EP1519788A1 - Procede d'hydrogenation d'acetylenes - Google Patents

Procede d'hydrogenation d'acetylenes

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Publication number
EP1519788A1
EP1519788A1 EP02748159A EP02748159A EP1519788A1 EP 1519788 A1 EP1519788 A1 EP 1519788A1 EP 02748159 A EP02748159 A EP 02748159A EP 02748159 A EP02748159 A EP 02748159A EP 1519788 A1 EP1519788 A1 EP 1519788A1
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Prior art keywords
weight percent
metal
support
catalytic composite
dispersed
Prior art date
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EP02748159A
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German (de)
English (en)
Inventor
Hayim Abrevaya
Deng-Yang Jan
Karl Z. Steigleder
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Honeywell UOP LLC
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UOP LLC
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Priority to EP06021462A priority Critical patent/EP1754535A1/fr
Publication of EP1519788A1 publication Critical patent/EP1519788A1/fr
Withdrawn legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
    • B01J21/04—Alumina
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/72—Copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/75—Cobalt
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/755—Nickel
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/889—Manganese, technetium or rhenium
    • B01J23/8892—Manganese
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8926—Copper and noble metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/31—Density
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
    • B01J35/51—Spheres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/615—100-500 m2/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0072—Preparation of particles, e.g. dispersion of droplets in an oil bath
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0238—Impregnation, coating or precipitation via the gaseous phase-sublimation
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts

Definitions

  • Butadiene is an important starting material for the production of high molecular weight polymers and is used extensively to form synthetic rubber including styrene-butadiene rubber, nitrile-butadiene rubber, buna-S rubber, and trans-polybutadiene rubber, and adiponitrile and styrene butadiene latex in paints.
  • Butadiene is usually a by-product from steam cracking naphtha.
  • the product butadiene regularly contains impurities that must be removed before the butadiene may be used as a starting material.
  • the principal impurities are acetylenes including ethylacetylene, methylacetylene and vinylacetylene.
  • two approaches have been used to remove the acetylenes: extractive distillation using a solvent to selectively absorb the acetylenes, or selective hydrogenation of the acetylenes.
  • US-A-4,493,906 discloses copper-containing catalytic composites for selective hydrogenation of acetylenes in the form of 1600 ⁇ m (1/16 inch) extrudates.
  • US-A-4,440,956 discloses the catalysts as 1/8 inch (3mm) pellets.
  • US-A-3,912,789, and US-A-3,218,268 disclose the catalysts as 3/16 inch tablets.
  • US-A-3,751 ,508 discloses the catalysts as 3 mm tablets (1/8 inch tablet).
  • a microsphere catalyst has been discovered to have much improved stability and selectivity versus similar catalysts having particles of 1/16 inch (1600 ⁇ m) diameter.
  • the present invention is an improved process for selectively hydrogenating C -acetylenes in a liquid hydrocarbon stream containing largely butadiene with the benefit of increased catalyst stability.
  • Hydrogen and the hydrocarbon stream contact a catalytic composite comprising an inorganic oxide support having dispersed thereon finely divided copper metal and optionally an activator metal selected from the group consisting of nickel, cobalt, platinum, palladium, manganese, and a combination.
  • At least 70 weight percent of the copper metal and the activator metal are dispersed on the outer 200 ⁇ m layer of the support.
  • at least 80 weight percent of the copper metal is dispersed on the outer 200 ⁇ m layer of the support.
  • hydrogen and the hydrocarbon stream contacted a spherical catalytic composite having an average diameter of 800 ⁇ m (1/32 inch) or less.
  • the catalytic composite comprises an inorganic oxide support having dispersed thereon finely divided copper metal and optionally an activator metal selected from the group consisting of nickel, cobalt, platinum, palladium, manganese.
  • FIG. 1 and FIG. 2 show the weight percent conversion of vinyl acetylene and total acetylenes respectively.
  • FIG. 3 shows 1 ,3-butadiene retention over time.
  • FIG. 4 shows weight percent hydrogen conversion.
  • FIG 5. shows the hydrogen:acetylene usage ratio (moles hydrogen consumed divided by moles acetylenes consumed).
  • FIG. 6 shows selectivity to polymeric byproducts. DETAILED DESCRIPTION OF THE INVENTION
  • the invention is a process for selectively hydrogenating C -acetylenes in the presence of large amounts of butadiene by contacting the hydrocarbons with a supported catalytic composite.
  • at least 50 weight percent of the active catalytic agents preferably at least 70 weight percent, more preferably at least 80 weight percent, and most preferably at least 88 weight percent, are located on the outer 200 ⁇ m layer of the support.
  • the support is spherical and has an average diameter of less than 800 ⁇ m (1/32 inch). The invention further reduces the production of undesired high molecular weight polymerized byproducts thereby extending the stability and enhancing the selectivity of the catalyst.
  • C -acetylenes as used herein is meant to include vinylacetylene, ethylacetylene, and methylacetylene.
  • the vinylacetylene is hydrogenated to 1 ,3-butadiene
  • the ethylacetylene is hydrogenated to 1-butene
  • the methylacetylene is hydrogenated to propylene.
  • the C 4 -acetylenes are typically formed as a byproduct in butadiene production and must be removed before the butadiene can be further processed.
  • the acetylenes may be in a concentration ranging from 0.5 to 3 weight percent, or higher, of the product liquid hydrocarbon stream from a butadiene production reactor.
  • the liquid hydrocarbon stream generally contains butadiene (40-50 weight percent), butenes (40-50 weight percent), butanes (5-10 weight percent) and C 4 -acetylenes. Propane and C 3 -acetylenes are also present in minor quantities.
  • hydrogen and the hydrocarbon stream enter a fixed bed reactor.
  • Various methods of introducing hydrogen to the reactor are known and any such method is suitable for use in this invention.
  • the preferred method admixes the hydrocarbon stream with a stoichiometric amount of hydrogen and then introduces the mixture to a fixed bed reactor.
  • the fixed bed reactor contains a catalytic composite effective to catalyze the selective hydrogenation of the acetylenes.
  • the catalytic composite must be "selective" to the acetylenes so as to minimize hydrogenation of the desired butadiene.
  • the catalytic composite contains finely divided copper metal and one or more activator metals which are bound to a support.
  • the activator metals are those which are normally introduced in the form of salts and whose oxides are reducible by hydrogen. Suitable activator metals include nickel, cobalt, manganese, platinum, palladium, or a combination thereof.
  • the most preferred activator metal is nickel.
  • the copper is present in an amount ranging from 5 to 15 weight percent of the whole finished catalytic composite in the oxidized form and the activator metal is present in an amount ranging from 0.1 to 1 weight percent of the whole finished catalytic composite in the oxidized form.
  • the support may be refractory inorganic oxide materials such as silica, alumina, carbon, titania, magnesia, zirconia, clays, zeolites, and a combination thereof.
  • the aluminas for supports include gamma, theta, delta, and alpha alumina with gamma and theta alumina being preferred.
  • Suitable zeolites include faujasites, zeolite Beta, L-zeolite, ZSM-5, ZSM-8, ZSM-11 , ZSM-12, and ZSM-35.
  • the support may be of any suitable size and shape including spherical and extruded supports.
  • the extruded support is prepared as commonly known in the art.
  • An extrudate is preferably cylindrical with a 800 ⁇ m (1/32 inch) diameter.
  • the support may also be a shaped support such as a trilobe, quadrulobe, irregular shaped particles, pellets, or hollow tube which preferably posses a maximum diffusion path of 800 ⁇ m (1/32 inch) or less.
  • the support may also be spherical with typical sphere sizes used in process such as these include 1600 ⁇ m (1/16 inch) and 3200 ⁇ m (1/8 inch).
  • a preferred spherical support is of a "microsphere" size, which includes spheres of support material nominally having a diameter of 800 ⁇ m (1/32 inch) or less.
  • the spheres are preferably produced by commonly known oil-dropping techniques such as described in United States Patent No. 2,620,314, which is incorporated by reference.
  • the oil drop method comprises forming an aluminum hydrosol, preferably by reacting aluminum metal with hydrochloric acid; combining the hydrosol with a suitable gelling agent, e.g., hexamethylenetetramine; and dropping the resultant mixture into and oil bath maintained at elevated temperatures. The mixture droplets remain in the oil bath until they set and form hydrogel spheres.
  • the spheres are then continuously withdrawn from the oil bath and typically subjected to specific aging and drying treatments in oil and ammoniacal solutions to further improve their physical characteristics.
  • Aged gel spheres undergo washing at 70°C to 100°C, drying at a temperature of 65°C to 260°C, and calcining for 1 to 20 hours at a temperature of 455°C to 705°C. This treatment converts the hydrogel to the corresponding crystalline gamma-alumina. If theta alumina is desired then the hydrogel spheres are calcined at a temperature of 950°C to 1200°C.
  • microspheres are preferred, a variety of support shapes are suitable, as discussed above. It is preferred that the support, whether spherical or not, have an effective diameter of 800 ⁇ m (1/32 inch) or less. For a non- spherical support, effective diameter is defined as the diameter of the shaped article would have if it were molded into a sphere.
  • the catalytic metal copper, and the activator metal(s) may be dispersed onto the support by means well known in the art such as impregnation, coprecipitation, cogellation . or ion exchange.
  • the preferred method of incorporating the metal copper and the activator metals is impregnation of the support with a solution containing one or more decomposable compound of the desired metal(s) followed by calcination.
  • Illustrative of the decomposable compounds which can be used are: copper nitrate, copper acetate, copper acetylacetonate, nickel nitrate, nickel carbonate, nickel acetate, nickel acetylacetonate, manganese nitrate, manganese acetate, manganese acetylacetonate, manganese carbonate, manganese carbonyl, cobalt nitrate, cobalt acetate, cobalt acetylacetonate, cobalt carbonate, chloroplatinic acid, platinum tetrachloride, palladic acid, palladium chloride, and palladium nitrate.
  • Suitable impregnation techniques include dip, evaporative and vacuum impregnation.
  • a preferred impregnation method uses of a steam-jacketed rotary evaporator. The desired support is immersed in an impregnating solution containing the desired metal(s) in the drier and the support is tumbled therein by the rotary motion of the drier. Evaporation of the solution in contact with the tumbling support is expedited by applying the steam to the drier jacket. The resultant catalytic composite is dried and then calcined.
  • microspherical catalytic composite in this invention has several advantages over previously disclosed catalysts.
  • a portion of the acetylenes present in the hydrocarbon stream will tend to polymerize and form high molecular weight undesirable byproducts, see, Sarkany, A.; Weiss, A. H.; Szilagyi, T.; Sandor P.; Guczi L. Applied Catalysis 1984, 12, 373-379.
  • much of the polymerization occurs within the pores of the catalytic composite with the polymerized products remaining trapped within the pores and decreasing the activity of the catalyst.
  • the selective nature of the hydrogenation decreases and the amount of hydrogenation of butadiene relative to the amount of hydrogenation of acetylenes increases.
  • the residence time of the acetylene within the catalyst before being hydrogenated is reduced thereby decreasing the opportunity for the acetylene to polymerize.
  • the diffusion path length of the acetylene through the composite is reduced allowing for more rapid hydrogenation and less acetylene is available for polymerization.
  • Reducing the amount of acetylene polymerization results in increased catalytic composite stability and enhanced selectivity.
  • the catalyst may be operated at less severe conditions for a longer period of time with fewer periodic regeneration cycles and no loss of acetylene conversion.
  • the product effluent has higher purity and requires less intense downstream purification processing. Larger diameter catalysts are expected to provide the same advantages as discussed above when at least 50 and preferably 70 weight percent of the copper metal and the activator metals are dispersed on the outer 200 ⁇ m of the catalyst support.
  • the evaporative impregnation technique may incorporate may incorporate copper and the activator metals on the catalytic support such that at least 50 weight percent of the metals are located in the outer 200 ⁇ m layer of the support, preferably at least 70 weight percent of the metals are located in the outer 200 ⁇ m layer of the support, and more preferably at least 80 weight percent of the metals are located in the outer 200 ⁇ m layer of the support. It is most preferred that at least 88 weight percent of the metals are located on the outer 200 ⁇ m layer of the support.
  • Layer is meant to describe a stratum of substantially uniform thickness
  • outer is meant to define the exterior layer of the support. In general terms.
  • Surface impregnation can be carried out using metal complexes that have a high affinity for the support surface or complexes which are bulky in nature or by spray impregnation techniques in which the volume of the impregnating solution is less than that required to fill the pore volume.
  • Techniques for surface impregnation are described in US-A-3,259,454; US-A-3,259,589; US-A-3,388,077, Lee, S.; Aris, R. Catal. Rev.-Sci. Eng. 1985, 27(2), 207-340; Komiyama, M. Catal. Rev.-Sci. Eng. 1985, 27(2), 341-372; and Dougherty, R. C; Verykios, X. E. Catal. Rev.-Sci. Eng. 1987, 29(1), 101-150.
  • Selective hydrogenation of the acetylenes contacts the hydrocarbons with the above-described catalytic composite in a fixed bed system.
  • a heated reactant mixture enters a single bed, or multiple sub-beds of the fixed bed system. Heating means between the individual beds may maintain the reactants at the desired temperature.
  • the fixed bed system may operate in a swing bed mode, with one sub-bed on-line and receiving the reactant mixture while another sub-bed is off-line. The off-line sub-bed may be undergoing regenerated, or may have completed regeneration and is ready for use.
  • the acetylenes are hydrogenated leaving the effluent stream essentially acetylene-free.
  • Examples of the selective hydrogenation reactions include hydrogenating vinyl acetylene to form 1 ,3-butadiene, hydrogenating ethyl acetylene to form 1-butene, and hydrogenating methyl acetylene to form propylene.
  • the amount of residual acetylenes expected in the reactor effluent is typically less than 15 wt-ppm.
  • Conditions for the selective hydrogenation of C 4 -acetylenes include a temperature in the range of 20°C to 80°C, pressures in the range of from 1500 kPa (15 bars) to 5,000 kPa (50 bars) and liquid hourly space velocities in the range of from 0.5 to 10 hr "1 . Hydrogen is also added at a hydrogen to acetylene ratio of from 1.0 to 5.0.
  • EXAMPLE 1 The specific embodiment involves a process for selectively hydrogenating C 4 -acetylenes in a liquid hydrocarbon stream containing largely butadiene comprising contacting hydrogen and the hydrocarbon stream with a catalytic composite which is an inorganic oxide support having dispersed thereon finely divided copper metal and optionally an activator metal selected from the group consisting of nickel, cobalt, platinum, palladium, manganese, and a combination thereof where the catalytic composite is spherical and has an average diameter of up to 800 ⁇ m (1/32 inch).
  • Alumina spheres were prepared by the oil drop method. Dissolving aluminum in hydrochloric acid formed an aluminum hydrosol.
  • hexamethylene tetraamine to the hydrosol gelled the mixture into spheres when dispersing droplets into an oil bath maintained at 93°C.
  • the droplets remained in the oil bath until they set and formed hydrogel spheres.
  • the spheres were removed from the hot oil, pressure aged at 130°C, washed with dilute ammonium hydroxide solution, dried to 260°C and calcined at 640°C for 1.5 hours to give gamma alumina spheres having an average diameter of 1600 ⁇ m (1/16 inch).
  • the metal incorporation was performed using the evaporative impregnation technique. Dissolving copper nitrate, nickel nitrate, cobalt nitrate, and manganese nitrate in water prepared the impregnation solution. The resultant solution was then added to a rotary evaporator loaded with the gamma alumina spheres. After cold rolling the mixture for 1 hour steam was introduced to the outer jacket to evaporate the excess water. The metal impregnated catalyst was dried at 210°C for 1 hour and calcined at 400°C for 2 hours. The above process was repeated three times to give three reference catalysts having 1600 ⁇ m (1/16 inch) diameter spheres, identified as Reference 1 , Reference 2, and Reference 3.
  • alumina spheres were prepared by the well known oil drop method involving forming an aluminum hydrosol by dissolving aluminum in hydrochloric acid. To this hydrosol, where was added hexamethylene tetraamine to gel the mixture into spheres when dispersed into droplets into an oil bath maintained at 93°C. The droplets remained in the oil bath until they set and formed hydrogel microspheres. After the microspheres were removed from the hot oil, they were pressure aged at 120°C and washed with dilute ammonium hydroxide solution, dried at 205°C and calcineb 1 at 640°C for 1.5 hours to give gamma alumina microspheres having an average diameter of 800 ⁇ m (1/32 inch).
  • the metal incorporation was performed in the manner described for example 1.
  • the microspherical catalyst was analyzed and compared to the reference catalysts prepared in Example 1.
  • Table 1 shows the results of the microspherical catalyst analysis as compared to the typical result for the three reference catalysts with all concentration units in weight percent of the catalytic composite.
  • the catalysts prepared in Examples 1 and 2 were evaluated in a selective hydrogenation process with the results demonstrating the enhanced stability and selectivity of the microspherical catalyst of Example 2 as compared to Reference catalysts 1 , 2, and 3 of Example 1.
  • a reactor was loaded with 16 g of the microspherical catalyst prepared in Example 2 and heated to an inlet temperature of 60°C.
  • a crude C hydrocarbon stream from a naphtha cracker complex and containing 38 wt. % 1 ,3-butadiene and 0.35 weight percent of vinyl acetylene and 0.13 wt. % ethylacetylene was introduced to the reactor at an acetylene weight hourly space velocity of 0.15.
  • the hydrogen to acetylene molar ratio was 2.1.
  • Figure 1 shows the weight percent conversion of vinyl acetylene that occurred over time during each of the experiments.
  • the data clearly shows the increased stability of the microspherical catalyst over time as compared to the reference catalysts.
  • the microspherical catalyst of Example 2 remained at greater than 90 weight percent conversion of vinyl acetylene for 70 hours on stream, while the reference catalysts of Example 1 showed less than 80 weight percent conversion at 70 hours on stream.
  • Figure 2 shows the microspherical catalyst of Example 2 remained at greater than 78 weight percent conversion of total acetylenes at 70 hours on stream, while the reference catalysts of Example 1 showed less than 75 weight percent conversion total acetylenes at 70 hours on stream.
  • the enhanced selectivity of the microspherical catalyst is demonstrated in Figure 3 which shows higher butadiene retention (weight percent of butadiene in the effluent divided by weight percent butadiene in the feed) with the microspherical catalyst; in Figure 4 which shows overall less hydrogen conversion when using the microspherical catalyst; and in Figure 5 which shows lower hydrogen to acetylene usage ratio indicating that less hydrogen is being consumed through hydrogenation of butadiene when using the microspherical catalyst.
  • Figure 6 indicates that the selectivity for polymeric byproducts, or green oil, is less when using the microspherical catalyst of Example 1.

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Abstract

L'invention porte sur un procédé d'hydrogénation sélective de C4-acétylènes dans un flux d'hydrocarbures liquides contenant une quantité élevée de butadiène. Les flux d'hydrogène et d'hydrocarbures sont mis en contact avec un composite catalytique contenant un support d'oxyde inorganique sur lequel sont répartis du métal de cuivre finement divisé et un métal activateur de nickel, cobalt, platinium, palladium, manganèse, ou une combinaison de ces derniers, 1) le composite catalytique présentant un diamètre moyen pouvant atteindre 800 νg(m)m (1/32 pouces) et/ou 2) au moins 70 % en poids de métal de cuivre et le métal activateur étant répartis sur la couche externe de 200 νm du support.
EP02748159A 2002-07-08 2002-07-08 Procede d'hydrogenation d'acetylenes Withdrawn EP1519788A1 (fr)

Priority Applications (1)

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EP06021462A EP1754535A1 (fr) 2002-07-08 2002-07-08 Procede d'hydrogenation d'acetylenes

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US7408089B2 (en) * 2004-03-19 2008-08-05 Catalytic Distillation Technologies Ni catalyst, process for making catalysts and selective hydrogenation process
KR101384407B1 (ko) * 2006-07-17 2014-04-10 바스프 에스이 구리 및 아연을 포함하는 촉매의 존재하에 불포화 탄화수소를 수소화하는 방법
FR2970881B1 (fr) * 2011-01-31 2015-03-20 IFP Energies Nouvelles Catalyseur thioresistant, procede de fabrication et utilisation en hydrogenation selective
CN104001520B (zh) * 2013-11-27 2016-06-22 大连理工大学 一种低温锰基复合金属氧化物脱硝催化剂的合成方法

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CN1638867A (zh) 2005-07-13
CN1309473C (zh) 2007-04-11
AU2002318331A1 (en) 2004-01-23
EP1754535A1 (fr) 2007-02-21
WO2004004901A1 (fr) 2004-01-15

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