GB747493A - Improved oxo aldehyde synthesis - Google Patents

Improved oxo aldehyde synthesis

Info

Publication number
GB747493A
GB747493A GB9184/53A GB918453A GB747493A GB 747493 A GB747493 A GB 747493A GB 9184/53 A GB9184/53 A GB 9184/53A GB 918453 A GB918453 A GB 918453A GB 747493 A GB747493 A GB 747493A
Authority
GB
United Kingdom
Prior art keywords
feed
stock
cobalt
carbonylation
catalyst
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
GB9184/53A
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
ExxonMobil Technology and Engineering Co
Original Assignee
Exxon Research and Engineering Co
Esso Research and Engineering Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Exxon Research and Engineering Co, Esso Research and Engineering Co filed Critical Exxon Research and Engineering Co
Publication of GB747493A publication Critical patent/GB747493A/en
Expired legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C11/00Aliphatic unsaturated hydrocarbons
    • C07C11/02Alkenes
    • C07C11/08Alkenes with four carbon atoms
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/49Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide
    • C07C45/50Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide by oxo-reactions

Abstract

Aldehydes are prepared by a carbonylation process from a mono-olefinic feed-stock containing a minor proportion of polyolefines inhibiting carbonylation of the feed-stock, which comprises treating the feed-stock in a hydrogenation zone with a hydrogen gas containing carbon monoxide in the presence of a non-carbonyl forming hydrogenation catalyst at elevated temperatures and pressures whereby the polyolefines contained in the feed-stock are substantially converted to mono-olefines and passing the hydrogen-treated feed-stock to a carbonylation zone wherein the treated feedstock is reacted with carbon monoxide and hydrogen at elevated temperature and pressure in the presence of a carbonylation catalyst to form aldehydes containing at least one more carbon atom than the mono-olefines in the treated feed-stock; the aldehydes may then be hydrogenated to alcohols. The pretreatment of the feed-stock results in reduction of the carbonylation inhibition and reaction times, increased yield of aldehydes of improved colour and elimination of resin-forming bodies. Feedstocks which may be treated include olefine fractions, especially the C6-18 fractions, obtained by thermally cracking wax, cracked petrolatum fractions, butene fractions containing butadienes and the liquid stream from the lowpressure cracking of gas oil. The preferred pretreatment catalysts are the sulphide type of hydrogenation catalysts, e.g. molybdenum sulphide on active carbon and tungsten sulphide; platinum and palladium are also mentioned. Suitably, the catalyst is contacted with the feed-stock in the liquid or vapour phase at 200 DEG to 500 DEG F. and at pressures up to the aldehyde synthesis pressures of 2500 to 3500 p.s.i.g. in the presence of a hydrogen-carbon monoxide mixture, which is preferably the carbonylation synthesis gas or hydrogen-fortified synthesis gas. The carbonylation is preferably carried out at about 350 DEG to 450 DEG F. under pressures of about 2500 to 3500 p.s.i.g., using a synthesis gas containing H2 and CO in equal volumes, the catalyst being preferably in the form of a fatty acid salt, e.g. of stearic, palmitic, oleic or naphthenic acid such as the cobalt salt, though cobalt carbonyl, cobalt oxide, cobalt carbonate, cobalt acetate or formate or aqueous solutions containing the cobalt carbonyl anion are also suitable. The hydrogenation of the aldehydes to alcohols is effected at temperatures between 150 DEG and 550 DEG F. under pressures of about 1500 to 4500 p.s.i.g. with such catalysts as metallic nickel or cobalt, tungsten, molybdenum and nickel sulphides and copper chromite. A process described with reference to apparatus (not shown) comprises feeding synthesis gas and olefinic feed-stock having, say, 2 to 25 per cent of polyolefinic compounds into a hydrogenation reactor under synthesis temperature and pressure using molybdenum sulphide catalyst, the residence time being sufficient to reduce the polyolefine content of the feed to below inhibiting proportions; the reaction mixture is then fed to a gas-liquid separator from which the liquid passes to an oxo reactor while part of the gas is recycled to the hydrogenator and the remainder with more synthesis gas passes to the oxo reactor which contains a cobalt catalyst. The synthesis product is fed to a decobalting zone where it is treated in various specified ways for removal of cobalt and thereafter the aldehydes are converted into alcohols. If desired, the hydrogenation pretreatment and carbonylation may be effected in the one vessel, the pretreatment catalyst and feedstock being supplied to the bottom of the reactor and cobalt catalyst introduced downstream in the direction of flow, all the synthesis gas being fed in at the bottom or part being fed at the bottom and the remainder introduced downstream. An example describes the carbonylation of an olefinic naphtha, obtained by steam cracking and clay treating, and shows the reduction of the inhibition period when the feed-stock is pretreated as above described. Experiments are also described showing the inhibiting effects of (1) polyolefines in a crude C7-8 olefine fraction; and (2) 2-methyl-1:3-pentadiene in a heptene fraction obtained by copolymerization of propylene and butylene, in conventional carbonylations. Specification 684,958 is referred to.
GB9184/53A 1952-06-07 1953-04-02 Improved oxo aldehyde synthesis Expired GB747493A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US747493XA 1952-06-07 1952-06-07

Publications (1)

Publication Number Publication Date
GB747493A true GB747493A (en) 1956-04-04

Family

ID=22121467

Family Applications (1)

Application Number Title Priority Date Filing Date
GB9184/53A Expired GB747493A (en) 1952-06-07 1953-04-02 Improved oxo aldehyde synthesis

Country Status (1)

Country Link
GB (1) GB747493A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115430368A (en) * 2022-08-31 2022-12-06 兖矿鲁南化工有限公司 System and process for preparing butanol and octanol by carbonylation slurry gas-liquid mixing

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115430368A (en) * 2022-08-31 2022-12-06 兖矿鲁南化工有限公司 System and process for preparing butanol and octanol by carbonylation slurry gas-liquid mixing

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