Großtechnische Herstellung von Oxo‐Alkoholen aus Propylen in der BASF

Abstract

Die autokatalytische Veresterung wird in der BASF auch fur die Umsetzung von Phthalsaureanhydrid mit anderen Oxoalkoholen, wie Isooctanol, Isononanol und Isodecanol, technisch angewendet, 1131. Sie wurde unter etfwas abgewandelten Bedingungen a.uf die Herstellung von Est,ern aliphabischer Dicarbonsauren mit Oxoalkoholen iibertragen. Die Methode erwies sich damit als allgemein brauchbar und leistungsfahig. Bewufit wurde dabei das Arbeiten bei Atmospharendruck und in einer Kaskade von Riihrkesseln, welche im Vergleich zu anderen verfahrenstechnischen Moglichkeiten relativ grofie Reaktionsvolumina je Kessel hat, in Kauf genommen. Trotz grofierer Verweilzeit erhalt man so das beste Produkt. AuBerdem erwies sich die neue Verfahrensweise als aufierordentlich flexibel gegeniiber Betriebsstorungen. -I n der BASF werden heute 90 bis 95% der Weichmacher-Produktion nach dieser Methode hergestellt. Diese Rationalisierung der Weichmacher-Erzeugung wurde von G. Pohler veranlaot. Die kinetischen Messungen stammen von P. Haug. An der Ubertragung in die Fabrikation

Controlling the Depolymerization of Paraformaldehyde with Pd–Phosphine Complexes

“…Most often the CO molecule is added to an alkene or alkyne whereas the products range from aldehydes over ketons to esters and carboxylic acids depending on the reaction conditions, catalysts and cosubstrates. [3] CO gas is easily available on al arge scale, shows the necessary reactivity and is cheap so that it is the CO source of choice for industrial processes like the BASF-oxo process [4,5] and Ruhrchemie/Rhone-Poulenc process. [6,7] Unfortunately CO gas is toxic and it is difficult to handle on as maller scale or when it cannotb ep roduced on site.…”

Iron Catalyzed Hydroformylation of Alkenes under Mild Conditions: Evidence of an Fe(II) Catalyzed Process

“…3 The first and second generation catalysts developed by BASF and ICI were based on cobalt. 4 However, the cobalt catalyzed process requires harsh conditions such as 100−350 bar syngas (1:1 mixture of CO:H 2 ) pressure and around 100−200 °C temperature. Widespread academic and industrial research to address this bottleneck led to a rhodium catalyzed low-pressure oxo-process (LPO) (10−60 bar and 80−135 °C), 5 which was developed by Union Carbide and Celanese in the mid-1970s.…”

“…11 Although it was not clear which metal was responsible for the observed hydroformylation activity, a synergistic effect between the two metals was claimed to be responsible. The latest report in iron catalyzed hydroformylation was published in 2000, utilizing an isolated iron complex [Fe(η 6 -CHT)(η 4 -COD)], (CHT: 1,3,5cycloheptatriene; COD: 1,5-cyclooctadiene). 12 Iron catalyzed hydroformylation of 1-hexene and styrene at 100 °C and 100 bar syngas pressure was investigated (Figure 1, left).…”

Palladium‐Catalyzed Hydroformylation of Alkenes and Alkynes

“…In consequence, the cobalt‐based processes were introduced early to the industry already in 1953. A significant amount of oxo products is still produced using the processes invented in the 1950s [7,14,15] . However, the cobalt‐catalyzed reactions suffer from severe reaction conditions, low regioselectivity, and many side processes.…”

“…A significant amount of oxo products is still produced using the processes invented in the 1950s. [7,14,15] However, the cobaltcatalyzed reactions suffer from severe reaction conditions, low regioselectivity, and many side processes. In contrast, the rhodium-catalyzed hydroformylation, which was discovered and reported by Wilkinson in 1965, proceeds with superior chemoand regioselectivity under milder conditions than those of the cobalt-catalyzed processes.…”