WO2001049809A1 - Amelioration des catalyseurs de synthese d'hydrocarbures avec de l'hydrogene et de l'ammoniac - Google Patents

Amelioration des catalyseurs de synthese d'hydrocarbures avec de l'hydrogene et de l'ammoniac Download PDF

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WO2001049809A1
WO2001049809A1 PCT/US2000/035329 US0035329W WO0149809A1 WO 2001049809 A1 WO2001049809 A1 WO 2001049809A1 US 0035329 W US0035329 W US 0035329W WO 0149809 A1 WO0149809 A1 WO 0149809A1
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catalyst
hydrogen
reducing gas
ammonia
process according
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PCT/US2000/035329
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English (en)
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Albert L'vovich Lapidus
Alla Jurievna Krylova
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Exxon Research And Engineering Company
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Priority to EP00986751A priority Critical patent/EP1246886A1/fr
Priority to CA002395682A priority patent/CA2395682A1/fr
Priority to JP2001550339A priority patent/JP2003519011A/ja
Priority to AU22933/01A priority patent/AU2293301A/en
Publication of WO2001049809A1 publication Critical patent/WO2001049809A1/fr
Priority to NO20023229A priority patent/NO20023229L/no

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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
    • C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
    • C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
    • C10G2/33—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used
    • C10G2/331—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/16—Reducing
    • B01J37/18—Reducing with gases containing free hydrogen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
    • C07C1/04—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon monoxide with hydrogen
    • C07C1/0425—Catalysts; their physical properties
    • C07C1/0445—Preparation; Activation
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
    • C07C2521/02—Boron or aluminium; Oxides or hydroxides thereof
    • C07C2521/04—Alumina
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
    • C07C2521/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
    • C07C2521/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • C07C2521/08—Silica
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
    • C07C2521/12—Silica and alumina
    • 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
    • C07C2523/46—Ruthenium, rhodium, osmium or iridium
    • 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
    • C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
    • C07C2523/74—Iron group metals
    • C07C2523/75—Cobalt
    • 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
    • C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
    • C07C2523/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with noble metals

Definitions

  • the invention relates to enhancing a hydrocarbon synthesis catalyst with hydrogen and ammonia. More particularly, the invention relates to improving the performance of a hydrocarbon synthesis catalyst, including a Fischer- Tropsch type of hydrocarbon synthesis catalyst, by contacting the catalyst with a reducing gas comprising a mixture of hydrogen and ammonia, at catalyst reduction conditions, and to a hydrocarbon synthesis process using the enhanced catalyst.
  • hydrocarbons including oxygenated hydrocarbons such as methanol
  • a synthesis gas comprising a mixture of H 2 and CO
  • the synthesis gas feed is contacted with a Fischer-Tropsch catalyst at conditions effective for the H 2 and CO in the feed gas to react and form hydrocarbons.
  • the synthesis is known as a Fischer-Tropsch hydrocarbon synthesis.
  • the hydrocarbons may range from oxygenated compounds such as methanol and higher molecular weight alcohols, to high molecular weight paraffins which are waxy solids at room temperature.
  • the process also makes, in lesser amounts, alkenes, aromatics, organic acids, ketones, aldehydes and esters.
  • Hydrocarbon synthesis catalysts are also well known and typically include a composite of at least one iron group catalytic metal component supported on, or composited with, with at least one inorganic refractory metal oxide support material, such as alumina, amorphous, silica-alumina, zeolites and the like.
  • Various catalyst preparation methods have been used to form hydrocarbon synthesis catalysts, including impregnation, incipient wetness, compositing, ion exchange and other known techniques, to form a catalyst precursor. The precursor must be activated to form the catalyst.
  • Typical activation methods include oxidation or calcination, followed by reduction in flowing hydrogen, multiple oxidation-reduction cycles and also reduction without prior oxidation.
  • Examples of catalyst preparation and activation methods for Fischer-Tropsch hydrocarbon synthesis catalysts are disclosed in, for example, US patents US 4,086,262 ; 4,492,774 and 5,545,674.
  • the invention relates to enhancing or improving the performance of an active hydrocarbon synthesis catalyst, including a Fischer-Tropsch type of hydrocarbon synthesis catalyst, by contacting the catalyst with a reducing gas comprising a mixture of hydrogen and ammonia, at conventional catalyst reduction conditions effective to form a active catalyst, and to a hydrocarbon synthesis process using the enhanced catalyst.
  • catalyst is meant an active hydrocarbon synthesis catalyst wherein at least a portion, and preferably only a portion, of the one or more catalytic metals (e.g., Co, Fe, Ni) is in the reduced or catalytically active metal form, as a consequence of reduction achieved by contacting the catalyst precursor in a hydrogen reducing gas without ammonia, at conventional hydrogen reducing conditions.
  • the catalyst may be completely reduced and fully active prior to contact with the hydrogen and ammonia mixture in the practice of the invention, it is preferred that it be partially reduced in hydrogen without ammonia and partially reduced in a reducing gas comprising hydrogen and ammonia, to achieve complete reduction and activation. It has been found that contacting the catalyst with a reducing gas comprising a mixture of hydrogen and ammonia enhances the hydrocarbon synthesis properties of the resulting active catalyst, with respect to at least one of; increased C 5+ selectivity, increased alpha (Schultz-Flory alpha) of the synthesis reaction, and a reduction in methane make. These benefits are unexpected, in view of the fact that ammonia is a well known hydrocarbon synthesis catalyst poison.
  • enhanced catalyst in the context of the invention, is meant that at least one, preferably at least two, and more preferably all three of the following are achieved during hydrocarbon synthesis: (i) the C 5+ selectivity of the catalyst is greater than it otherwise would be if the catalyst had not been contacted with a reducing gas comprising a mixture of hydrogen and ammonia; (ii) the alpha of the synthesis reaction is greater than it would otherwise be if the catalyst had not been contacted with a reducing gas comprising a mixture of hydrogen and ammonia, and (iii) the methane make is reduced to a level lower than it would otherwise be if the catalyst had not been contacted with a reducing gas comprising a mixture of hydrogen and ammonia.
  • the catalyst precursor may or may not be calcined prior to activation by reduction.
  • Either or both the hydrogen reducing gas, and the reducing gas comprising the mixture of hydrogen and ammonia may or may not contain one or more diluent gasses which do not adversely effect or interfere with the reduction and concomitant activation of the catalyst.
  • gasses include methane, argon and the like.
  • the amount of ammonia present in the hydrogen reducing gas will broadly range from 0.01 to 15 mole %, preferably 0.01 to 10 mole %, more preferably from 0.1 to 10 mole % and still more preferably from 0.5 to 7 mole , based on the total gas composition.
  • the hydrogen to ammonia mole ratio in the gas will range from 1000:1 to 5:1 and preferably from 200:1 to 10:1.
  • the invention is a process which comprises enhancing a Fischer-Tropsch type of hydrocarbon synthesis catalyst, comprising at least one catalytic metal component, and preferably at least one catalytic metal component and a metal oxide support type of component, by contacting the catalyst with a reducing gas comprising a mixture of hydrogen and ammonia, at catalyst reduction conditions effective to reduce the one or more catalytic metal components to the reduced, catalytically active metal form, and preferably wherein a portion of the one or more catalytic metal components is reduced to the catalytically active metal form as a result of the contacting.
  • the invention comprises a process for synthesizing hydrocarbons from a synthesis gas which comprises a mixture of H 2 and CO, wherein the synthesis gas is contacted with an enhanced Fischer-Tropsch type of hydrocarbon synthesis catalyst, at reaction conditions effective for the H 2 and CO in the gas to react and form hydrocarbons, wherein the enhanced catalyst comprises a composite of at least one catalytic metal component and metal oxide support component, and has been enhanced by contacting the catalystwith a reducing gas comprising a mixture of hydrogen and ammonia, at catalyst reduction conditions effective to reduce the one or more catalytic metal components to the reduced, catalytically active metal form, and preferably wherein a portion of the one or more catalytic metal components is reduced to the catalytically active metal form as a result of the contacting.
  • a reducing gas comprising a mixture of hydrogen and ammonia
  • At least a portion of the synthesized hydrocarbons are liquid at the reaction conditions.
  • conventional catalyst reduction conditions conditions of temperature, pressure, hydrogen partial pressure and the space velocity of a conventional hydrogen reducing gas, sufficient to reduce the one or more catalytic metal components of the precursor to the metal and form an active catalyst.
  • Hydrocarbon synthesis catalysts are well known and a typical Fischer- Tropsch hydrocarbon synthesis catalyst will comprise, for example, catalytically effective amounts of one or more Group VIII metal catalytic components such as Fe, Ni, Co and Ru.
  • the catalyst comprises a supported catalyst, wherein the one or more support components of the catalyst will comprise an inorganic refractory metal oxide.
  • the metal oxide support component is preferably one which is difficult to reduce, such an oxide of one or more metals of Groups III, IV, V, VI, and VII.
  • the metal Groups referred to herein are those found in the Sargent- Welch Periodic Table of the Elements, ⁇ 1968.
  • Typical support components include one or more of alumina, silica, and amorphous and crystalline aluminosilicates, such as zeolites. Particularly preferred support components are the Group IVB metal oxides, especially those having a surface area of 100 m /g or less and even 70 m /g or less. These support components may, in turn, be supported on one or more support materials. Titania, and particularly rutile titania, is a preferred support component, especially when the catalyst contains a cobalt catalytic component. Titania is a useful component, particularly when employing a slurry hydrocarbon synthesis process, in which higher molecular weight, primarily paraffinic liquid hydrocarbon products are desired.
  • the catalyst comprises catalytically effective amounts of Co
  • it will also comprise one or more components or compounds of Re, Ru, Fe, Ni, Th, Zr, Hf, U, Mg and La, some of which are effective as promoters.
  • Re, Ru, Fe, Ni, Th, Zr, Hf, U, Mg and La some of which are effective as promoters.
  • a combination of Co and Ru is often preferred.
  • Useful catalysts and their preparation are known and illustrative, but nonlimiting examples may be found, for example, in U.S. patents 4,568,663; 4,663,305; 4,542,122; 4,621,072 and 5,545,674.
  • the catalysts are prepared by any convenient and known method, such as impregnation, incipient wetness, ion exchange, kneading, precipitation or coprecipitation, melt deposition or any other compositing techniques to form the catalyst precursor.
  • the catalytic metal component is typically applied as a solution of a compound which decomposes during the subsequent calcination and/or reduction.
  • a cobalt component is typically applied as a nitrate salt. It is not uncommon to calcine the precursor after each application of reducible catalytic metal compound, to achieve better catalytic metal dispersion. After forming and extruding the precursor composite, it is typically pilled and dried.
  • the precursor is then reduced or calcined and reduced, to form the catalyst.
  • the reduction is achieved by contacting the precursor with flowing hydrogen or a hydrogen reducing gas, at conditions effective to reduce the catalytically active metal component (e.g., cobalt) to the metal form.
  • a common method is known as the R-O-R method, in which the precursor is reduced in hydrogen, then calcined, followed by reducing again.
  • the reducing hydrogen gas can be neat (all hydrogen), or mixed with one or more diluent gasses (e.g., methane, argon) which are inert towards the reduction.
  • the R-O-R method may also be used and a conventional hydrogen reducing gas used for the first and at least a portion of the second reduction, and preferably with a portion of the final reduction achieved by a reducing gas comprising a mixture of hydrogen and ammonia.
  • Typical reducing conditions effective for forming the catalyst comprising the reduced metal component on the support from the precursor range from Vi to 24 hours, 200-500°C, 1-100 bar, and a GHSV of 50-10000. The actual conditions will depend on the hydrogen concentration in the reducing gas, as well as the metal to be reduced and its precursor form (e.g., salt or oxide).
  • the at least partially reduced and active catalyst is contacted with a mixture of a hydrogen reducing gas and ammonia, at typical reducing conditions, as set forth above, similar to those used for normal reduction and concomitant activation.
  • the catalyst enhancement may be conducted according to the process of the invention, either prior to loading it into the hydrocarbon synthesis reactor or in-situ in the hydrocarbon synthesis reactor.
  • the enhanced catalyst may be used in either a fixed bed, fluid bed or slurry hydrocarbon synthesis processes, for forming hydrocarbons from a synthesis gas comprising a mixture of H 2 and CO. These processes are well known and documented in the literature. In all of these processes, the synthesis gas is contacted with a suitable Fischer-Tropsch type of hydrocarbon synthesis catalyst, at reaction conditions effective for the H 2 and CO in the gas to react and form hydrocarbons. Depending on the process, the catalyst and synthesis reaction variables, some of these hydrocarbons will be liquid, some solid (e.g., wax) and some gas at standard room temperature conditions of temperature and pressure of 25°C and one atmosphere, particularly if a catalyst having a catalytic cobalt component is used.
  • a suitable Fischer-Tropsch type of hydrocarbon synthesis catalyst at reaction conditions effective for the H 2 and CO in the gas to react and form hydrocarbons.
  • some of these hydrocarbons will be liquid, some solid (e.g., wax) and some gas at standard room temperature conditions of temperature and
  • reaction products In a fluidized bed hydrocarbon synthesis process, all of the products are vapor or gas at the reaction conditions. In fixed bed and slurry processes, the reaction products will comprise hydrocarbons which are both liquid and vapor at the reaction conditions. Slurry hydrocarbon synthesis processes are sometimes preferred, because of their superior heat (and mass) transfer characteristics for the strongly exothermic synthesis reaction and because they are able to produce relatively high molecular weight, paraffinic hydrocarbons when using a cobalt catalyst.
  • a synthesis gas comprising a mixture of H 2 and CO is bubbled up as a third phase through a slurry in a reactor which comprises a particulate Fischer- Tropsch type hydrocarbon synthesis catalyst dispersed and suspended in a slurry liquid comprising hydrocarbon products of the synthesis reaction which are liquid at the reaction conditions.
  • the mole ratio of the hydrogen to the carbon monoxide in the synthesis gas may broadly range from about 0.5 to 4, but is more typically within the range of from about 0.7 to 2.75 and preferably from about 0.7 to 2.5.
  • the stoichiometric mole ratio for a Fischer-Tropsch hydrocarbon synthesis reaction is 2.0, but it can be increased to obtain the amount of hydrogen desired from the synthesis gas for other than the hydrocarbon synthesis reaction.
  • the mole ratio of the H 2 to CO is typically about 2.1/1. Reaction conditions effective for the various hydrocarbon synthesis processes will vary somewhat, depending on the type of process, catalyst composition and desired products.
  • Typical conditions effective to form hydrocarbons comprising mostly C 5+ paraffins, (e.g., C 5+ -C 2 oo) and preferably C ⁇ o + paraffins, in a slurry process employing a catalyst comprising a supported cobalt component include, for example, temperatures, pressures and hourly gas space velocities in the range of from about 320-600°F, 80-600 psi and 100-40,000 V/hr/V, expressed as standard volumes of the gaseous CO and H mixture (0°C, 1 atm) per hour per volume of catalyst, respectively. These conditions nominally apply to the other processes as well.
  • Hydrocarbons produced by a hydrocarbon synthesis process according to the practice of the invention are typically upgraded to more valuable products, by subjecting all or a portion of the C 5+ hydrocarbons to fractionation and/or conversion.
  • conversion is meant one or more operations in which the molecular structure of at least a portion of the hydrocarbon is changed and includes both noncatalytic processing (e.g., steam cracking), and catalytic processing (e.g., catalytic cracking) in which a fraction is contacted with a suitable catalyst.
  • hydroconversion If hydrogen is present as a reactant, such process steps are typically referred to as hydroconversion and include, for example, hydroisomerization, hydrocracking, hydrodewaxing, hydrorefimng and the more severe hydrorefimng referred to as hydrotreating, all conducted at conditions well known in the literature for hydroconversion of hydrocarbon feeds, including hydrocarbon feeds rich in paraffins.
  • More valuable products formed by conversion include one or more of a synthetic crude oil, liquid fuel, olefins, solvents, lubricating, industrial or medicinal oil, waxy hydrocarbons, nitrogen and oxygen containing compounds, and the like.
  • Liquid fuel includes one or more of motor gasoline, diesel fuel, jet fuel, and kerosene
  • lubricating oil includes, for example, automotive, jet, turbine and metal working oils.
  • Industrial oil includes well drilling fluids, agricultural oils, heat transfer fluids and the like.
  • a commercially available silica gel known as KCKG #4 manufactured by Salavat Catalyst Factory of the Salavat Petrochemical Complex, Salavant, Russia, 2-4 mm diameter, was ground and sieved to obtain a 0.106-0.250 mm size fraction. This material was then calcined in flowing air at 450°C for 5 hours, to form the support for the catalysts prepared below.
  • a solution of 5.18 gm of Co(N0 3 ) 2 *6H 2 0 in 15 ml of distilled water was prepared. This solution was added to 21 ml (8.38 gm) of the calcined silica support from Example 1 , with stirring, to form a catalyst precursor. Then the catalyst precursor was dried on a steam bath. At this stage, the catalyst precursor contained nominally 11 wt % cobalt and is the catalyst A precursor.
  • the so-formed catalyst B precursor contained 27 wt. % cobalt and 4.1 wt. % zirconium oxide.
  • the catalyst B precursor of Example 3 (20 ml) was mixed with 80 ml of 1-3 mm quartz particles and the mixture placed into a 25 mm ID quartz reactor.
  • the catalyst/quartz mixture was held in place with glass wool at the bottom of the reactor and a layer consisting of 10 ml of the 1-3 mm quartz particles on top of the catalyst/quartz mixture.
  • Hydrogen was then passed through the reactor at room temperature and atmospheric pressure at a gas hourly space velocity (GHSV) of 100 hr "1 for 15 minutes. Prior to entering the reactor, the hydrogen was passed through a column of KOH pellets (pellet diameter nominally 3-5 mm) for removal of impurities.
  • the reactor temperature was increased to 450°C over 40-45 minutes. This condition was held for 5 hours.
  • the reactor was allowed to cool to room temperature in flowing hydrogen. After the reactor had cooled, the hydrogen flow was replaced with a flow of 2:1 H 2 :CO synthesis gas at 100 hr "1 GHSV, for 15 minutes at atmospheric pressure. As with the hydrogen, the synthesis gas was passed through a column of KOH pellets for removal of impurities. Then valves were closed at the inlet and outlet of the reactor, storing the catalyst under the synthesis gas.
  • Example 5 (Catalyst B reduction in H 2 and then NH 3 / ⁇ 2 )
  • a 20 ml sample of the catalyst B precursor of Example 3 was mixed with 80 ml of 1-3 mm quartz particles and the mixture placed into a 25 mm ID quartz reactor.
  • the catalyst/quartz mixture was held in place with glass wool at the bottom of the reactor and a layer consisting of 10 ml of the 1-3 mm quartz particles on top of the catalyst/quartz mixture.
  • Hydrogen was then passed through the reactor at room temperature and atmospheric pressure at a gas hourly space velocity (GHSV) of 100 hr "1 for 15 minutes. Prior to entering the reactor, the hydrogen was passed through a column of KOH pellets (pellet diameter nominally 3-5 mm) for removal of impurities and through a 3-necked flask containing NaOH pellets.
  • GHSV gas hourly space velocity
  • the center neck of the 3-necked flask was equipped with a syringe for addition of 29 wt % NH_J 71 wt % H 2 0 solution.
  • the NaOH in the 3-necked flask served to absorb the water from the NH 3 H 2 0 solution, liberating the NH 3 vapor, which was then swept out of the flask and into the reactor.
  • the reactor temperature was increased to 400°C over 40-45 minutes.
  • the procedure used in Example 4 in which the reactor temperature was increased from room temperature to 450°C over 40-45 minutes and held at 450°C for 5 hours was used until the reactor reached the 450°C temperature.
  • the total reduction time was 5 hours, as shown in Table 2.
  • the reactor was allowed to cool to room temperature in flowing hydrogen. After the reactor had cooled, the hydrogen flow was replaced with a flow of 2:1 H 2 :CO synthesis gas at 100 hr "1 GHSV for 15 minutes at atmospheric pressure. As with the hydrogen, the synthesis gas was passed through a column of KOH pellets, for removal of impurities. Then valves were closed at the inlet and outlet of the reactor, storing the catalyst under the synthesis gas.
  • a 20 ml sample of the catalyst A precursor of Example 2 was mixed with 80 ml of 1-3 mm quartz particles and the mixture placed into a 25 mm ID quartz reactor.
  • the catalyst/quartz mixture was held in place with glass wool at the bottom of the reactor and a layer consisting of 10 ml of the 1-3 mm quartz particles on top of the catalyst/quartz mixture.
  • Hydrogen was then passed through the reactor at room temperature and atmospheric pressure at a gas hourly space velocity (GHSV) of 3000 hr "1 for 15 minutes. Prior to entering the reactor, the hydrogen was passed through a column of KOH pellets (pellet diameter nominally 3-5 mm) for removal of impurities and through a 3-necked flask containing NaOH pellets.
  • GHSV gas hourly space velocity
  • the center neck of the 3-necked flask was equipped with a syringe for addition of 29 wt % NH ⁇ 71 wt % H 2 0 solution.
  • the NaOH in the 3-necked flask served to absorb the water from the NH 3 /H 2 0 solution, liberating the NH 3 vapor, which was then swept out of the flask to the reactor.
  • the reactor temperature was increased to 400°C over 40-45 minutes. After reaching 400°C, drop- ise addition of the 29 wt % NH ⁇ 71 wt. % H 2 0 solution was commenced from the syringe.
  • the addition rate was varied to give a nominal concentration of NH 3 in the reducing gas between 0 (H 2 -only) and 3.0 mole %. This condition was held for 1 hour. Then the reactor was allowed to cool to room temperature in flowing hydrogen. After the reactor had cooled, the hydrogen flow was replaced with a flow of 2:1 H 2 :CO synthesis gas at 100 hr "1 GHSV, for 15 minutes at atmospheric pressure. As with the hydrogen, the synthesis gas was passed through a column of KOH pellets for removal of impurities. Then valves were closed at the inlet and outlet of the reactor, storing the catalyst under the synthesis gas.
  • the flow of synthesis gas into the reactor was resumed with the catalyst of Example 6 (Catalyst A reduced with H 2 +NH 3 ) at 100 hr "1 GHSV and 1 arm pressure.
  • the synthesis gas Prior to entering the reactor, the synthesis gas was passed through a column of KOH pellets (pellet diameter nominally 3-5 mm) for removal of impurities.
  • the synthesis gas composition was 2:1 H 2 :CO by volume.
  • the reactor temperature was increased from room temperature to 160°C in about 40 minutes. This condition was held for 5 hours, after which the reactor was cooled down to room temperature in the flowing synthesis gas and the catalyst stored under the synthesis gas as described in Example 6. Testing was resumed the next day following the same procedure, except that the test temperature was 10°C higher.
  • the optimum operating temperature was defined as the temperature where the yield of Cs + products is maximized, as measured in gm of C 5+ product per standard cubic meter of synthesis gas fed to the reactor. Finding the optimum operating temperature entailed increasing the reactor temperature in 10°C steps until the C 5+ yield decreased from the previous test. The temperature from the previous test is the optimum temperature. Catalyst performance was determined by measuring the gas contraction, product gas composition by gas chromatography, and C 5+ liquid product yield. The C 5+ liquid product was recovered form the reactor effluent using two traps. The first trap was water cooled and the second was cooled with dry ice/acetone (-80°C).
  • the C 5+ product in the first trap was weighted directly.
  • the liquid product in the second trap was first warmed to room temperature, to vaporize C - components prior to weighing.
  • the combined weights of the hydrocarbon liquid product in both traps was used to determine the C 5+ product yield.
  • the C 5+ product from the optimum temperature was further analyzed, to determine hydrocarbon type and carbon chain length distribution. From time to time, the C 5+ products from the non- optimum temperature tests were combined and analyzed.
  • the catalyst precursor was not calcined prior to reduction in these experiments. The results are shown in Table 1 below.
  • Example 8 (Catalyst B testing after Reduction with H 2 and then with H 2 +NH 3 )
  • the synthesis gas flow was resumed into the reactor with the catalyst of Example 5 (Catalyst B reduced first with H 2 then with H 2 +NH 3 ) at 100 hr "1 GHSV and 1 atm pressure.
  • the synthesis gas Prior to entering the reactor, the synthesis gas was passed through a column of KOH pellets (pellet diameter nominally 3-5 mm) for removal of impurities.
  • the synthesis gas composition was 2: 1 H 2 :CO by volume.
  • the reactor temperature was increased from room temperature to 160°C in about 40 minutes. This condition was held for 5 hours, after which the reactor was cooled to room temperature in the flowing synthesis gas and the catalyst stored under the synthesis gas. Testing was resumed the next day following the same procedure, except that the test temperature was 10°C higher.
  • the catalyst performance was determined by measuring the gas contraction, product gas composition by gas chromatography, and C 5+ liquid product yield.
  • the C 5+ liquid was recovered form the reactor effluent using two traps. The first trap was water cooled and the second was cooled with dry ice/acetone (-80°C). The C 5+ product in the first trap was weighted directly. The liquid product in the second trap was first warmed to room temperature to vaporize C 4- components prior to weighing. The combined weights of the hydrocarbon liquid product in both traps was used to determine the C 5+ product yield.
  • the Cs + product from the optimum temperature was further analyzed to determine hydrocarbon type and carbon chain length distribution.
  • Table 2 shows how, at a constant reducing time of 5 hours, the performance of Catalyst B is affected by the presence of NH 3 in the H 2 reducing gas, when sequentially reduced with H 2 followed by H 2 +NH 3 , and also when reduced in only H 2 +NH 3 . It should be noted, that tests revealed optimum catalytic properties for the catalyst reduced under hydrogen, at a hydrogen treat gas ratio of 100 hr "1 GHSV, were achieved at a reduction time of five hours. This is why the total reduction time of 5 hours was chosen for this experiment. However, a portion of the metal reduction and concomitant activation is achieved in one hour.
  • an active catalyst existed prior to contact with the hydrogen and ammonia reducing gas, for the runs in Table 2 above, in which the contact time with the hydrogen reducing gas was, 1, 2, 3 and 4 hours.
  • the contact time with the hydrogen reducing gas was, 1, 2, 3 and 4 hours.
  • it was a precursor that was contacted with the hydrogen and ammoma mixture for 5 hours.
  • this last run and the first run with only hydrogen reduction are not within the scope of the invention and are presented for comparative purposes.
  • Table 2 shows, in the second through the fifth runs, the precursor was at least partially reduced prior to contact with the hydrogen and ammonia mixture.

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  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
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Abstract

Pour améliorer la qualité de catalyseurs de synthèse d'hydrocarbures, on met le catalyseur en contact avec un gaz réducteur comprenant un mélange d'hydrogène et d'ammoniac, à une température élevée et une pression efficace pour effectuer la réduction classique du catalyseur de synthèse. Il est préférable qu'une partie de la réduction totale soit effectuée avec un gaz réducteur comprenant de l'ammoniac et de l'hydrogène et que le reste soit effectué avec un gaz réducteur sans ammoniac.
PCT/US2000/035329 2000-01-04 2000-12-26 Amelioration des catalyseurs de synthese d'hydrocarbures avec de l'hydrogene et de l'ammoniac WO2001049809A1 (fr)

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EP00986751A EP1246886A1 (fr) 2000-01-04 2000-12-26 Amelioration des catalyseurs de synthese d'hydrocarbures avec de l'hydrogene et de l'ammoniac
CA002395682A CA2395682A1 (fr) 2000-01-04 2000-12-26 Amelioration des catalyseurs de synthese d'hydrocarbures avec de l'hydrogene et de l'ammoniac
JP2001550339A JP2003519011A (ja) 2000-01-04 2000-12-26 水素およびアンモニアによる炭化水素合成触媒の増強
AU22933/01A AU2293301A (en) 2000-01-04 2000-12-26 Hydrocarbon synthesis catalyst enhancement with hydrogen and ammonia
NO20023229A NO20023229L (no) 2000-01-04 2002-07-03 Hydrokarbonsyntesekatalysatorforbedring med hydrogen og ammoniakk

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WO2003002252A1 (fr) * 2001-06-28 2003-01-09 Isis Innovation Limited Procede d'activation d'un catalyseur contenant un compose de cobalt et un support
WO2003064040A1 (fr) * 2002-01-29 2003-08-07 Exxonmobil Research And Engineering Company Traitement de catalyseurs supportes
WO2005071044A1 (fr) * 2004-01-13 2005-08-04 Syntroleum Corporation Reaction de fischer-tropsch en presence de contaminants azotes
WO2007113965A1 (fr) * 2006-03-31 2007-10-11 Nippon Oil Corporation Catalyseur de réduction pour monoxyde de carbone, procédé de préparation de ce catalyseur et procédé de production d'hydrocarbures
JP2007268477A (ja) * 2006-03-31 2007-10-18 Nippon Oil Corp 一酸化炭素の還元触媒およびその調製方法
CN102015584A (zh) * 2008-04-16 2011-04-13 开普敦大学 由合成气生产包括烯烃的碳氢化合物的方法
AU2007288693B2 (en) * 2006-08-25 2011-10-13 Nippon Steel Engineering Co., Ltd. Catalyst for producing hydrocarbon from synthetic gas, method for producing catalyst, method for regenerating catalyst, and method for producing hydrocarbon from synthetic gas
CN102863306A (zh) * 2011-07-04 2013-01-09 中国石油化工股份有限公司 一种浆态床费托合成方法

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US6753286B2 (en) * 2002-01-29 2004-06-22 Exxonmobil Research And Engineering Company Supported catalyst regeneration
JP2007270049A (ja) * 2006-03-31 2007-10-18 Nippon Oil Corp 一酸化炭素の還元による炭化水素の製造方法
JP6007167B2 (ja) * 2013-11-18 2016-10-12 Ｊｘエネルギー株式会社 フィッシャー・トロプシュ合成用触媒の製造方法及び炭化水素の製造方法

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US4196100A (en) * 1978-01-10 1980-04-01 The International Nickel Co., Inc. Catalyst useful for methanation and preparation thereof
US4565831A (en) * 1981-12-16 1986-01-21 Exxon Research And Engineering Co. Process for producing aromatic hydrocarbons from carbon monoxide and water

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7183329B2 (en) 2001-06-28 2007-02-27 Isis Innovation Process for the activation of a catalyst comprising a cobalt compound and a support
US7511080B2 (en) 2001-06-28 2009-03-31 Isis Innovation Limited Process for the activation of a catalyst comprising a cobalt compound and a support
WO2003002252A1 (fr) * 2001-06-28 2003-01-09 Isis Innovation Limited Procede d'activation d'un catalyseur contenant un compose de cobalt et un support
AU2002304467B2 (en) * 2001-06-28 2007-12-06 Isis Innovation Limited A process for the activation of a catalyst comprising a cobalt compound and a support
AU2002360794B2 (en) * 2002-01-29 2008-04-03 Exxonmobil Research And Engineering Company Supported catalyst treatment
US6787496B2 (en) 2002-01-29 2004-09-07 Exxonmobil Research And Engineering Company Supported catalyst treatment
WO2003064040A1 (fr) * 2002-01-29 2003-08-07 Exxonmobil Research And Engineering Company Traitement de catalyseurs supportes
CN1617766B (zh) * 2002-01-29 2011-08-17 埃克森美孚研究工程公司 载体催化剂的处理
WO2005071044A1 (fr) * 2004-01-13 2005-08-04 Syntroleum Corporation Reaction de fischer-tropsch en presence de contaminants azotes
WO2007113965A1 (fr) * 2006-03-31 2007-10-11 Nippon Oil Corporation Catalyseur de réduction pour monoxyde de carbone, procédé de préparation de ce catalyseur et procédé de production d'hydrocarbures
JP2007268477A (ja) * 2006-03-31 2007-10-18 Nippon Oil Corp 一酸化炭素の還元触媒およびその調製方法
AU2007232013B2 (en) * 2006-03-31 2012-04-19 Nippon Oil Corporation Reduction catalyst for carbon monoxide, process for preparing the catalyst and process for producing hydrocarbon
AU2007288693B2 (en) * 2006-08-25 2011-10-13 Nippon Steel Engineering Co., Ltd. Catalyst for producing hydrocarbon from synthetic gas, method for producing catalyst, method for regenerating catalyst, and method for producing hydrocarbon from synthetic gas
US9295976B2 (en) 2006-08-25 2016-03-29 Nippon Steel Engineering Co., Ltd Catalyst for producing hydrocarbon from syngas, method for producing catalyst, method for regenerating catalyst, and method for producing hydrocarbon from sysngas
CN102015584A (zh) * 2008-04-16 2011-04-13 开普敦大学 由合成气生产包括烯烃的碳氢化合物的方法
US8558047B2 (en) * 2008-04-16 2013-10-15 University Of Cape Town Process for the production of hydrocarbons including olefins from synthesis gas
CN102863306A (zh) * 2011-07-04 2013-01-09 中国石油化工股份有限公司 一种浆态床费托合成方法

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AR026794A1 (es) 2003-02-26
NO20023229D0 (no) 2002-07-03
EP1246886A1 (fr) 2002-10-09
CA2395682A1 (fr) 2001-07-12
NO20023229L (no) 2002-08-30
JP2003519011A (ja) 2003-06-17
AU2293301A (en) 2001-07-16

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