkyl, a 3-10C cycloalkylene; a-d are each 0 or 1; R and R are each a 4-26C alkyl, a (substituted) 6-10C aryl, a 6-10C cycloalkyl, benzyl or the like], typically, distearylammonium 1,3-bis-(di-m-sulfonatophenylphosphino)propane. The compound of formula I is prepared by sulfonation of a diphosphine of formula III obtained from a secondary phosphine oxide of formula II as a starting substance with fuming sulfuric acid, diluting the sulfonation mixture with water and adding a water-insoluble amine NR R R dissolved in a water-insoluble organic solvent thereto.

公开(公告)号：JPH11222450A

公开(公告)日：1999-08-17

申请号：JP32797798

申请日：1998-11-18

Applicant: HOECHST AG

Inventor： BAHRMANN HELMUT DR ,  GREB WOLFGANG ,  HEYMANNS PETER ,  LAPPE PETER ,  SZAMEITAT JUERGEN ,  MUELLER THOMAS DR ,  WIEBUS ERNST

IPC: B01J31/24 ,  C07B61/00 ,  C07C27/22 ,  C07C29/141 ,  C07C29/17 ,  C07C31/125 ,  C07C45/50 ,  C07C45/74 ,  C07C47/21 ,  C07C67/08 ,  C07C69/80

Abstract: PROBLEM TO BE SOLVED: To provide a hydroformylation method for producing a decyl alcohol isomer mixture in which the hydroformylation of butadiene to provide an aldehyde mixture, the separation of the obtained aldehyde mixture from the reaction product, the condensation of the aldehyde mixture and the separation of an aldol mixture, during the formation of the aldol mixture, and the hydrogenation of the aldol mixture to provide a decyl alcohol isomer mixture are included, and by which the butadiene can be industrially readily converted to a desired alcohol. SOLUTION: Butadiene is subjected to hydroformylation in the presence of water and water-soluble rhodium-, alkyl- or aryl-diphosphine-complex as a catalyst at 70-150 deg.C under 0.4-30 MPa pressure. The volume ratio of the aqueous phase to the organic phase is (0.1-100):1, the rhodium concentration in the aqueous catalytic solution is 20-2,000 ppm, and the phosphine of 4-100 mol per mol rhodium is used.

公开(公告)号：JPH1072395A

公开(公告)日：1998-03-17

申请号：JP12450497

申请日：1997-05-14

Applicant: HOECHST AG

Inventor： BAHRMANN HELMUT DR ,  THOMAS MYUURAA ,  LUKAS RAINER

IPC: B01J31/02 ,  B01J31/24 ,  B01J31/40 ,  B01J38/00 ,  C07B61/00 ,  C07C45/50 ,  C07C45/78 ,  C07C47/02 ,  C07C47/34 ,  C07F9/50

Abstract: PROBLEM TO BE SOLVED: To provide a method for producing an aldehyde by which the aldehyde can be obtained in high activity and high selectivity by hydroformylating an olefinic unsaturated compound in a homogeneous phase from which the whole catalyst system can be separated. SOLUTION: The objective aldehyde is produced by hydroformylating an olefinic unsaturated compound with H2 and CO in the presence of a catalyst system containing a rhodium complex salt compound and an excess molar amount of an aromatic phosphine of the formula [X is a sulfonate residue, etc.; (a) to (c) are each 0 or 1 with the proviso that at least one of (a) to (c) is 1; (n) is 1, 2 or 3; R and R are each an 8-30C alkyl residue, etc., with the proviso that the total number of C in the R and the R is at least 30] in a homogenous phase and separating the catalyst system from the reaction mixture by using an aromatic polyamide semipermeable membrane and performing pressure filtration. Moreover, the hydroformylation is performed at pH2.5-4.3, by regulating the mol ratio of the phosphine to the rhodium to at least 60 and the rhodium concentration based on the amount of the olefinic unsaturated compound to at least 10wt.ppm.

公开(公告)号：JPH1059889A

公开(公告)日：1998-03-03

申请号：JP16712497

申请日：1997-06-24

Applicant: HOECHST AG

Inventor： REGNAT DIETER DR ,  KLEINER HANS-JERG DR ,  BAHRMANN HELMUT DR

IPC: B01J31/02 ,  C07B61/00 ,  C07C41/09 ,  C07C41/16 ,  C07C43/164 ,  C07C43/20 ,  C07C43/205

Abstract: PROBLEM TO BE SOLVED: To obtain the subject new compound insensitive to oxygen and/or sulfur and not hydrolyzed under hydroformylation conditions or having complex characteristics. SOLUTION: A compound of formula I [R -R are each independently H, a 1-4C alkyl or alkoxy, a 2-4C alkenyl, etc.; (m), (n) are each independently 0, 1 wherein [(m)+(n)] is 1 or 2; R is not substituted or is phenyl or naphthyl which may be substituted with a 1-4C alkyl, etc.,], e.g. 2,2'-bis(phenoxymethyl)-1,1'-binaphthyl. The compound of formula I is obtained by reacting a compound of formula II (A is OH, etc.,) with a compound of formula III [B is a releasable group: Z (Cl, Br, I, etc.,), when A is OH, or B is OH, when A is the releasable group Z] in a molar ratio of 1:(2-2.2) in the presence of a base and in an organic solvent inactive under the reaction conditions, in the presence (absence) of a phase transfer catalyst and water at 10-100 deg.C. The compound of formula I can exhibit an effect as a hydroformylation catalyst for the production of aldehyde compounds.

公开(公告)号：JPH1017519A

公开(公告)日：1998-01-20

申请号：JP6675297

申请日：1997-03-19

Applicant: HOECHST AG

Inventor： BAHRMANN HELMUT DR

IPC: B01J31/02 ,  B01J31/24 ,  C07B61/00 ,  C07C45/50 ,  C07C47/02

Abstract: PROBLEM TO BE SOLVED: To provide a method for producing an n-aldehyde in high conversion and high selectivity by hydroformylating a higher olefin in a multiphase system constituted of an aqueous catalyst solution, an organic raw material and optionally a reaction product and a gaseous reactant. SOLUTION: This method for producing an aldehyde comprises a reaction of (D) a >=3C olefinic unsaturated compound with (E) carbon monoxide and (F) hydrogen in the presence of a catalyst system of (A) water, (B) a solubilizing agent which is a compound of formula I [A is a (branched) 6-25C alkyl, a 6-25C ω-hydroxyalkyl, etc.; B, C and D are each a 1-4C (branched) alkyl or an ω- hydroxyalkyl or the C and the D can form a 5- or 6-member heterocycle with N; E is an inorganic or organic anion] and (C) a water-soluble rhodium complex having a compound of formula II substituted by one or more sulfonic acid groups [X is a 1-9C alkyl, a 6-10C cycloalkyl, etc.; R is H, a 1-14C alkyl, a 1-14C alkoxy, etc.; (m) is 0-5; (n) is 0-4] as a ligand in a liquid phase.

公开(公告)号：JPH107613A

公开(公告)日：1998-01-13

申请号：JP5514697

申请日：1997-03-10

Applicant: HOECHST AG

Inventor： BAHRMANN HELMUT DR ,  KLEINER HANS-JERG DR ,  REGNAT DIETER DR

IPC: B01J31/24 ,  B01J31/28 ,  B01J31/40 ,  C07B61/00 ,  C07C45/50 ,  C07C45/78 ,  C07C47/02

Abstract: PROBLEM TO BE SOLVED: To produce an aldehyde in high yield at a low cost with a long life of a readily reutilizable catalyst by reacting an olefinic compound with carbon monoxide and hydrogen in the presence of a specific catalyst and separating the resultant reactional product from the catalyst. SOLUTION: (C) A 2-20C olefinic compound is reacted with (D) carbon monoxide and (E) hydrogen in the presence (or absence) of (B) a solvent in the presence of (A) a catalyst comprising (A1 ) rhodium and (A2 ) a compound represented by formula I [R is H or a 1-12C alkyl; R is a 1-8C straight-chain alkylene, a 2-4C oxygen-containing alkylene, a group represented by formula II or III or a 3-10C cycloalkylene; R is a 1-25C alkyl or a 6-10C aryl; A is COO or SO3 ; (x), (y), (m) and (n) are as follows: (x)=0, (y)=(m)=(n)=1;(x)=(y)=1 and (m) and (n) are each 1 or 2 or (x) is 1; (y) is 0 and (m) and (n) are each 0 or 1 when R is a group represented by formula II or III] at 50-190 deg.C temperature under 0.1-45MPa pressure and the resultant reactional product is then separated from the component A.