EP1150936A1 - Procede d'hydrogenation d'alcyne - Google Patents

Procede d'hydrogenation d'alcyne

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Publication number
EP1150936A1
EP1150936A1 EP00907282A EP00907282A EP1150936A1 EP 1150936 A1 EP1150936 A1 EP 1150936A1 EP 00907282 A EP00907282 A EP 00907282A EP 00907282 A EP00907282 A EP 00907282A EP 1150936 A1 EP1150936 A1 EP 1150936A1
Authority
EP
European Patent Office
Prior art keywords
hydrocarbon
alkali metal
catalyst
alkyne
reaction zone
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.)
Withdrawn
Application number
EP00907282A
Other languages
German (de)
English (en)
Other versions
EP1150936A4 (fr
Inventor
Ricardo J. Callejas
L. Alberto Morales
James B. Kimble
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.)
ConocoPhillips Co
Original Assignee
Phillips Petroleum 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 Phillips Petroleum Co filed Critical Phillips Petroleum Co
Publication of EP1150936A1 publication Critical patent/EP1150936A1/fr
Publication of EP1150936A4 publication Critical patent/EP1150936A4/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
    • C07C5/08—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of carbon-to-carbon triple bonds
    • C07C5/09—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of carbon-to-carbon triple bonds to carbon-to-carbon double bonds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C7/00—Purification; Separation; Use of additives
    • C07C7/148—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound
    • C07C7/163—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound by hydrogenation
    • C07C7/167—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound by hydrogenation for removal of compounds containing a triple carbon-to-carbon bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the alkali- or alkaline earth metals or beryllium
    • C07C2523/04—Alkali metals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
    • C07C2523/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals of the platinum group metals
    • C07C2523/44—Palladium
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
    • C07C2523/48—Silver or gold
    • C07C2523/50—Silver
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
    • C07C2523/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
    • C07C2523/66—Silver or gold

Definitions

  • This invention relates to an improved process for catalytically hydrogenating hydrocarbon-containing fluid comprising at least one alkyne in a single- stage reaction zone.
  • alkynes which generally are present in small amounts in alkene-containing streams (e.g., acetylene contained in ethylene streams from thermal ethane crackers), is commercially carried out in the presence of alumina-supported palladium hydrogenation catalysts.
  • alumina-supported palladium/silver hydrogenation catalyst such as in accordance with the disclosure in U.S. Patent 4,404,124 and its division, U.S. Patent 4,484,015.
  • the removal of heat requires a multi-stage reactor system, such as, for example, at least two catalyst beds, with expensive heat removal apparatus, such as, for example, inter-stage cooling apparatus such as a heat exchanger, between stages, e.g., between catalyst beds.
  • expensive heat removal apparatus such as, for example, inter-stage cooling apparatus such as a heat exchanger
  • a catalyst also referred to as "catalyst B”
  • an alkali metal compound where such process prevents the uncontrollable hydrogenation of an alkene(s) (e.g., ethylene) to an alkane(s) (e.g., ethane) in a single
  • an alkene(s) e.g., ethylene
  • alkane(s) e.g., ethane
  • the present invention is directed to a process of improving the operation of a process system used for selectively hydrogenating, i.e., for the conversion of, a hydrocarbon-containing fluid comprising at least one alkyne, preferably acetylene (ethyne), containing about 2 carbon atoms to about 6 carbon atoms per molecule with hydrogen, preferably hydrogen gas, to at least one corresponding alkene, preferably ethylene (ethene), containing about 2 carbon atoms to about 6 carbon atoms per molecule.
  • a hydrocarbon-containing fluid comprising at least one alkyne, preferably acetylene (ethyne), containing about 2 carbon atoms to about 6 carbon atoms per molecule with hydrogen, preferably hydrogen gas, to at least one corresponding alkene, preferably ethylene (ethene), containing about 2 carbon atoms to about 6 carbon atoms per molecule.
  • the process system utilizes a volumetric amount of a hydrogenation catalyst (also referred to as "hydrogenation catalyst A") which can comprise, for example, an alumina-supported palladium hydrogenation catalyst or alumina-supported palladium/silver hydrogenation catalyst required for providing the conversion of the at least one alkyne so as to provide a conversion product containing less alkyne than the hydrocarbon-containing fluid.
  • a hydrogenation catalyst also referred to as "hydrogenation catalyst A”
  • hydrogenation catalyst A can comprise, for example, an alumina-supported palladium hydrogenation catalyst or alumina-supported palladium/silver hydrogenation catalyst required for providing the conversion of the at least one alkyne so as to provide a conversion product containing less alkyne than the hydrocarbon-containing fluid.
  • the process of improving the operation of such process system utilizing a volumetric amount of a hydrogenation catalyst A comprises substituting such hydrogenation catalyst A with a conversion-improving volumetric amount of a catalyst B comprising palladium, silver, and an alkali metal compound contained in a single- stage adiabatic reaction zone.
  • the conversion-improving volumetric amount of a catalyst B comprising palladium, silver, and an alkali metal compound is less than the volumetric amount of such hydrogenation catalyst A present in the process system before utilizing the process of improving.
  • the process also includes contacting under reaction conditions such hydrocarbon-containing fluid with such catalyst B comprising palladium, silver, and an alkali metal compound and charging the hydrocarbon- containing fluid to the single-stage reaction zone at a temperature sufficient to provide for the desired selective hydrogenation.
  • the improved process system does not contain any heat removal apparatus such as a heat exchanger, i.e., the improved process system is an adiabatic system.
  • the conversion-improving volumetric amount of a catalyst B comprising palladium, silver, and an alkali metal compound is generally at least 20 percent of the volumetric amount of hydrogenation catalyst A present in the process system before utilizing the process of improving.
  • the present invention is also directed to a process of charging, at reaction conditions, a hydrocarbon-containing fluid comprising at least one alkyne containing about 2 carbon atoms to about 6 carbon atoms per molecule with hydrogen to a single- stage adiabatic reaction zone containing a catalyst B comprising palladium, silver, and an alkali metal compound.
  • the process then includes converting the at least one alkyne containing about 2 carbon atoms to about 6 carbon atoms per molecule to at least one corresponding alkene containing about 2 carbon atoms to about 6 carbon atoms per molecule.
  • the process then includes yielding a conversion product containing less alkyne than the hydrocarbon-containing fluid and further, the conversion of the at least one alkyne is at least as high as the conversion of the at least one alkyne would otherwise be for a multi-stage reaction zone having intercooling between stages of such multi-stage reaction zone.
  • the present invention is also directed to a process of modifying a multistage reaction zone, e.g., two or more reactor vessels in series, having intercooling between stages of such multi-stage reaction zone, used for the selective hydrogenation, i.e., conversion, of a hydrocarbon-containing fluid comprising at least one alkyne containing about 2 carbon atoms to about 6 carbon atoms per molecule with hydrogen to at least one corresponding alkene containing about 2 carbon atoms to about 6 carbon atoms per molecule.
  • Such multi-stage reaction zone utilizes a volumetric amount of a hydrogenation catalyst A required for providing the conversion of the at least one alkyne so as to provide a conversion product containing less alkyne than the hydrocarbon- containing fluid.
  • the process comprises modifying such multi-stage reaction zone by providing for a single-stage adiabatic reaction zone having a conversion-improving volumetric amount of a catalyst B comprising palladium, silver, and an alkali metal compound that is less than the volumetric amount of hydrogenation catalyst A present in the multi-stage reaction zone before modifying such multi-stage reaction zone.
  • the modifying of such multi-stage reaction zone can comprise converting e.g., one or more stages (e.g., one or more reactor vessels) of such multi-stage reaction zone into a single- stage adiabatic reaction zone (comprising, for example, an adiabatic reactor vessel or one or more adiabatic reactor vessels) or into a set of single-stage adiabatic reaction zones (comprising, for example, a set of adiabatic reactor vessels).
  • the inventive process offers several benefits such as: (1) a smaller and less expensive reaction zone, (2) the ability to convert an existing multi-stage reaction zone to several single-stage adiabatic reaction zones with at least one single-stage adiabatic reaction zone in service with at least one single-stage adiabatic reaction zone in stand-by allowing an essentially unlimited time to pass between shut-down of the entire reaction system, and (3) expansion of existing reactor capacity with minimal economic investment.
  • Catalyst B which is employed in the selective hydrogenation process, i.e., conversion process, of this invention can be any supported palladium catalyst composition which also comprises silver and an alkali metal compound.
  • the alkali metal compound is selected from the group consisting of alkali metal halides, alkali metal hydroxides, alkali metal carbonates, alkali metal bicarbonates, alkali metal nitrates, alkali metal carboxylates, and the like and mixtures thereof.
  • the alkali metal compound is an alkali metal fluoride.
  • the alkali metal of such alkali metal compound is selected from the group consisting of potassium, rubidium, cesium, and the like and mixtures thereof.
  • the alkali metal of such alkali metal compound is potassium.
  • the alkali metal compound is potassium fluoride.
  • Catalyst B can be fresh or it can be a used and thereafter oxidatively regenerated catalyst composition.
  • Catalyst B can contain any suitable inorganic solid support material.
  • the inorganic support material is selected from the group consisting of alumina, titania, zirconia, and the like and mixtures thereof.
  • the presently more preferred support material is alumina, most preferably alpha-alumina.
  • catalyst B contains in the range of from about 0.001 weight percent palladium (on a total catalyst composition weight basis) to about 1 weight percent palladium. More preferably, catalyst B contains in the range of from about 0.01 weight percent palladium to about 0.5 weight percent palladium and, most preferably, in the range from 0.01 weight percent palladium to 0.2 weight percent palladium.
  • catalyst B contains in the range of from about 0.05 weight percent alkali metal (on a total catalyst composition weight basis) to about 5 weight percent alkali metal. More preferably, catalyst B contains in the range of from about 0.05 weight percent alkali metal to about 3 weight percent alkali metal and, most preferably, in the range from 0.1 weight percent alkali metal to 1 weight percent alkali metal.
  • the weight ratio of alkali metal to palladium is in the range of from about 0.05:1 to about 500:1.
  • the weight ratio of alkali metal to palladium is in the range of from about 0.2:1 to about 100:1.
  • catalyst B comprises an alkali metal fluoride
  • the catalyst contains in the range of from about 0.03 weight percent fluorine (chemically bound as fluoride) (on a total catalyst composition weight basis) to about 10 weight percent fluorine. More preferably, catalyst B contains in the range of from about 0.1 weight percent fluorine to about 5 weight percent fluorine and, most preferably, in the range from 0.2 weight percent fluorine to 1 weight percent fluorine.
  • the atomic ratio of fluorine to alkali metal is in the range of from about 0.5:1 to about 4:1.
  • the atomic ratio of fluorine to alkali metal is in the range of from about 1 :1 to about 3:1.
  • catalyst B contains in the range of from about 0.01 weight percent silver (on a total catalyst composition weight basis) to about 10 weight percent silver. More preferably, catalyst B contains in the range of from about 0.01 weight percent silver to about 5 weight percent silver and, most preferably, in the range from 0.02 weight percent silver to 2 weight percent silver.
  • the silver:palladium (Ag:Pd) weight ratio in the catalyst is in the range of from about 2:1 to about 10:1.
  • the particles of catalyst B have a size in the range of about 1 mm to about 10 mm, preferably in the range of from about 2 mm to about 6 mm.
  • the particles of catalyst B can have any suitable shape, preferably spherical or cylindrical.
  • the surface area of the catalyst is in the range of from about 1 m 2 /g to about 100 m 2 /g.
  • the presently preferred catalysts for use as catalyst B are those described in U.S. Pat. Nos. 5,585,318 and 5,587,348, the disclosures of which are incorporated herein by reference.
  • the selective hydrogenation process, i.e., conversion process, of this invention is generally carried out by contacting a hydrocarbon-containing fluid which comprises at least one alkyne containing about 2 carbon atoms to about 6 carbon atoms per molecule and hydrogen with a catalyst B comprising palladium, silver, an alkali metal compound, and an inorganic support material in a single-stage reaction zone, preferably in a single-stage adiabatic reaction zone, wherein such single-stage adiabatic reaction zone does not utilize heat removal apparatus.
  • adiabatic generally means without a significant loss or significant gain of heat.
  • the selective hydrogenation process of this invention can be used to improve the method of operation of a process system used for selectively hydrogenating, i.e., for the conversion of, a hydrocarbon-containing fluid comprising at least one alkyne, preferably acetylene (ethyne), containing about 2 carbon atoms to about 6 carbon atoms per molecule with hydrogen to at least one corresponding alkene, preferably ethylene (ethene), containing about 2 carbon atoms to about 6 carbon atoms per molecule wherein such process system utilizes a volumetric amount of a hydrogenation catalyst A required for providing the conversion of the at least one alkyne so as to provide a conversion product containing less alkyne than the hydrocarbon-containing fluid.
  • a hydrocarbon-containing fluid comprising at least one alkyne, preferably acetylene (ethyne), containing about 2 carbon atoms to about 6 carbon atoms per molecule with hydrogen to at least one corresponding alkene, preferably ethylene (e
  • Hydrogenation catalyst A can comprise, for example, an alumina-supported palladium hydrogenation catalyst or alumina-supported palladium/silver hydrogenation catalyst such as in accordance with the disclosure in U.S. Patent 4,404,124 and its division, U.S. Patent 4,484,015.
  • the process of improving the operation of such process system utilizing a volumetric amount of a hydrogenation catalyst A comprises substituting such hydrogenation catalyst A with a conversion-improving volumetric amount of a catalyst B comprising palladium, silver, and an alkali metal compound (preferably such alkali metal compound is an alkali metal fluoride) contained in a single-stage reaction zone, preferably in a single-stage adiabatic reaction zone.
  • the conversion-improving volumetric amount of a catalyst B comprising palladium, silver, and an alkali metal compound is less than the volumetric amount of hydrogenation catalyst A present in the process system before utilizing the method of improvement.
  • the process of improving includes contacting under reaction conditions such hydrocarbon-containing fluid with such catalyst B comprising palladium, silver, and an alkali metal compound.
  • the phrase "substituting" generally refers to substituting in whole or substituting in part hydrogenation catalyst A with a conversion-improving volumetric amount of a catalyst B comprising palladium, silver, and an alkali metal compound.
  • the phrase “substituting” can refer to the conversion-improving volumetric amount of a catalyst B taking the place of in whole or in part, or being put in the place of in whole or in part, or being exchanged for in whole or in part, the hydrogenation catalyst A present in the process system before utilizing the method of improvement.
  • the conversion-improving volumetric amount of a catalyst B comprising palladium, silver, and an alkali metal compound is generally in the range of from about 20 volume percent to about 80 volume percent of the volumetric amount of hydrogenation catalyst A (hydrogenation catalyst A can comprise, for example, an alumina-supported palladium hydrogenation catalyst or alumina-supported palladium/silver hydrogenation catalyst), present in the process system before utilizing the method of improvement.
  • the conversion-improving volumetric amount of a catalyst B comprising palladium, silver, and an alkali metal compound is in the range of from about 25 volume percent to about 75 volume percent of the volumetric amount of hydrogenation catalyst A present in the process system before utilizing the method of improvement. More preferably, the conversion-improving volumetric amount of a catalyst B comprising palladium, silver, and an alkali metal compound is in the range of from about 30 volume percent to about 70 volume percent of the volumetric amount of hydrogenation catalyst A present in the process system before utilizing the method of improvement.
  • the conversion-improving volumetric amount of a catalyst B comprising palladium, silver, and an alkali metal compound is in the range of from 35 volume percent to 65 volume percent of the volumetric amount of hydrogenation catalyst A present in the process system before utilizing the method of improvement.
  • conversion- improving volumetric amount refers to the volumetric amount of catalyst B comprising palladium, silver, and an alkali metal compound which can be used to improve the conversion of a hydrocarbon-containing fluid in accordance with the inventive processes disclosed herein.
  • the selective hydrogenation process of this invention can also comprise charging, at reaction conditions, a hydrocarbon-containing fluid comprising at least one alkyne containing about 2 carbon atoms to about 6 carbon atoms per molecule with hydrogen to a single-stage adiabatic reaction zone containing a catalyst B comprising palladium, silver, and an alkali metal compound (preferably such alkali metal compound is an alkali metal fluoride).
  • the process then includes converting the at least one alkyne containing about 2 carbon atoms to about 6 carbon atoms per molecule to at least one corresponding alkene containing about 2 carbon atoms to about 6 carbon atoms per molecule.
  • the process then includes yielding a conversion product containing less alkyne than the hydrocarbon-containing fluid and further, the conversion of the at least one alkyne is at least as high as the conversion of the at least one alkyne would otherwise be for a multi-stage reaction zone having intercooling between stages of such multi-stage reaction zone.
  • the selective hydrogenation process of this invention can also be used to modify a multi-stage reaction zone, e.g., two or more reactor vessels in series, having intercooling between stages (e.g., having heat exchanger(s) between reactor vessels) of such multi-stage reaction zone, used for conversion of a hydrocarbon-containing fluid comprising at least one alkyne containing about 2 carbon atoms to about 6 carbon atoms per molecule with hydrogen to at least one corresponding alkene containing about 2 carbon atoms to about 6 carbon atoms per molecule.
  • a hydrocarbon-containing fluid comprising at least one alkyne containing about 2 carbon atoms to about 6 carbon atoms per molecule with hydrogen to at least one corresponding alkene containing about 2 carbon atoms to about 6 carbon atoms per molecule.
  • Such multi-stage reaction zone utilizes a volumetric amount of a hydrogenation catalyst A (such hydrogenation catalyst A can comprise, for example, an alumina-supported palladium hydrogenation catalyst or alumina-supported palladium/silver hydrogenation catalyst) required for providing the conversion of the at least one alkyne so as to provide a conversion product containing less alkyne than the hydrocarbon-containing fluid.
  • a hydrogenation catalyst A can comprise, for example, an alumina-supported palladium hydrogenation catalyst or alumina-supported palladium/silver hydrogenation catalyst
  • the process comprises modifying such multi-stage reaction zone by providing for a single-stage adiabatic reaction zone having a conversion-improving volumetric amount of a catalyst B comprising palladium, silver, and an alkali metal compound (preferably such alkali metal compound is an alkali metal fluoride) that is less than the volumetric amount of hydrogenation catalyst A present in such multi-stage reaction zone before utilizing such process of modifying.
  • a catalyst B comprising palladium, silver, and an alkali metal compound (preferably such alkali metal compound is an alkali metal fluoride) that is less than the volumetric amount of hydrogenation catalyst A present in such multi-stage reaction zone before utilizing such process of modifying.
  • the modifying of such multi-stage reaction zone can comprise converting one or more stages (e.g., one or more reactor vessels) of such multi-stage reaction zone into a single-stage adiabatic reaction zone (comprising, for example, an adiabatic reactor vessel or one or more adiabatic reactor vessels) or into a set of single-stage adiabatic reaction zones (comprising, for example, a set of adiabatic reactor vessels) with each single-stage adiabatic reaction zone having a conversion-improving volumetric amount of a catalyst B comprising palladium, silver, and an alkali metal compound (preferably such alkali metal compound is an alkali metal fluoride) that is less than the volumetric amount of hydrogenation catalyst A present in such multi-stage reaction zone before utilizing such process of modifying.
  • a single-stage adiabatic reaction zone comprising, for example, an adiabatic reactor vessel or one or more adiabatic reactor vessels
  • a set of single-stage adiabatic reaction zones comprising,
  • the modifying of such multi-stage reaction zone may comprise modifying such multi-stage reaction zone to several single-stage adiabatic reaction zones with one single-stage adiabatic reaction zone to be in service while bypassing the other single-stage adiabatic reaction zones (e.g., the other single-stage adiabatic reaction zones can be in stand-by, to be used when the single-stage adiabatic reaction in service needs to be shut down, or to be used for further acetylene removal if necessary) allowing an essentially unlimited time to pass between shut-down of the entire reaction system.
  • the other single-stage adiabatic reaction zones can be in stand-by, to be used when the single-stage adiabatic reaction in service needs to be shut down, or to be used for further acetylene removal if necessary
  • the modifying of such multi-stage reaction zone may comprise modifying such multi-stage reaction zone to several single-stage adiabatic reaction zones, which can be operated, for example, in parallel or in series, allowing an expansion of existing reactor capacity.
  • the actual physical modifications of such multistage reaction zone into a single-stage adiabatic reaction zone or into a set of single- stage adiabatic reaction zones in accordance with the inventive process, i.e., for example, the piping and equipment changes necessary to modify such multi-stage reaction zone in accordance with the inventive process described herein, are within the capabilities of persons of ordinary skills in the field of selective hydrogenation technology.
  • the conversion-improving volumetric amount of a catalyst B comprising palladium, silver, and an alkali metal compound (preferably such alkali metal compound is an alkali metal fluoride) used in the modifying of such multi-stage reaction zone is generally in the same ranges of volume percents of the volumetric amount of a hydrogenation catalyst A as disclosed above.
  • the conversion-improving volumetric amount of a catalyst B comprising palladium, silver, and an alkali metal compound is generally in the range of from about 20 volume percent to about 80 volume percent of the volumetric amount of hydrogenation catalyst A present in the process system before utilizing the process of modifying.
  • Hydrogenation catalyst A can comprise, for example, an alumina-supported palladium hydrogenation catalyst or alumina-supported palladium/silver hydrogenation catalyst as described above.
  • the conversion- improving volumetric amount of a catalyst B comprising palladium, silver, and an alkali metal compound is in the range of from about 25 volume percent to about 75 volume percent, more preferably, in the range of from about 30 volume percent to about 70 volume percent, and most preferably, in the range of from 35 volume percent to 65 volume percent of the volumetric amount of hydrogenation catalyst A present in the process system before utilizing the process of modifying.
  • any suitable hydrocarbon-containing fluid which comprises at least one C 2 -C 6 alkyne can be used as the fluid to the single-stage reaction zone, preferably single- stage adiabatic reaction zone, of this invention.
  • the term "fluid" is used herein to denote gas, liquid, vapor, or combinations thereof.
  • such hydrocarbon- containing fluid contains at least one alkyne as an impurity at a level of about 1 part by weight alkyne per million parts by weight hydrocarbon-containing fluid to about 50,000 parts by weight alkyne per million parts by weight hydrocarbon-containing fluid (i.e., about 1 ppm alkyne to about 50,000 ppm alkyne).
  • such hydrocarbon- containing fluid contains at least one alkyne as an impurity at a level of about 1 ppm alkyne to about 30,000 ppm alkyne, more preferably such hydrocarbon-containing fluid contains at least one alkyne as an impurity at a level of about 1 ppm alkyne to about 20,000 ppm alkyne and, most preferably, such hydrocarbon-containing fluid contains at least one alkyne as an impurity at a level of about 1 ppm alkyne to about 10,000 ppm alkyne.
  • such hydrocarbon-containing fluid is a C 2 -C 6 alkene stream.
  • Non-limiting examples of suitable, available hydrocarbon-containing fluid include ethylene, propylene, and butylene streams, such as those from thermal hydrocarbon-(e.g., ethane, propane, butane, and naphtha) cracking processes, and mixtures thereof.
  • a particularly preferred hydrocarbon-containing fluid is an ethylene stream from a thermal ethane-cracking process.
  • Preferred alkynes include acetylene, propyne, butyne-1, butyne-2 and the like and mixtures thereof.
  • a particularly preferred alkyne is acetylene.
  • These alkynes are primarily hydrogenated to the corresponding alkenes, i.e., acetylene is primarily hydrogenated to ethylene, propyne is primarily hydrogenated to propylene, and the butynes are primarily hydrogenated to the corresponding butenes (butene-1, butene-2).
  • a particularly preferred corresponding alkene is ethylene.
  • the sulfur compounds are present in the hydrocarbon-containing fluid in trace amounts, preferably at a level of less than about 1 weight percent sulfur, and preferably at a level of about 0.01 ppm by weight sulfur to about 1,000 ppm by weight sulfur (i.e., about 0.01 to about 1,000 parts by weight sulfur per million parts by weight hydrocarbon-containing fluid).
  • the molar ratio of hydrogen to hydrocarbon of the hydrocarbon- containing fluid in the single-stage adiabatic reaction zone should be in the range of from about 0.01 :1 to about 25:1.
  • the molar ratio of hydrogen to hydrocarbon should be in the range of from about 0.01 : 1 to about 10:1. More preferably, the molar ratio of hydrogen to hydrocarbon should be in the range of from about 0.05:1 to about 5:1, and, most preferably, the molar ratio of hydrogen to hydrocarbon should be in the range from 0.10:1 to 1:1.
  • the molar ratio of hydrogen to C 2 -C 6 alkyne is in the range of from about 0.5:1 to about 200:1, preferably about 1 :1 to about 100:1.
  • the hydrogen and the hydrocarbon-containing fluid can be charged to the single-stage adiabatic reaction zone by any manner or method(s) which maintains the molar ratio of hydrogen to hydrocarbon.
  • the hydrocarbon-containing fluid and the hydrogen are premixed before their contact with a catalyst in the single-stage adiabatic reaction zone.
  • the single-stage reaction zone preferably single-stage adiabatic reaction zone, comprises a structure having an inlet, an outlet, and a length-to-diameter ratio (L:D ratio) in the range of from about 0.25:1 to about 40:1, preferably in the range of from about 0.5:1 to about 30:1, more preferably in the range of from about 0.5:1 to about 20:1, and, most preferably, in the range from 0.5:1 to 5:1.
  • Such structure can comprise, for example, a reactor vessel, preferably an adiabatic reactor vessel.
  • the contacting step i.e., the contacting of hydrocarbon-containing fluid with a catalyst in the single-stage adiabatic reaction zone
  • a solid catalyst bed is generally used although conceptually a moving catalyst bed or a fluidized catalyst bed can be employed. Any of these operational modes have advantages and disadvantages, and those skilled in the art can select the one most suitable for a particular fluid and catalyst.
  • Reaction conditions of the single-stage reaction zone, preferably single- stage adiabatic reaction zone, of the contacting step of the inventive process include a reaction temperature in the range of from about 24 °C to about 260 °C (about 75 °F to about 500 °F).
  • the reaction temperature can be in the range of from about 27°C to about 204°C (about 80°F to about 400°F) and, most preferably, the reaction temperature can be in the range from about 32°C to about 149°C ( 90°F to 300°F).
  • the reaction pressure of the single-stage adiabatic reaction zone can be in the range of from below atmospheric pressure upwardly to 6.89MPa (about 1000 pounds per square inch absolute (psia)), preferably, from 689kPa to about 6201kPa (about 100 psia to about 900 psia) and, most preferably, 1378kPa to 4832kPa from (200 psia to 700 psia).
  • 6.89MPa about 1000 pounds per square inch absolute (psia)
  • 689kPa to about 6201kPa about 100 psia to about 900 psia
  • 1378kPa to 4832kPa from (200 psia to 700 psia).
  • the flow rate at which the hydrocarbon-containing fluid is charged (i.e., the charge rate of hydrocarbon-containing fluid) to the single-stage reaction zone, preferably single-stage adiabatic reaction zone, is such as to provide a gas hourly space velocity ("GHSV") in the range of from exceeding 0 hour "1 upwardly to about 100,000 hour "1 .
  • GHSV gas hourly space velocity
  • the preferred GHSV of the hydrocarbon-containing fluid to the single-stage adiabatic reaction zone can be in the range of from about 500 hour "1 to about 50,000 hour "1 and, most preferably, in the range from 1000 hour "1 to 20,000 hour "1 .
  • the GHSV of the hydrogen gas stream is chosen so as to provide the molar ratios of hydrogen to hydrocarbon of the hydrocarbon-containing fluid as disclosed above.
  • the catalyst can be reactivated by any means or method(s) known to one skilled in the art such as, for example, calcining in air to burn off deposited coke and other carbonaceous materials, such as oligomers or polymers, preferably at a temperature in the range of from about 399°C to about 982°C (about 750°F to about 1800°F).
  • the oxidatively regenerated catalyst is reduced with H 2 or a suitable hydrocarbon before its redeployment in the selective alkyne hydrogenation of this invention.
  • the optimal time periods of the calcining depend generally on the types and amounts of deactivating deposits on the catalyst composition and on the calcination temperatures. These optimal time periods can easily be determined by those possessing ordinary skill(s) in the art and are omitted herein in the interest of brevity.
  • the data presented in Table I below was developed by testing the novel process in a Phillips Petroleum Company ethylene plant at Sweeny, Texas.
  • the ethylene plant utilized a multi-stage reactor system, i.e., two reactor vessels in series, with intercooling between stages, i.e., with heat removal apparatus comprising a heat exchanger between the two reactor vessels.
  • Each reactor vessel contained a catalyst bed, approximately 3 metres length by 3 metres width (10 feet in length and 10 feet in width), comprising approximately 22.4m 3 (800 cubic feet) (approximately 60,000 pounds) of a commercially available catalyst, available from Phillips Petroleum Company, comprising palladium, silver, and alkali metal fluoride.
  • the hydrocarbon-containing feed was passed through the first reactor vessel and then through the second reactor vessel with the product exiting the second reactor vessel. Heat was removed between the first and second reactor vessel via the heat exchanger.
  • a hydrocarbon-containing feed consisting of an ethylene stream, from a thermal ethane cracker, containing about 25 volume percent hydrogen, about 10 volume percent methane, about 25 volume percent ethane, about 40 volume percent ethylene, about 0.35 volume percent acetylene, and about 0.025 volume percent carbon monoxide was introduced into the first reactor vessel at a pressure of 3803 kPa (about 552 pounds per square inch absolute (psia)) and at a gas hourly space velocity of about 9400 hour "1 .
  • the hydrogen to hydrocarbon molar ratio was about 0.33: 1.
  • the hydrogen to acetylene molar ratio was greater than 50:1.
  • the inlet temperature to the first reactor vessel was slowly raised and the heat removal between the first and second reactor vessels was slowly increased.
  • the inlet of the second reactor vessel had been reduced from a normal operating condition of 93.3°C (about 200°F) to less than about 65.5°C (about 150°F) while still maintaining the required product specifications of the product exiting the second reactor vessel.
  • the concentration of acetylene in the product exiting from the outlet of the second reactor vessel controlled the inlet temperature of the first reactor vessel.
  • Product specifications required a concentration of acetylene in the product exiting the second reactor vessel of less than 0.3 ppm (i.e., 0.3 parts by weight acetylene per million parts by weight product) throughout the approximately 60-hour run.
  • An increase in concentration of acetylene in the product resulted in an increase in the inlet temperature of the first reactor vessel thus increasing the hydrogenation of acetylene to ethylene, i.e., increasing the severity of the reaction.
  • the inlet temperature of the first reactor vessel was obtained from a thermocouple 3 metres (about 10 feet) from the actual inlet of the first reactor vessel.
  • the outlet temperature of the first reactor vessel was obtained from a thermocouple at the immediate exit, i.e. bottom, of the first reactor vessel.
  • the change in temperature across the first reactor vessel was the difference between the inlet and outlet temperatures.
  • the inlet temperature of the second reactor vessel was obtained by averaging the temperatures from three thermocouples axially located (i.e., one near the wall of the vessel, one about half-way to the center of the vessel, and one near the center of the vessel) about 0.76m (about 2.5 feet) into the second reactor vessel.
  • the outlet temperature of the second reactor vessel was obtained from a thermocouple at the immediate exit, i.e. bottom, of the second reactor vessel.
  • the change in temperature across the second reactor vessel was the difference between the inlet and outlet temperature.
  • Trend data were obtained throughout the approximately 60-hour run testing the above-described novel process.
  • data were also obtained from specific points in time during the testing of the novel process and are presented in Table I below. The data presented in Table I below were verified against the trend data to ensure that the data presented in Table I are a true reflection of what was indicated in the trend data. TABLE I
  • the trend data indicated that when the carbon monoxide content of the feed fluctuated as a result of bringing a cold furnace into operation, the inventive process was able to handle the fluctuations in carbon monoxide and subsequent increases in inlet temperature without a "runaway" reaction occurring, i.e., without uncontrollable hydrogenation of ethylene to ethane occurring.
  • the data in Table I also indicate that the change in temperature across the first reactor vessel increased only slightly from about 22 °F to about 26 °F.
  • a single-stage adiabatic reaction zone comprising, for example, one or more adiabatic reactor vessels, utilizing a catalyst comprising palladium, silver, and an alkali metal compound such as alkali metal fluoride, can be used in place of a traditional multi-stage reaction zone, with heat removal apparatus between one or more stages, while still maintaining the product specifications required for products exiting the final stage of such multi-stage reaction zone.
  • the data demonstrate that the single-stage adiabatic reaction zone of the inventive process can be used in place of an existing multi-stage reaction zone, the data therefore demonstrate that the volumetric amount of a catalyst comprising palladium, silver, and an alkali metal compound such as alkali metal fluoride, used in the inventive process is significantly less than the volumetric amounts of catalyst present in such multi-stage reaction zone before utilizing the inventive process.
  • the volumetric amount of catalyst comprising palladium, silver, and an alkali metal compound such as alkali metal fluoride, used in the single-stage adiabatic reaction zone of the inventive process was about half, i.e., about 50 percent of, that used in a two-stage reaction zone with heat removal apparatus between stages.
  • the selective hydrogenation process of the invention can be used to modify at least one stage (e.g., at least one reactor vessel), and conceptually all stages (e.g., all reactor vessels), of a multi-stage reaction zone into a single-stage adiabatic reaction zone (comprising, for example, an adiabatic reactor vessel or one or more adiabatic reactor vessels), or, e.g., into a set of single-stage adiabatic reaction zones (e.g., a set of adiabatic reactor vessels), wherein each single- stage adiabatic reaction zone contains a catalyst comprising palladium, silver, and an alkali metal compound such as alkali metal fluoride.
  • a catalyst comprising palladium, silver, and an alkali metal compound such as alkali metal fluoride.
  • Modifying such multi-stage reaction zone eliminates the need to have intercooling between one or more stages of such multi-stage reaction zone.
  • the above-described modification of a multi-stage reaction zone to several single-stage adiabatic reaction zones allows at least one single- stage adiabatic reaction zone to be in service with at least one single-stage adiabatic reaction zone to be in stand-by or to be used for additional acetylene removal allowing an essentially unlimited time to pass between shut-down of the entire reaction system.

Abstract

Cette invention a trait à un procédé permettant d'améliorer le fonctionnement d'un processus de conversion d'alcynes portant de 2 à 6 atomes de carbone (de l'acétylène, de préférence) contenus dans un fluide contenant un hydrocarbure au moyen d'hydrogène pour produire les alcènes correspondants. Avant que des améliorations n'y aient été apportées, ce processus utilisait un certain volume de catalyseur d'hydrogénation nécessaire pour assurer la conversion des alcynes portant de 2 à 6 atomes de carbone en produit converti contenant moins d'alcynes que le fluide contenant un hydrocarbure. Les améliorations apportées consistent à mettre en contact, dans une zone de réaction adiabatique à un seul étage, dans des conditions de réaction, le fluide contenant un hydrocarbure renfermant des alcynes portant de 2 à 6 atomes de carbone (de l'acétylène, de préférence) avec un catalyseur contenant du palladium, de l'argent et un composé à base de fluorure de métal alcalin, sous un volume de conversion approprié inférieur au volume de catalyseur d'hydrogénation.
EP00907282A 1999-02-18 2000-02-14 Procede d'hydrogenation d'alcyne Withdrawn EP1150936A4 (fr)

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US25295499A 1999-02-18 1999-02-18
US252954 1999-02-18
PCT/US2000/003659 WO2000048970A1 (fr) 1999-02-18 2000-02-14 Procédé d'hydrogénation d'alcyne

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WO2005103025A1 (fr) * 2004-04-21 2005-11-03 Novogen Research Pty Ltd Procede de synthese d'isoflavene et catalyseur
CN114442561A (zh) * 2020-10-20 2022-05-06 中国石油化工股份有限公司 碳二前加氢反应器的自动控制方法及系统

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US4762956A (en) * 1983-04-13 1988-08-09 Beijing Research Institute Of Chemical Industry He Ping Li Novel catalyst and process for hydrogenation of unsaturated hydrocarbons
US5488024A (en) * 1994-07-01 1996-01-30 Phillips Petroleum Company Selective acetylene hydrogenation
US5583274A (en) * 1995-01-20 1996-12-10 Phillips Petroleum Company Alkyne hydrogenation process
US5587348A (en) * 1995-04-19 1996-12-24 Phillips Petroleum Company Alkyne hydrogenation catalyst and process
DE19636064A1 (de) * 1996-09-05 1998-03-12 Basf Ag Verfahren zur Hydrierung

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