DE1911631A1 - Process for the hydroformylation of olefins - Google Patents

Description

The invention relates to a new process for the hydroforming, synthesis of olefins, including aldehydes and / or Alcohols as well as a new complex catalyst.

In the oxy process, an olefin becomes carbon monoxide and hydrogen reacted using elevated temperature and pressure. The products can be aldehydes or Be alcohols or a mixture of both · Previously cobalt complexes, especially the octacarbonyl and themselves species derived therefrom have been the most widely used catalysts, but recently it has been shown that a number of Rhodi'umkomplexe the reaction, under catalyzed more favorable conditions.

9088 ^ 1/1730 - 2 -

The published Dutch patent application no. 66.08122 shows that complexes such as IrH ,, / "* P (phenyl) ^ ₉ ethylene hydroformylates at very high pressures above 250 atm.

Surprisingly, it has now been found that certain complex carbonyl hydrides of iridium olefins under a lot hydroformylate in milder conditions.

Thus, according to the invention, a process for the hydroformylation of olefins is provided, which therein consists that one is an olefin with carbon monoxide and Hydrogen hydrofermylated at elevated temperature in the presence of a complex of iridium, which one Carbonyl ligands, one hydride ligand, and three others contains neutral ligands.

Suitable neutral complexing ligands are those containing an atom of an element from group Vb or VXb, which is a single pair of Has electrons that are available for donation, in particular Phosphorus, nitrogen, arsenic, antimony or sulfur.

Al »ligands are primarily trialkyl- '" ■■ phosphines, triarylphosphines, trialkyl- or triaryl ^ arsines or stibines, pyridines, such as pyridine, 2,2 ¹ ^ di- "· pyridyl or 2-methylpyridiii, Alkyl or aryl amines, '

909841/1730

such as aniline, p-toluidine or ethylenediamine. Dimethyl and diphenyl sulfoxides can also be used.

The preferred ligands are trialkyl or triaryl phosphines and in particular triphenyl phosphine, triethyl phosphine, tri-n-propylphosphine and tri-n-butylphosphine. A particularly suitable complex is ··, IrHCO (Ph ₃ P) ₃ , Ph m phenyl. These iridium complexes are of particular interest because other iridium carbonyl hardnesses appear to hydroformylate olefins rather than hydroformylate them.

Suitable starting materials are olefins, which have between 2 and 20 carbon atoms per molecule, and especially propylene, hexenes and heptenes.

The catalyst can be dissolved in a solvent or introduced into the feed or re-circulated product. The solvent can be a saturated or aromatic hydrocarbon. Normal paraffins such as η-hexane, n-heptane and α-oetane are suitable. However, any aromatic or aliphatic monohydric alcohol can also be used, but the circulated product alcohol is preferred. On the other hand, there are aliphatic monohydric alcohols which have between k and 20 carbon atoms per molecule,

9098-1 / 173 0

suitable. Lower alcohols tend to de.au, with the 'through the first stage of the reaction formed aldehyde acetals to build.

The hydroformylation is useful in one Pressure between 0 and 281 atmospheres (θ and 4000 psig), preferably between 0 and 56 atmospheres (θ and 800 psig).

Preferably, the temperature "is as above 20 and 250 ⁰ C, in particular between 60 and 180 ⁰ C.

The ratio of hydrogen to carbon monoxide in the feed may be between 4t1 and tk. 1 The preferred ratios are 2i1 and ItI.

Preferably the catalyst is in amounts between 1t30 and ItI OOO 000 fetches per mole of the olefin content present "in particular" between 1 * 300 and 1: 50,000 moles per mole of feed. ·

According to a further feature of the invention is a Catalyst created, which is a complex of iridium is, which has a carbonyl ligand, a hydride ligand and contains three neutral ligands. \

The catalyst is preferably IrHCO (Ph "P)" _f where Ph ■ is phenyl.

The catalyst can be fed into the reactor before it is fed manufactured, cleaned and labeled.

9O0Ö41 / 1730

The invention is illustrated by the following examples ■ explained in more detail, but not restricted.

■ ^ ■ t * '* EXAMPLES

General method ι

Ee were 0.2 g of the catalyst together with 15al Place hot-1 and 30 ml of n-heptane in a stainless steel container. The container was in a heated shaking autoclave and three times with hydrogen-carbon monoxide in a molar ratio of 1: 1 cleaned and then pressurized with the same gas. Then the heating started and the Shaking movement started. After the reaction had occurred, the autoclave was allowed to cool down Excess gas was released and the product removed and analyzed

The results are shown in the table below.

Experiments 2 and 3 are not examples of the invention, but are merely intended for comparison.

Example 1 shows the result obtained for the said iridium complex IrH (CO) (Ph ₃ P) ". Examples 2 and 3 show that IridiuMhjrdride generally catalyze hydrogenation of this" olefin "to hydrocarbon.

9G98A1 / T730 ^!

Starting olefin ι Solvent ι gas ratio!

Witches-1

n- ^ heptane

1: 1 molar ratio H ₂ / C0

ft
catalyst Time
^δ σ Te-p. pressure
P s iff
max - min Olefin
conversion
f Product distribution
(# Mole free »olefin) Hexane branching
ter aldehyde normalor
aldehyde Alcohols 1 IrH (CO) (Ph ₃ P) ₃
2 IrH (CO) (Ph ₃ P) ₂ Eq ₂
3 .XxH ₂ (CO) (Ph ₃ P) ₃ Cl 3.0
1.0
4.0 95-5
τοοίι
1 7θί 1 600-295
650-610
700-510 1 00
43
81 2
45;
65 28
1.6
i.1 70
38 no
no
no

CD O CD CD

C5

cn 00

Claims (1)

PATENT CLAIMS 1 . Process for the hydroformylation of olefins, characterized in that an olefin with carbon monoxide and hydrogen at elevated temperature in Presence of a complex of iridium hydroforroylated, the one carbonyl ligand, one hydride ligand and contains three other neutral ligands. 2. The method according to claim 1, characterized in that the catalyst is alkyl or arylamine, Phosphine, arsine, stibine, phoaphite, arsinite, stibinite, Mercaptan, sulfoxide, pyridine or substituted ones Contains pyridine ligands. 3. Process according to claim 1 or 2, characterized in that the catalyst contains methylamine, ethylamine, n-propylamine, triphenyl, phosphine, triphenylarsine, triphenylstibine, triphenylphosphine, triethylphosphite pyridine or oC-picoline ligands. 4. The method according to claim 1 or 2, characterized gekennaelehnet that the catalyst contains trialkylphosphine ligands. 90 9841/173 0. 5. The method according to any one of claims 1,. 2 or 4, characterized in that the catalyst triethylphosphine, tri-n-propylphosphine, tri-n-butylphosphine, Tri-cyclohexylphosphine or trioctylphosphine ligands contains. 6. The method according to claim 1 or 3 »characterized in that the catalyst is IrHCO (Ph-P) ~. 7 · procedure '^; «A $ jji ,. any one of the preceding claims, characterized in that the feed is an olefin having between 2 and 20 carbon atoms per molecule. " ^Ώ -, 8. The method according to claim 7, characterized in that the olefin is propylene, a hexene or a Hepten is. . 9. Process according to Claim 8, characterized in that the olefin is 3-ethylpentene-1 or 3-ethylpentene-2. 10. The method according to any one of the preceding claims, characterized in that the catalyst in a »solvent or dissolved in the feed or recirculated product is introduced. 9 0 9 8 4 1/17 3 0 11. The method according to claim 10, characterized in that the solvent is a saturated or is aromatic hydrocarbon. 12, method according to claim 11, characterized in, that the solvent is a normal paraffin. 13. The method according to claim 12, characterized in that that the solvent is η-hexane, n-heptane or n-octane " 14. The method according to claim 1 to 10, characterized characterized in that the solvent is an alcohol. 15. The method according to claim 1 ^, characterized in that the alcohol is a monohydric alcohol which has between k and 20 carbon atoms per molecule. 16. The method according to claim 10, characterized in that the solvent is the recirculated Product is. ~ 10 9098 4 1/1730 17. Proceed according to one of the preceding Claims, characterized in that at a total pressure between 0 and 281 atü (between 0 and 4000 psig). 18. The method according to claim 17 »characterized in that the pressure is between 0 and 141 atü (0 and 2000 psig). ^ .: "'' ^i? ^, _n 19 · Method according to one of the preceding Sayings, characterized in that it is called one Temperature between 20 and 250 ° C is carried out. 20 * Method according to claim 19 · characterized in that the temperature is between 60 and 180 C
lies. 21. Method according to one of the preceding
Claims, characterized in that the ratio of hydrogen eu carbon nonoxide in the charge
is between 4: 1 and 1: 4. 22. The method according to claim 21, characterized in that that the ratio of hydrogen to carbon monoxide 2: 1 is. - 11 - 90 984 1/1730 23i method according to claim 21, characterized in that the ratio of hydrogen to carbon monoxide is 1: 1 Zk. Process according to any one of the preceding claims, characterized in that the ratio of catalyst to olefin feed is between 1:30 and is 1: 1,000,000 moles per mole. * ° 1 1 K " $ [: 25. The method according to claim 2k, characterized in that the ratio of catalyst to olefin is between 1t36O and 1:50,000 mol per mol. 26. Sin catalyst for a method according to any one of the preceding claims, characterized in that the catalyst is a complex of iridium which contains an carbonyl ligand, a hydride ligand and three other neutral ligands. 27. Catalyst according to claim 26, characterized in that it has the formula IrHCO (Ph_P) _. 28. The procedure described in Example 1. 29. Aldehydes or alcohols, characterized in that they are prepared by the method according to any one of claims 1-26 or 28. 909841/1730