Exxonmobil Chemical Patents Inc.

Exxon Chemical Patents, Inc.

Ronald Dean Garton

Raphael Frans Caers

Arie Van Vliet

Eddy T A Van Driessche

James T Ritchie

Corey W Reed

Krishna Kulai Rao

Hubertus Joseph Beckers

Hans Georg Korsten

Krishnan Sankaranarayanan

David G Woods

Pierre J Osterrieth

Brian C McClaine

Matthew Findlay

Bruce D Lilly

Ramzi Yanni Saleh

Eddy Theophile Van Driessche

Stephen Wayne Beadle

Magdiel Agosto

Kenneth Joseph Buturla

Jan Martin De Rijke

Edwin Kooke

Hubertus Jozeph Beckers

Donald Q Brown

John J Houben

Nico A De Munck

Dominic T Clausi

Michel J P Lepagnol

Bertrand Raymond Da Cruz

An improved hydroformylation catalyst cycle is disclosed wherein the cobalt catalyst is recycled to the hydroformylation reaction mainly as a water soluble carbonyl salt, obtained from extraction of the acidic form of the homogeneous cobalt carbonyl catalyst from the hydroformylation product with an aqueous solution of a salt of a weaker acid. The organic product after extraction is submitted to a further demetalling step in the presence of a dilute acid and an oxidant. The water from this further demetalling step is suitable for use in the upstream extraction step. A free water phase present in the hydroformylation reaction product may be separated upstream from the extraction step and is suitable for use in the further demetalling step, such that the catalyst cycle has no waste water stream.

Hydroformylation process including catalyst recycle

In the hydroformylation of C5-C14 olefins with cobalt catalyst to produce C6-C15 oxygenates, where offgasses from the hydroformylation or cobalt removal step contain volatile cobalt compounds, the cobalt compounds are recovered by scrubbing the offgas with a liquid, and recycling the liquid to the cobalt removal step. Suitable scrubbing liquids are the organic cobalt-depleted hydroformylation reaction product or a downstream derivative thereof, or an aqueous solution of a Cosalt, preferably such salt of formic acid.

Offgas cleanup in olefin hydroformylation

Acetals are formed from an aldehyde hydrogenation product mixture comprising alcohols and at most 2% of alde-hydes and the product is distilled to yield purified alcohols and a second stream containing acetals and/or unsaturated ethers.

Manufacture of purified alcohols

Oxidative recovery methods that use oxygen or air for recovery of homogeneous metal catalysts, such as cobalt catalysts, used in for example hydroformylation processes, can be hazardous. Explosive or flammable gas mixtures may be generated inside the process equipment, which can deflagrate upon any ignition source such as a static electricity discharge. The use of a flammable diluent has been found to be a very effective way of optimizing the recovery method, by bringing the resulting gas mixtures above their upper flammability limit. The offgas produced is then also easier to dispose of as a fuel, as compared to when a non-flammable diluent is used.

Oxidative demetalling

In a hydroformylation reaction, the circulation and recovery of cobalt carbonyl in a cobalt catalyst cycle using carbonylate as an intermediate and acidification thereof, is improved by supplying an aqueous sulfuric acid solution containing less than 16% wt of sulfuric acid to the carbonylate to control sulfuric acid concentration in the carbonylate/acid mixture, before accounting for any acid consuming reaction, to a value of from 2% to 10% by weight. Single step and multistage liquid/liquid extraction techniques as well as vapor/liquid extraction techniques followed by the absorption of cobalt from the vapor in an organic liquid both benefit from this improvement.

Cobalt recovery from cobalt catalysed hydroformylation reactions

The invention relates to improvements in internal loop reactors. The reactor of the invention is characterized by a plurality of cooling tubes which form the annulus between the riser and the downcomer path of said internal loop reactor. The reactor also provides improvements in hydroformylation reactions using the improved reactor.

Internal loop reactor and Oxo process using same

The invention provides a system for designing, operating, monitoring and/or diagnosing a chemical reaction, particularly a hydrotreating process, using a fixed bed catalytic reactor.

Fixed bed reactor

Acetals are formed from a mixture comprising alcohols and aldehydes and the product is distilled to yield purified alcohols and/or acetals and/or unsaturated ethers.

Manufacture of alcohols

Method of operating a fixed bed reactor under predetermined hydraulic conditions

The gas cycle in a high pressure hydroformylation reaction using a series of at least two reactors is controlled to optimise yield, conversion and selectivity and to control reaction temperature. The control is achieved through balancing fresh gases and recycle gases in each of the reactors and as an optional feature the use of hydrogen off gases from the downstream hydrogenation used in the conversion of the hydroformylation reaction product to product alcohols.

Hydroformylation

The Cobalt Flash Process is modified by replacing formic acid with acetic acid as process acid. Efficiency using acetic acid as process acid is achieved by two improvements which may be added separately and independently: (1) separation of acetic acid and water from the condensate distilled off in the cobalt salt concentration stage; and (2) removal of formic acid from the system by reaction with the product alcohol in the preformer.

Cobalt flash process

The Oxo Process that recycles its cobalt primarily as cobalt salt is improved by concentration of the cobalt salt solution from the demetalling section and the addition of a separation step for organic acid and water. This allows for a higher reuse of acid in the process and thus a lower amount of acid in the waste water. Injecting a higher concentration of cobalt salt solution to the reaction section also reduces the requirement for cobalt source.

Oxo process

In the process of hydrogenating a crude aldehyde product formed from the oxo process into a crude alcohol product, which process includes: feeding the crude aldehyde product into a first reactor which contains a hydrogenation catalyst, thereby forming a first hydrogenated product; feeding the first hydrogenated product from the first reactor through at least one intermediate reactor, each intermediate reactor being connected in series and containing a hydrogenation catalyst, thereby forming at least one intermediate hydrogenated product; and feeding the intermediate hydrogenated product from a last intermediate reactor to a final reactor which contains a hydrogenation catalyst, thereby forming the crude alcohol product; the improvement including a step wherein: at least a portion of the first hydrogenated product is recycled to the first hydrogenation reactor; or at least a portion of the intermediate hydrogenated product is recycled to the first hydrogenation reactor or an intermediate reactor upstream of the intermediate reactor from which the intermediate hydrogenated product is removed.

Growing community of inventors

Baton Rouge, LA, United States of America

Ronald Dean Garton