Exxon Research and Engineering Company

Ciba-geigy Ag

Ciba-geigy Corporation

Other

Exxon Research & Engineering

Alexis A Oswald

Paul L Valint

I-Der Huang

Andrew A Westner

Edmund John Mozeleski

Ram N Bhatia

Torris G Jermansen

Lawrence L Murrell

Wolfgang H Mueller

Torris G Jermasen

Francis A Daniher

Douglas Brenner

Alexandr P Glivicky

John R Hooton

Harry W Barnum

Barry G Brueggeman

Charles M Smith

Daniel N Hall

Kenneth Lewtas

Albert Rossi

Darrell W Brownawell

Robert Dryden Tack

Thomas L Ashcraft

Chang S Hsu

David H Rehrer

Robert L Zapp

Guido Sartori

Warren A Thaler

David William Savage

Frank J Chen

Gary L Harting

Ramon L Espino

John S Huang

Kuo L Peng

Rodney V Kastrup

Paul Valint, Jr

Helen Huang

John C Reisch

Joseph S Merola

Joseph H Lesser

Peter J Kozak

A catalytic process for the hydroformylation of olefinic, sulfur containing thermally cracked petroleum streams to produce aldehydes and/or alcohols is disclosed. The catalysts are homogeneous transition metal carbonyl complexes. Especially preferred catalysts for low and medium pressure hydroformylation are cobalt and rhodium carbonyl hydride complexes in which some of the carbonyl ligands have been replaced by trivalent phosphorus ligands. In a preferred high pressure hydroformylation, the sulfur-containing naphtha and gas oil distillate feeds are produced from vacuum residua by high temperature thermal cracking. Such feeds contain more than 20% olefins with 1-n-olefins as the single major types. These olefin components are hydroformylated in the presence of a cobalt carbonyl complex to produce a novel type of semilinear aldehyde and/or alcohol product containing an average of less than one alkyl branch per molecule. The alcohols are converted to dialkyl phthalates and other esters having a unique balance of plasticizer properties. They are also useful for producing novel surfactants, particularly ethoxylated derivatives. For the preparation of products containing minimal concentrations of sulfur compounds, narrow distillate fractions of thermally cracked residua are preferred. In the C.sub.6 to C.sub.11 carbon range, single carbon fractions of sharply reduced aromatic hydrocarbon and thiophenic sulfur content can be obtained. These fractions of increased linear olefin content can be advantageously used as hydroformylation feeds in the derivation of low sulfur containing alcohols and related products of increased linearity.

Process for the hydroformylation of sulfur-containing thermally cracked

A catalytic process for the hydroformylation of olefinic, sulfur containing thermally cracked petroleum streams to produce aldehydes and/or alcohols is disclosed. The catalysts are homogeneous transition metal carbonyl complexes. Especially preferred catalysts for low and medium pressure hydroformylation are cobalt and rhodium carbonyl hydride complexes in which some of the carbonyl ligands have been replaced by trivalent phosphorus ligands. In a preferred high pressure hydroformylation, the sulfur-containing naphtha and gas oil distillate feeds are proudced from vacuum residue by high temperature thermal cracking. Such feeds contain more than 20% olefins with 1-n-olefins as the single major types. These olefin components are hydroformylated in the presence of a cobalt cabonyl complex to produce a novel type of semilinear aldehyde and/or alcohol product containing an average of less than one alkyl branch per molecule. The alcohols are converted to dialkyl phthalates and other esters having a unique balance of plasticizer properties. They are also useful for producing novel surfactants, particularly ethoxylated derivatives. For the preparation of products containing minimal concentrations of sulfur compounds, narrow distillate fractions of thermally cracked residua are preferred. In the C.sub.6 to C.sub.11 carbon range, single carbon fractions of sharply reduced aromatic hydrocarbon and thiophenic sulfur content can be obtained. These fractions of increased linear olefin content can be advantageously used as hydroformylation feeds in the derivation of low sulfur containing alcohols and related products of increased linearity.

A multistep process is disclosed for the manufacture of synthetic lubricants from the C.sub.8 to C.sub.24 linear olefin components of below liquid fuel value petroleum distillate fractions derived via the high temperature thermal cracking of petroleum residua. Such feeds contain major amounts of 1-n-olefins, n-paraffins and greater than 0.1% concentration of sulfur mostly in the form aromatic, thiophene type sulfur compounds. In the first step of the present process such feeds are enriched in the straight chain aliphatic hydrocarbon components by one or more separation processes, preferably via urea adduction or by crystallization. In the second step, the olefin components are oligomerized to sulfur containing C.sub.30 to C.sub.60 polyolefins, preferably in the presence of BF.sub.3 complex catalysts. In the third step, the polyolefins are hydrogenated to novel isoparaffin lubricants in the presence of sulfur resistant catalysts, preferably transition metal sulfides.

Multistep process for the manufacture of novel polyolefin lubricants

There are disclosed novel compositions of matter comprising monoalkylphenols prepared by selectively alkylating the olefin component of a thermally cracked sulfur-containing petroleum distillate derived from residua. The monoalkylphenols have certain ortho to para ratios and may be used to prepare a number of useful derivatives such as ethoxylated and propoxylated surfactants, sulfoalkylated products, sulfurized antioxidants, overbased phenates, dithiophosphate derivatives, formaldehyde reaction products and similar methylene bridged products which are useful demulsifiers.

Alkylphenols and derivatives thereof via phenol alkylation by cracked

A catalytic process for the hydroformylation of olefinic, sulfur containing thermally cracked petroleum streams to produce aldehydes and/or alcohols is disclosed. The catalysts are homogeneous transition metal carbonyl complexes. Especially preferred catalysts for low and medium pressure hydroformylation are cobalt and rhodium carbonyl hydride complexes in which some of the carbonyl ligands have been replaced by trivalent phosphorus ligands. In a preferred high pressure hydroformylation, the sulfur-containing naphtha and gas oil distillate feeds are produced from vacuum residue by high temperature thermal cracking. Such feeds contain more than 20% olefins with 1-n-olefins as the single major types. These olefin components are hydroformylated in the presence of a cobalt carbonyl complex to produce a novel type of semilinear aldehyde and/or alcohol product containing an average of less than one alkyl branch per molecule. The alcohols are converted to dialkyl phthalates and other esters having a unique balance of plasticizer properties. They are also useful for producing novel surfactants, particularly ethoxylated derivatives. For the preparation of products containing minimal concentrations of sulfur compounds, narrow distillate fractions of thermally cracked residua are preferred. In the C.sub.6 to C.sub.11 carbon range, single carbon fractions of sharply reduced aromatic hydrocarbon and thiophenic sulfur content can be obtained. These fractions of increased linear olefin content can be advantageously used as hydroformylation feeds in the derivation of low sulfur containing alcohols and related products of increased linearity.

This invention is a catalytic process for the hydroformylation of olefinic, sulfur-containing thermally cracked petroleum streams to produce aldehydes and/or alcohols. The catalysts are homogeneous transition metal carbonyl complexes. Especially preferred catalysts for low and medium pressure hydroformylation are cobalt and rhodium carbonyl hydride complexes in which some of the carbonyl ligands have been replaced by trivalent phosphorus ligands. In a preferred high pressure hydroformylation, the sulfur-containing gas oil distillate feed is produced from vacuum residua by high temperature thermal cracking. Such a feed contains more than 20% olefins with 1-n-olefins as the single major types. These olefin components are hydroformylated in the presence of a cobalt carbonyl complex to produce a novel type of semilinear aldehyde or alcohol product containing an average of less than one alkyl branch per molecule.

Process for the hydrofomylation of sulfur-containing thermally cracked

Compositions of matter are disclosed which are highly useful in hydroformylation processes. The compositions are non-charged, non-chelated bis- and tris-(alkyl diaryl phosphine) rhodium carbonyl hydrides. The substituents of the alkyl group include heteroorganic radicals containing silane, silicone, ether, ester, keto and hydroxy oxygen, phosphine oxide and phosphorus ester phosphorus, amine, amide, amine oxide and heterocyclic nitrogen groups. These compositions are highly stable and selective catalysts for the hydroformylation of olefins under certain conditions. The disclosed catalyst systems contain a large excess of phosphine ligand and employ alpha-olefin plus synthesis gas reactant mixtures having a high H.sub.2 /CO ratio at relatively low pressures. They produce mostly aldehydes derived from terminal attack on the alpha-olefin reactant. In the case of low olefins, such as butene-1, the products can be advantageously removed in a continuous manner, as distillate components from a ligand reaction mixture kept at an elevated temperature and continuously fed by an appropriate mixture of the reactants.

Ligand exchange process for producing alkyl diaryl phosphine rhodium

Compositions of matter are disclosed which are highly useful in hydroformylation processes. The compositions are non-charged, non-chelated bis- and tris-(alkyl diaryl phosphine) rhodium carbonyl hydrides. The substituents of the alkyl group include heteroorganic radicals containing ether, ester, keto and hydroxy oxygen, phosphine oxide and phosphorus ester phosphorus, amine, amide, amine oxide and heterocyclic nitrogen groups. These compositions are highly stable and selective catalysts for the hydroformylation of olefins under certain conditions. The disclosed catalyst systems contain a large excess of phosphine ligand and employ alpha-olefin plus synthesis gas reactant mixtures having a high H.sub.2 /CO ratio at relatively low pressures. They produce mostly aldehydes derived from terminal attack on the alpha-olefin reactant. In the case of low olefins, such as butene-1, the products can be advantageously removed in a continuous manner, as distillate components from a ligand reaction mixture kept at an elevated temperature and continuously fed by an appropriate mixture of the reactants.

Selective hydroformylation process using alkyl diaryl phosphine rhodium

Compositions of matter are disclosed which are highly useful in hydroformylation processes. The compositions are non-charged, non-chelated bis- and tris-(alkyl diaryl phosphine) rhodium carbonyl hydrides. The substituents of the alkyl group includes heteroorganic radicals containing ether, ester, keto and hydroxy oxygen, phosphine oxide and phosphorus ester phosphorus, amine, amide, amine oxide and heterocyclic nitrogen groups. These compositions are highly stable and selective catalysts for the hydroformylation of olefins under certain conditions. The disclosed catalyst systems contain a large excess of phosphine ligand and employ alpha-olefin plus synthesis gas reactant mixtures having a high H.sub.2 /CO ratio at relatively low pressures. They produce moslty aldehydes derived from terminal attack on the alpha-olefin reactant. In the case of low olefins, such as butene-1, the products can be advantageously removed in a continuous manner, as distillate components from a ligand reaction mixture kept at an elevated temperature and continuously fed by an appropriate mixture of the reactants.

Transition metal complex catalysts

Heterocycle-substituted alkyl diaryl phosphine rhodium caronyl hydride

Branched alkyl diaryl phosphine rhodium carbonyl hydride complexes are surprisingly effective, stable and selective hydroformylation catalysts particularly in the presence of a large excess of t-phosphine ligands. As such, they are advantageously employed as catalysts in a novel low pressure rhodium hydroformylation process producing normal and iso aldehydes by reacting olefins with H.sub.2 and CO.

Hydroformylation catalysis by branched alkyl diaryl phosphine rhodium

The present invention relates to an alkaline salt promoter system which includes an N-aminoalkyl alkylpiperazine, preferably the compound 1-(3-aminopropyl)-2,5-dimethylpiperazine (APDP), an alkali metal salt or hydroxide (e.g., K.sub.2 CO.sub.3) and water. These scrubbing compositions may be used for removing CO.sub.2 from gaseous streams containing CO.sub.2.

N-aminoalkyl alkylpiperazine promoted acid gas scrubbing process

An additive combination for improving the cold flow properties of distillate fuels comprises a combination of:

Additive combinations and fuels containing them

Certain triarylphosphine rhodium carbonyl hydride complexes

High temperature hydroformylation in the presence of triarylphosphine

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Mountainside, NJ, United States of America

Alexis A Oswald