Chemical Research & Licensing Company

Catalytic Distillation Technologies

Other

Dennis Hearn

Lawrence A Smith, Jr

Edward M Jones, Jr

Robert P Arganbright

Gary R Gildert

Hugh M Putman

John R Adams

Speros P Nemphos

Thomas P Hickey

Kyte H Terhune

Willibrord A Groten

Clifford S Crossland

A process for the isomerization of mono-olefins in aliphatic hydrocarbon streams is carried out at 40 to 300&deg; F. under low hydrogen partial pressure in the range of about 0.1 psi to less than 70 psi at 0 to 350 psig in a distillation column reactor containing a hydrogenation catalyst which serves as a component of a distillation structure, such as supported PdO encased in tubular wire mesh. Essentially no hydrogenation of the mono-olefins occurs.

Olefin isomerization process

A process for treating a light cracked naphtha to be used as an etherification feed stock is disclosed in which mercaptans, H S and diolefins are removed simultaneously in a distillation column reactor using a reduced nickel catalyst. The mercaptans and H S are reacted with the diolefins to form sulfides which are higher boiling than that portion of the naphtha which is used as feed to the etherification unit. The higher boiling sulfides are removed as bottoms along with any C and heavier materials. Any diolefins not converted to sulfides are selectively hydrogenated to mono-olefins for use in the etherification process.

Process for removal of mercaptans from hydrocarbon streams

A process for the selective hydrogenation of the diolefins and acetylenic compounds in a olefin rich aliphatic hydrocarbon streams is disclosed wherein the selective hydrogenation is carried out at 40 to 300&deg; F. under low hydrogen partial pressure in the range of about 0.1 psi to less than 70 psia at 0 to 350 psig in a distillation column reactor containing a hydrogenation catalyst which serves as a component of a distillation structure, such as supported PdO encased in tubular wire mesh. Essentially no hydrogenation of the olefins occurs.

Selective hydrogenation of highly unsaturated compounds in hydrocarbon streams

A process for the alkylation of benzene contained in a mixed refinery stream is disclosed wherein the refinery stream is first subjected to hydrogenation of higher olefins prior to alkylation of the benzene with selected types and quantities of lower olefins. Streams containing sulfur compounds may be pretreated by hydrodesulfurization. All of the process steps are advantageously carried out in distillation column reactors to take advantage of that mode of operation.

Process for the alkylation of benzene

The hydroconversion of heavy petroliferous stocks boiling mainly above 400.degree. F. is carried out in a distillation column reactor where concurrently a petroleum stream is fed into a feed zone; hydrogen is fed at a point below said feed zone; the petroleum stream is distilled and contacted in the presence of a cracking catalyst prepared in the form of a catalytic distillation structure at total pressure of less than about 300 psig and a hydrogen partial pressure in the range of 1.0 to less than 70 psia and a temperature in the range of 400 to 1000.degree. F. whereby a portion of the petroleum stream is cracked to lighter products boiling below the boiling point of the feed and products are distilled to remove a vaporous overhead stream comprising products mainly boiling below the boiling point of the feed and a liquid bottoms stream.

Hydroconversion process

Process for alkylation of benzene

A process for the removal of vinylacetylene, ethylacetylene and 1,2-butadiene from C.sub.4 aliphatic hydrocarbon streams comprising, concurrently: (1) feeding hydrogen and a hydrocarbon stream comprising C.sub.4 hydrocarbons including butanes, butenes, butadienes and vinylacetylene to a distillation column reactor containing a bed comprising a hydrogenation catalyst of the type characterized by platinum, palladium or rhodium which is prepared as a distillation structure to selectively hydrogenate a portion of the vinylacetylene and the 1,2-butadiene and (2) fractionally distilling the reaction mixture to remove a heavier fraction and removing a fraction overhead comprising substantially all of the C.sub.4.

Process for concurrent selective hydrogenation of acetylenes and 1,2

A process for the hydrogenation of a selected aromatic, such as benzene contained in a naphtha stream to cyclohexane wherein the distillation column reactor is operated such that the portion of the naphtha containing the benzene is maintained in the catalyst bed such that essentially only benzene is hydrogenated. The reactor is operated at a pressure wherein the reaction mixture is boiling under low hydrogen partial pressure in the range of about 0.1 psi to less than 70 psia at 0 to 350 psig. The catalyst is provided as a catalytic distillation structure such that the reaction is concurrently occurring with a distillation. A portion of the overheads is returned as reflux to provide cooling within the catalyst bed and concurrent condensation of some of the gaseous material within the bed.

Selective hydrogenation of aromatics contained in hydrocarbon streams

A process for treating a light cracked naphtha to be used as an etherification or alkylation feedstock in which the mercaptans and diolefins reacted in a single pass fixed bed reactor and are removed in a distillation column reactor which hydrogenate the unreacted diolefins. The mercaptans are reacted with the diolefins to form sulfides which are higher boiling than that portion of the naphtha which is used as feed to the etherification or alkylation unit. The higher boiling sulfides are removed as bottoms along with any C.sub.6 and heavier materials. Any diolefins not converted to sulfides are selectively hydrogenated to mono-olefins for use in the etherification process. Certain C.sub.5 olefins, for example pentene-1 and 3-methyl butene-1 are isomerized during the process to more beneficial isomers.

Process for the treatment of light naphtha hydrocarbon streams

An alkene skeletal isomerization process is employed in an integrated process for the production of tertiary ether, e.g., tertiary amyl methyl ether (TAME) from the reaction of isoamylenes (iC.sub.5.sup.= 's) with methanol in the presence of an acid cation exchange resin. A light naphtha from a fluid catalytic cracking unit is used as the source of the iC.sub.5.sup.= 's in a process which separates the C.sub.5 containing fraction from the light naphtha, selectively hydrogenates the di-olefins contained in the C.sub.5 containing fraction, reacts the iC.sub.5.sup.= 's contained in the C.sub.5 containing fraction with methanol to form TAME, separates the TAME from the unreacted materials as a product, separates methanol from the unreacted materials, isomerizes a portion of the nC.sub.5.sup.= 's to iC.sub.5.sup.= 's , for example using a zeolite or an alumina treated with methanol, and use of the isomerization product as feed for a TAME reactor.

Integrated process for the production of tame

A process for the hydrodesulfurization of petroleum streams is disclosed wherein the sulfur containing petroleum stream is contacted along with hydrogen at a partial pressure of less than 70 psig in a distillation column reactor containing a hydrodesulfurization catalyst in the form of a catalytic distillation structure.

Hydrodesulfurization process utilizing a distillation column realtor

A process for the hydrogenation of unsaturated cyclic and polycyclic compounds to saturates is provided wherein the reactor is operated at a pressure wherein the reaction mixture is boiling under low hydrogen partial pressure in the range of about 0.1 psi to less than 70 psia at 0 to 350 psig. The catalyst is provided as a catalytic distillation structure such that the reaction is concurrently occurring with a distillation. A portion of the overheads is returned as reflux to provide cooling within the catalyst bed and concurrent condensation of some of the gaseous material within the bed. Although no separation is obtained all of the advantages of concurrent reaction with distillation are achieved.

Hydrogenation of unsaturated cyclic compounds

A mixed aromatic stream is hydrotreated to remove olefins and fractionated to separate C.sub.9 + heavies in a distillation column reactor and the C.sub.8 and lighter material is fed to a selective adsorption unit where the para-xylene is removed. The para-xylene depleted raffinate therefrom may be subjected to isomerization to form additional para-xylene. The effluent from the isomerization can be fed to the distillation column reactor for hydrogenation of any olefins formed during the isomerization or directly to the adsorption unit.

Process and apparatus for the production and recovery of p-xylene

A process for selectively reducing nitrile contaminants in fluids such as water, methanol or hydrocarbon streams containing mono olefins and which contain minor amounts of contaminants comprising nitriles in the presence of hydrogen and a supported cobalt catalyst. In the olefin stream the nitrile contaminants are substantially reduced without substantial reduction of the mono olefins.

Reduction of nitrite contaminants by selective hydrogenation

A method for producing dialkyl ethers comprising feeding a stream containing a C.sub.1 to C.sub.4 alcohol to a distillation column reactor into a feed zone, contacting the stream with a fixed bed zeolite prepared as a distillation structure to form the corresponding dialkyl ether and water, and concurrently fractionating the ether product from the water and unreacted materials wherein the improvement is the addition of a small amount of hydrogen to the reaction zone to inhibit catalyst fouling and substantially increasing the catalyst life and activity.

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Houston, TX, United States of America

Dennis Hearn