Exxon Research and Engineering Company

Exxon Chemical Patents, Inc.

Alexandr P Glivicky

Ram N Bhatia

Alexis A Oswald

Edmund John Mozeleski

John R Hooton

Charles M Smith

Barry G Brueggeman

Chang S Hsu

David E Vaughan

James D Bushnell

Bruce M Sankey

Milton D Leighton

Nur R Gurak

Donald J Norris

Joseph W Gabriel

Wilfried J Mortier

Norman C Murtaugh

The present invention provides a highly selective catalytic cracking process for the conversion of feedstocks containing a predominant content of C.sub.10 and higher mixed olefins into C.sub.9 and lower olefin products at efficiencies of greater than 20%. said products further characterized in that the content C.sub.6 to C.sub.9 olefins is maximized while the content of C.sub.2 to C.sub.4 olefins is minimized. The process involves contacting an olefin feedstock mixture containing at least about 50 weight %, more preferably at least about 70 weight %, of C.sub.10 and higher olefins under cracking conditions with a catalyst selected from the group consisting of amorphous precipitated silica, selected crystalline silicates and aluminosilicates, namely beta, mordenite and ZSM-5 types, as well as ion exchanged or acid variants thereof. Cracking conditions include a temperature within the range of from about 250.degree. up to about 450.degree. C., pressures from atmospheric up to about 300 psig and a space velocity within the range of from about 0.5 up to about 4 wt/wt/hour.

Process for catalytically converting C10 and higher olefins to C9 and

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pressure hydroformylation are cobalt and rhodium carbonyl hydride complexes in which some of the carbonyl ligands have been replaced by trivalent phosphorus ligands.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 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.

An improved process for oligomerizing olefins is provided in which olefin feed is contacted with phosphoric acid catalyst to form an olefin oligomerization product containing phosphorous-containing foulant precursors. The olefin oligomerization product is then contacted with a foulant adsorbent comprising at least one member selected from the group consisting of alumina, activated alumina and magnesium oxide in an amount and under conditions sufficient to effect removal of at least a portion of said foulant precursors. The treated olefin oligomerization product stream can then be passed to downstream recovery and process equipment with minimized fouling.

Process for reducing fouling in higher olefin plants

An asphalt containing mineral oil is simultaneously deasphalted and extracted in a combination zone by contacting the oil with a solvent comprising N-methyl-2-pyrrolidone (NMP) containing from 0-5 LV% water and a light hydrocarbon to produce a raffinate and extract phase, with the raffinate phase containing the desired oil, most of the hydrocarbon solvent and some NMP. The raffinate is then passed to a reduced pressure zone to remove most of the hydrocarbon solvent therefrom. The remaining raffinate oil and NMP solution is then chilled to produce bulk liquid-liquid immiscibility between the oil and NMP. The chilled oil and NMP are then passed to a settling zone wherein the NMP is separated from the oil and recycled back into the combination zone.

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Sarnia, Canada

Alexandr P Glivicky