Catalytic Distillation Technologies

Chemical Research & Licensing Company

Other

Sud-chemie Inc.

Abb Lummus Global Inc.

Gary R Gildert

Dennis Hearn

Hugh M Putman

Willibrord A Groten

Lawrence A Smith, Jr

Gary G Podrebarac

Edward M Jones, Jr

J Yong Ryu

Robert P Arganbright

Stephen J Stanley

Steven A Blankenship

Jennifer A Boyer

Robert J Gartside

Mitchell E Loescher

Charles Sumner

Clifford S Crossland

Francis D McCarthy

James R Fair

A Frank Seibert

A catalyst for selective hydrogenation of acetylenes and diolefins, particularly in a raw gas feed stream for front end selective hydrogenation. The catalyst contains a low surface area carrier with a surface area from about 2-20 m2/g, wherein the pore volume of the pores of the carrier is greater than about 0.4 cc/g, at least 90 percent of the pore volume of the pores is contained within pores having a pore diameter greater than about 500 &#x212b; and about 1 to about 2 percent of the total pore volume is contained in pores with a pore diameter from about 500 to about 1,000 &#x212b;. The palladium comprises about 0.01 to about 0.1 weight % and a Group IB metal comprises about 0.005 to about 0.06 weight % of the catalyst.

Selective hydrogenation catalyst designed for raw gas feed streams

A catalyst for selective hydrogenation of acetylenes and diolefins, particularly in a raw gas feed stream for front end selective hydrogenation. The catalyst contains a low surface area carrier with a surface area from about 2-20 m/g, wherein the pore volume of the pores of the carrier is greater than about 0.4 cc/g, wherein at least 90 percent of the pore volume of the pores is contained within pores having a pore diameter greater than about 500 &#x212b; and wherein from about 1 to about 2 percent of the total pore volume is contained in pores with a pore diameter from about 500 to about 1,000 &#x212b;, palladium, wherein the palladium comprises from about 0.01 to about 0.1 weight percent of the catalyst, and a Group IB metal, wherein the Group IB metal comprises from about 0.005 to about 0.06 weight percent of the catalyst.

Improved HETP is obtained in the operation of a distillation column containing trays with a packing of a porous container containing a particulate material intimately associated with a resilient component having at least 50 volume % open space, preferably at least 70 volume % positioned on the trays compared to the trays without the packing. The packing may contain a catalytic particulate material and the distillation may involve reaction and distillation of the reaction products. The particulate material may also be inert and the distillation of the conventional type to separate components in the distillation mixture without reaction.

Distillation system

Acetylenic compounds in olefin streams such as mixed 1,3-butadiene were selectively hydrogenated over the supported copper catalysts on highly porous supports such as alumina, silica, etc. The preferred supports have the average pore diameter larger than about 200 &angst;, no micro pores, total pore volume larger than about 0.65 cc/g, and preferably less than about 230 m /g BET surface area. The copper catalysts were preferably promoted with the Group VIII metal such as palladium to improve low activity of copper catalyst. The product stream typically contains less than 20 ppm total alkynes. Also the copper catalysts and the palladium promoted copper catalysts may be modified with zinc oxide to improve the performance of the catalysts. The reactor was loaded with two or more copper catalysts promoted with different levels of palladium. Preferably the copper catalysts were also modified with silver, gold or both silver and gold to reduce polymer formation by the copper component of the catalyst, improve the yield of olefins such as 1,3-butadiene, and prevent the loss of copper and/or palladium due to leaching out into the liquid phase of hydrocarbon.

Process for selective hydrogenation of alkynes and catalyst therefor

A process for the hydrodesulfurization of a cracked naphtha stream is disclosed where very little of the valuable olefins are saturated. The process is a two staged process wherein the H S is removed between the stages to prevent recombinant mercaptans formation. Because the H S is removed between the stages milder conditions can be used in the second stage polishing reactor to achieve the same desulfurization levels with less olefin loss.

Process for the desulfurization of petroleum feeds

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 concurrently fractionating and treating of a full range naphtha stream. The full boiling range naphtha stream is first subjected to simultaneous thioetherification or selective hydrogenation and splitting into a light boiling range naphtha, an intermediate boiling range naphtha and a heavy boiling range naphtha. The intermediate boiling range naphtha containing thiophene and thiophene boiling range mercaptans, dienes or mixtures may be subjected to a second thioetherification or selective hydrogenation, depending on its make-up, and then passed on to a polishing hydrodesulfurization reactor or the entire intermediate stream may be passed directly to the polishing reactor. The bottoms are subjected to concurrent hydrodesulfurization and fractional distillation and the combined overheads and bottoms are fed to the polishing reactor. The effluent from the polishing reactor may be combined with the light boiling range naphtha to produce a new full boiling range naphtha containing substantially less total sulfur than the original feed. The object being to meet higher standards for sulfur removal, by treating the components of the naphtha feed with the process that preserves the olefinic while most expediently removing the sulfur compounds.

Process for sulfur reduction in naphtha streams

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

The C to C cut from a cracking process containing propylene, butane, 1-butene, 2-butene and acetylenic and diene components including butadiene are preferentially converted to propylene. The cut is simultaneously fractionated and catalytically hydrogenated to hydrogenate the acetylenic and diene components. The fractionation and subsequent separation recovers a C component comprising a mixture of isobutene, 1-butene and 2-butene. This C component is then further simultaneously fractionated and catalytically hydrogenated and hydroisomerized to hydrogenate remaining butadiene, remove isobutene overhead and convert 1-butene to 2-butene leaving a bottoms of 2-butene. The 2-butene is then injected with ethylene and catalytically metathesized to form propylene.

Cracked gas processing and conversion for propylene production

A process for the selective hydrogenation of the methyl acetylene and propadiene (MAPD) in a propylene rich stream is disclosed wherein the selective hydrogenation is carried out stepwise (a) first in a single pass fixed bed reactor and then (b) in a distillation column reactor containing a supported PdO hydrogenation catalyst which serves as a component of a distillation structure. Conversion and selectivity to propylene in improved over the use of the single pass fixed bed reactor alone.

Process for the removal of MAPD from hydrocarbon streams

A process for the hydrodesulfurization of a cracked naphtha stream is disclosed where very little of the valuable olefins are saturated. The process is a two staged process wherein the H,S is removed between the stages to prevent recombinant mercaptans formation. Because the H,S is removed between the stages milder conditions can be used in the second stage polishing reactor to achieve the same desulfurization levels with less olefin loss.

A process is disclosed for the concurrent production and hydrogenation of diisobutene in a single distillation column reactor containing both a dimerization catalyst and a hydrogenation catalyst by the dimerized of isobutene to diisobutene. The catalysts may be in alternating beds or physically mixed together in one or more beds. Alternatively a bifunctional catalyst having both dimerization and hydrogenation properties may be used.

Catalytic distillation process for the production of C8 alkanes

A process for the production of cyclohexane by the hydrogenation of benzene 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 psia to less than 200 psia at 0 to 350 psig overhead pressure. The catalyst is provided as a catalytic distillation structure such that the reaction is concurrently occurring with a distillation. The benzene is fed at a point above the bed and the hydrogen is fed below the bed. All of the overheads may be returned as reflux to provide cooling within the catalyst bed.

Hydrogenation of benzene to cyclohexane

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.

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Houston, TX, United States of America

Gary R Gildert