[go: up one dir, main page]

WO2008147013A2 - Procédés de préparation d'hydrocarbures liquides à partir de gaz synthétique à l'aide de catalyseurs fischer-tropsch à base d'oxyde de zirconium et d'aluminium - Google Patents

Procédés de préparation d'hydrocarbures liquides à partir de gaz synthétique à l'aide de catalyseurs fischer-tropsch à base d'oxyde de zirconium et d'aluminium Download PDF

Info

Publication number
WO2008147013A2
WO2008147013A2 PCT/KR2008/000547 KR2008000547W WO2008147013A2 WO 2008147013 A2 WO2008147013 A2 WO 2008147013A2 KR 2008000547 W KR2008000547 W KR 2008000547W WO 2008147013 A2 WO2008147013 A2 WO 2008147013A2
Authority
WO
WIPO (PCT)
Prior art keywords
catalyst
cobalt
zirconia
alumina
support
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.)
Ceased
Application number
PCT/KR2008/000547
Other languages
English (en)
Other versions
WO2008147013A3 (fr
Inventor
Ki-Won Jun
Jong-Wook Bae
Seung-Moon Kim
Jong-Hyeok Oh
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.)
Korea Research Institute of Chemical Technology KRICT
Hyundai Engineering Co Ltd
KOREA INTERNATIONAL CORP
Doosan Mecatec Co Ltd
SK Energy Co Ltd
DL Holdings Co Ltd
Original Assignee
Korea Research Institute of Chemical Technology KRICT
Hyundai Engineering Co Ltd
Daelim Industrial Co Ltd
KOREA INTERNATIONAL CORP
Doosan Mecatec Co Ltd
SK Energy Co Ltd
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 Korea Research Institute of Chemical Technology KRICT, Hyundai Engineering Co Ltd, Daelim Industrial Co Ltd, KOREA INTERNATIONAL CORP, Doosan Mecatec Co Ltd, SK Energy Co Ltd filed Critical Korea Research Institute of Chemical Technology KRICT
Priority to EP08705003A priority Critical patent/EP2152413A2/fr
Publication of WO2008147013A2 publication Critical patent/WO2008147013A2/fr
Publication of WO2008147013A3 publication Critical patent/WO2008147013A3/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • 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
    • 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
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group 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
    • 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
    • B01J23/89—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
    • B01J23/8913—Cobalt 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
    • B01J35/60—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
    • 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
    • B01J35/66—Pore distribution
    • 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
    • B01J35/66—Pore distribution
    • B01J35/69—Pore distribution bimodal
    • 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
    • B01J37/03—Precipitation; Co-precipitation
    • 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
    • C10G2/332—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 of the iron-group
    • 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
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/066—Zirconium or hafnium; Oxides or hydroxides thereof
    • 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
    • B01J23/76—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
    • B01J23/8896—Rhenium
    • 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
    • B01J2523/30—Constitutive chemical elements of heterogeneous catalysts of Group III (IIIA or IIIB) of the Periodic Table
    • B01J2523/31—Aluminium
    • 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
    • B01J2523/40—Constitutive chemical elements of heterogeneous catalysts of Group IV (IVA or IVB) of the Periodic Table
    • B01J2523/48—Zirconium
    • 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
    • B01J35/63—Pore volume
    • B01J35/633—Pore volume less than 0.5 ml/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
    • 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
    • B01J35/63—Pore volume
    • B01J35/635—0.5-1.0 ml/g

Definitions

  • the present invention relates to a cobalt/zirconia- alumina catalyst, in which cobalt is supported as an active ingredient on zirconia- alumina prepared by co-precipitation.
  • the catalysts show a bimodal pore structure with different pore sizes and maintaining a specific pore volume ratio and a method for preparing liquid hydrocarbons with high yield during the Fischer- Tropsch synthesis of syngas (CO/H 2 /CO 2 ) in the presence of the cobalt/zirconia-alumina catalyst.
  • the GTL process has been refined and adjusted continuously.
  • the GTL technology based on the F-T synthesis not only improves the environmental problem at the gas field, but also enables the production of clean synthetic fuels through processing of the flared gas.
  • the GTL products which are clean liquid fuels with little sulfur content, may provide a better market value than those of the conventional petroleum products produced by refining a crude oil.
  • the US, Europe, Japan, etc. reduced the sulfur content in the diesel oil for cars from 500 ppm to 50 ppm and they are expected to further lower to below 10 ppm in the near future.
  • the F-T synthetic oil is a fuel that can effectively cope with the recently reinforced environmental regulations from developed countries, along with the recent regulations of the Kyoto Protocol.
  • the GTL synthetic fuel gives off less exhaust gas and nitrogen oxides and is capable of reducing the atmospheric acidification by more than 40 %. Further, the emission of particulate matters (PM) can be reduced by more than 40 % and the utilization of F-T synthetic oil in cars is expected to reduce the emission of greenhouse gas by at least 12 % through increased thermal efficiency.
  • PM particulate matters
  • the F-T synthesis originates from the preparation of synthetic fuel from syngas by coal gasification invented by German chemists Fischer and Tropsch in 1923.
  • the GTL process consists of the three major sub-processes of (1) reforming of natural gas, (2) F-T synthesis of syngas and (3) reforming of product.
  • the F-T reaction which is performed at a reaction temperature of 200 to 350 0 C and a pressure of 10 to 30 atm using iron and cobalt as catalyst can be described by the following four key reactions.
  • iron- and cobalt-based catalysts are used for the F-T reaction.
  • the iron- based catalysts were preferred in the past for F-T reaction.
  • the cobalt catalysts are predominant in order to increase the production of liquid fuel or wax and to improve conversion.
  • Iron-based catalysts are advaantageous for the F-T reaction as they are the most inexpensive F-T reaction catalysts producing less methane at high temperature and having high selectivity for olefins and the product can be utilized as source material in chemical industry as light olefin or ⁇ -olefin, as well as fuel.
  • many byproducts, including alcohols, aldehydes, ketones, etc. are produced in addition to hydrocarbons.
  • the iron-based catalyst mainly used in the low-temperature F-T reaction for wax production by Sasol comprises Cu and K components as cocatalyst and is produced by the precipitation using SiO 2 as a binder.
  • the Sasol's high-temperature F-T catalyst is prepared by melting magnetite, K, alumina, MgO, etc.
  • Cobalt-based catalysts are more expensive than Fe-based catalysts. But, they have higher activity, longer lifetime and higher yield of liquid paraffin-based hydrocarbon production with less CO 2 generation. However, they can be used only at low temperature because the excessive CH 4 is produced at high temperature. Further, with the usage of expensive cobalt, the catalysts are prepared by dispersing on a stable support with a large surface area, such as alumina, silica, titania, etc. A small amount of a precious metal cocatalyst such as Pt, Ru, Re, etc., is added as cocatalyst.
  • F-T synthesis reactors there are four types: circulating a fluidized bed reactor, a fluidized bed reactor, a multitubular fixed bed reactor and a slurry-phase reactor.
  • the reactor should be adequately selected considering the syngas composition and the final product, because they have different reaction properties.
  • the F-T process parameters are determined by the final product.
  • the high-temperature F-T process for producing gasoline and olefin is carried out in the fluidized bed reactor and the low-temperature F-T process for producing wax and lubricant base oil is carried out in the multitubular fixed bed reactor (MTFBR) or in the slurry-phase reactor.
  • MTFBR multitubular fixed bed reactor
  • slurry-phase reactor Usually, linear-chain paraffins are produced by the F-T synthesis reaction, but C n H 2n compounds having double bonds, ⁇ -olefins or alcohols are obtained as the byproduct from side reactions.
  • cobalt or other activation substance is introduced to a support having a large surface area, such as alumina, silica, titania, etc., to prepare a catalyst.
  • a catalyst prepared by dispersing cobalt on a single-component or multi-component support is commercially utilized.
  • the activity of the F-T reaction does not change much from the usage of one support to another [Applied Catalysis A 161 (1997) 59].
  • the activity of the F-T reaction is greatly affected by the dispersion and particle size of cobalt [ Journal of American Chemical Society, 128 (2006) 3956]. Accordingly, a lot of attempts are being made to improve the FTS activity and stability by modifying the surface property of the supports by pretreating them with different metal components.
  • the aforesaid F-T catalysts show various specific surface areas, but the activity of the F-T reaction is known to be closely related with the particle size of the cobalt component, pore size distribution of the support and reducing tendency of the cobalt component. To improve these properties, a preparation method of the F-T catalyst by including the cobalt component through a well-known method on the support prepared through a complicated process is reported.
  • Fischer- Tropsch reaction with superior activity and heat- and matter-transfer performance in order to solve the aforementioned problems in an economical and efficient way.
  • a catalyst having a bimodal pore structure was prepared on a zirconia- alumina support consisting of a predetermined proportion of ZrO 2 and Al 2 O 3 prepared by the co-precipitation.
  • the cobalt is supported by the co-precipitation to achieve uniform dispersion of cobalt on the support with a smaller pore size PSi and pores of a larger size PS 2 .
  • the catalyst exihibits better heat- and matter-transfer performance than the conventional unimodal catalyst.
  • the modification of alumina surface of the support by the zirconia component the chemical properties such as the dispersion of the active component, electronic state, reducible properties, are improved. This enables the improvement of F-T reaction using the catalyst, one-pass yield of carbon monoxide and hydrogen and long-term stability of the catalyst.
  • the objective of the present invention is to provide a cobalt/ zirconia- alumina catalyst having larger and smaller pores prepared by supporting cobalt on a zirconia-alumina support comprising ZrO 2 and Al 2 O 3 and having a predetermined specific surface area obtained through co-precipitation as an active ingredient and a preparation method of liquid hydrocarbons from a syngas using the same.
  • the cobalt/zirconia-alumina catalyst in accordance with the present invention offers advantages in the competitive design and development of a GTL process with significantly improved carbon efficiency. This enables the improvement of thermal efficiency and carbon efficiency in the GTL process, the systematic design of the F-T reaction process and reduced selectivity to methane and increased selectivity to liquid hydrocarbons having 5 or more carbon atoms.
  • Figure 1 shows the conversion of carbon monoxide with reaction time after performing Fischer- Tropsch using the catalyst of the present invention (Example 1, 0.5 wt% Ru/20 wt% Co/5 wt% ZrO 2 -Al 2 O 3 ) and the catalyst prepared in Comparative Example 1 (20 wt% Co/80 wt% Al 2 O 3 ).
  • Figure 2 shows the pore distribution of the catalyst of the present invention (Example
  • Example 3 20 wt% Co/5 wt% ZrO 2 -Al 2 O 3 ), as compared with those of Comparative Example 1 (20 wt% Co/Al 2 O 3 ) and Comparative Example 2 (0.5 wt% Ru/20 wt% Co/5 wt% Zr/Al 2 O 3 ).
  • the present invention provides a catalyst for Fischer- Tropsch reaction in which cobalt is supported on a support as an active ingredient.
  • the catalyst being a cobalt/ zirconia- alumina catalyst in which the cobalt is supported on a zirconia- alumina support comprising Al 2 O 3 and ZrO 2 as an active ingredients with a bimodal pore structure with pores of a relatively smaller size PSi and of a larger size PS 2 .
  • the pore sizes PSi and PS 2 are in the range described below.
  • the ZrO 2 being comprised in the amount of 1 to 30 wt% per 100 wt% of the Al 2 O 3 and the cobalt being comprised in the amount of 5 to 40 wt% per 100 wt% of the support:
  • a cobalt component or other active component is dispersed on a support having a large surface area, such as alumina, silica, titania, etc. If the only cobalt component is added, the dispersion and reducing property of the active component decreases as the pores may be clogged by the compounds having a high boiling point produced during the reaction, leads to accelerated deactivation of the catalyst.
  • FTS Fischer- Tropsch synthesis
  • the water produced during the reaction may cause the change of the surface property of the -alumina to that of boehmite, etc. Therefore, various methods of pre-treating with another component have been introduced to improve thermal stability of alumina. Besides, when silica is used as a support, a stronger interaction occurs between cobalt and the support than with an alumina support leads to the reducing tendency to cobalt metal and consequently decreases the activity. To overcome this problem, a method is proposed to pre-treat the silica surface with metal oxide as zirconium oxide. Especially, as an effective strategy, numerous attempts have been made to ensure long-term stability of the catalyst by improving the rate of transfer of compounds having a high boiling point and heat transfer, using a support having a bimodal pore structure.
  • a support comprising zirconia and alumina and having a bimodal pore structure is disclosed in Korean Patent No. 10-388310.
  • the pores of the support have sizes in the range of from 0.05 to 1 ⁇ m and from 1 to 10 ⁇ m.
  • Each powder component of the support is mixed with each other and then the active component is supported on it in order to prepare a catalyst having a broad pore distribution.
  • the aforesaid patent relates to a catalyst prepared by supporting an active component on a zirconia-alumina support having a bimodal pore distribution.
  • cobalt is supported on a zirconia-alumina support with unimodal pores smaller than 10 nm to obtain a catalyst having a bimodal pore structure.
  • the former relates to a support having a bimodal pore distribution
  • the present invention relates to a catalyst having a bimodal pore structure.
  • Such apparent difference leads to catalysts with totally different pore sizes, specific surface areas, and, consequently, to totally different applications. That is, the cited invention is for the conversion of hydrocarbons, while the present invention is for the Fischer- Tropsch reaction.
  • the present invention is characterized not by the support, but by performing the Fischer- Tropsch reaction using a cobalt/zirconia-alumina catalyst having a bimodal pore structure prepared by supporting cobalt as an active ingredient on a support having unimodal pores.
  • a cobalt/zirconia-alumina catalyst having a bimodal pore structure prepared by supporting cobalt as an active ingredient on a support having unimodal pores.
  • the present invention provides a preparation method for a zirconia-alumina catalyst comprising cobalt and having a bimodal pore structure different from the conventional one.
  • a catalyst having a bimodal pore structure is prepared by preparing a support comprising alumina and zirconia and then supporting cobalt, or the active component, on the support by co-precipitation.
  • the co- precipitation method is commonly known in the related art, but, in the present invention, zirconia and aluminum precursor are co-precipitated using an adequate pre- cipitant under appropriate precipitation condition in order to form pores in the support smaller than 10 nm only. Then, using the resultant zirconia- alumina support with unimodal pores, the cobalt component is co-precipitated to prepare a catalyst having a bimodal pore structure.
  • the methods of obtaining the porous support and preparing the F-T catalyst having a bimodal pore structure are not easily achievable from the conventional methods.
  • a zirconia-alumina support having pores of the size 10 nm or smaller on the first hand and then a cobalt component is co-precipitated to improve dispersion of the cobalt component and prevent clogging of the pores by the compounds having a high boiling point produced during the reaction.
  • the cobalt/zirconia-alumina catalyst having a bimodal pore structure of the present invention which is obtained by preparing a zirconia-alumina support having pores of the size 10 nm or smaller by co-precipitation and then supporting cobalt as an active ingredient on the support having unimodal pores by co-precipitation, offers the improved F-T catalytic activity.
  • a support comprising alumina has a broad pore distribution and is mainly prepared by sol-gel method or precipitation.
  • the unimodal pores are distributed over a large area and, when cobalt is supported on it the particle size distribution becomes non-uniform and the particle size tends to increase.
  • the compounds having a high boiling point produced during the reaction may clog the pores and, thereby, significantly reduces the activity of the catalyst.
  • the present invention provides a cobalt/ zirconia-alumina catalyst having a bimodal pore structure with relatively small-sized and large-sized pores prepared by the co-precipitation, ensures high yield of liquid hydrocarbons in the F-T reaction.
  • the zirconia-alumina support of the catalyst for the F-T reaction is prepared by the co-precipitation and has pores with a pore size of 10 nm or smaller with a specific surface area in the range 150 to 400 m 2 /g.
  • zirconium metal is comprised of 1 to 30 wt% per 100 wt% of alumina. If the content is smaller than 1 wt%, it does not improve much the dispersion and reducing property of the active component of cobalt. If it exceeds 30 wt%, specific surface area of the zirconia- alumina support decreases, which may result in the decrease of the dispersion of cobalt.
  • the catalyst of the present invention may be prepared by the following two methods.
  • the first method is a two-step process comprising: co-precipitating by adding a basic precipitant to an aqueous solution mixture including a zirconium precursor and an alumina precursor at pH 7 to 8, aging and baking at 300 to 900 0 C to prepare a zirconia- alumina support; and co-precipitating by adding an aqueous solution including a cobalt precursor and a basic precipitant to the prepared zirconia-alumina support at pH 7 to 8, aging and baking at 200 to 700 0 C to prepare a cobalt/ zirconia-alumina catalyst having a bimodal pore structure with a smaller pore size PSi and pores of a larger size PS 2 .
  • the second method is a three-step process comprising: co-precipitating by adding a basic precipitant to an aqueous solution including a zirconium precursor and an alumina precursor at pH 7 to 8 and aging to prepare a slurry-phase zirconia-alumina support; co-precipitating by adding a basic precipitant to an aqueous solution including a cobalt precursor at pH 7 to 8 and aging to prepare a cobalt slurry; and mixing the prepared slurry-phase zirconia-alumina support and the cobalt slurry, drying and baking at 200 to 700 0 C to prepare a cobalt/zirconia-alumina catalyst having a bimodal pore structure with a smaller pore size PSi and pores of a larger size PS 2 .
  • the zirconia-alumina support is prepared by co-precipitation.
  • the co-precipitation is performed using a precipitant commonly used in the art.
  • the precursors of the metals used in the preparation are those commonly used in the art and not particularly limited.
  • the alumina precursor may be aluminum nitrate (A1(NO 3 ) 3 9H 2 O) or aluminum isopropoxide (A1[OCH(CH 3 ) 2 ] 3 )
  • the zirconium precursor may be zirconium nitrate (Zr(NO 3 ) 2 2H 2 O) or zirconium chloroxide (ZrCl 2 O- 8H 2 O).
  • a basic precipitant is used to maintain pH at 7 to 8.
  • sodium carbonate (Na 2 CO 3 ), potassium carbonate (K 2 CO 3 ), ammonium carbonate ((NH 4) 2 CO 3 ), ammonia water, etc. may be used.
  • the alumina and zirconium precursors are co-precipitated in an aqueous solution of pH 7 to 8 using the aforesaid precipitant and aged at 40 to 90 0 C. Then, the precipitate is filtrated and washed.
  • the zirconia-alumina support is prepared so as to comprise 1 to 30 wt% of zirconium oxide and 70 to 99 wt% of Al 2 O 3 . If the aging temperature is below 40 0 C, it is difficult to obtain a zirconia-alumina support having unimodal pores adequate for the F-T reaction. And, if it exceeds 90 0 C, the particle size of the support increases and, thus, the specific surface area decreases.
  • the aging is performed for 0.1 to 15 hours, preferably for 0.5 to 10 hours, in order to form a structure advantageous to the activity. If the aging time is shorter than 0.1 hour, the structure of the zirconia- alumina support does not develop sufficiently. And, if it exceeds 15 hours, particle size increases and, thus the activity decreases and the synthesis time increases. [58]
  • the resultant precipitate is washed and dried for about a day in an oven of 100 0 C or higher. Then, a cobalt component is supported on the precipitate and baking is performed to apply for the F-T reaction. Alternatively, the cobalt component may be supported after baking the zirconia-alumina support.
  • the active component of cobalt may be included in the zirconia- alumina support by the following two methods.
  • a slurry solution is prepared using the prepared powdery zirconia-alumina support. Then, a cobalt precursor is co-precipitated in an aqueous solution at pH 7 to 8 using a co-precipitant. After aging at 40 to 90 0 C, the precipitate is filtrated and washed for use.
  • the F-T catalyst is prepared such that the cobalt component is comprised in the amount of 5 to 40 wt% per 100 wt% of the zirconia-alumina support. If the content of cobalt is less than 5 wt%, the shortage of the active component required for the F-T reaction may result in the reduction of conversion and decrease in the production of the compounds having a high boiling point.
  • a basic precipitant is used to maintain pH at 7 to 8, as described earlier.
  • the aging is performed at 40 to 90 0 C, preferably at 50 to 80 0 C. If the temperature of aging the catalyst is below 40 0 C, it is difficult to attain cobalt with uniform particle size and shape, which makes the supporting of the cobalt component difficult. If it exceeds 90 0 C, the particle size of cobalt increases due to coagulation, which results in the decrease of specific surface area and reaction activity.
  • the aging time is maintained for 0.1 to 15 hours, preferably for 0.5 to 10 hours, since the aging time in the recommended range is advantageous in the formation of a cobalt-supported zirconia-alumina catalyst with superior activity.
  • An aging time shorter than 0.1 hour is unfavorable with regard to the F-T reaction because of reduced dispersion of cobalt. And, if the aging time exceeds 15 hours, the number of active sites decreases and the synthesis time increases because of increased particle size of cobalt.
  • the resultant precipitate is washed and dried at 100 0 C or above, specifically for about a day in an oven of 100 to 150 0 C.
  • Such prepared precipitate may be directly used for the synthesis of the F-T reaction catalyst or may be baked after supporting a second precious metal catalyst component.
  • 700 0 C preferably at 300 to 600 0 C. If the baking temperature is below 200 0 C, interaction between cobalt and the support may be inadequate and particle size may increase during the reaction. And, if it exceeds 700 0 C, dispersion and catalytic activity may decrease because of the increased particle size of the cobalt component. Hence, the aforesaid range is preferable.
  • the F-T catalyst may also be prepared using the powdery zirconia-alumina support, as follows.
  • a cobalt precursor is co-precipitated in an aqueous solution of pH 7 to 8 and is aged at 40 to 90 0 C. Then, the precipitate is baked at 300 to 900 0 C, preferably at 400 to 800 0 C, to prepare a zirconia-alumina support.
  • the cobalt/zirconia-alumina catalyst is prepared by supporting the cobalt component.
  • the use of basic precipitant during the co-precipitation and the process of aging, washing and drying of the catalyst are the same as described above.
  • the prepared cobalt component is mixed with the zirconia- alumina support prepared by baking in water or an alcohol solution while stirring to prepare the wanted cobalt-supported zirconia-alumina catalyst.
  • Such prepared precipitate may be directly used for the synthesis of the F-T reaction catalyst after washing and drying for about a day in an oven of 100 0 C or higher or may be baked after supporting a second precious metal catalyst component.
  • the resultant cobalt-supported zirconia-alumina catalyst for F-T reaction has a bimodal pore structure, the final specific surface area ranging from 100 to 300 m 2 /g and having pores of smaller size ranging from 2 to 10 nm and pores of larger size ranging from 10 to 200 nm. And, the proportion of the volume PVi of the smaller pores of 2 to 10 nm to the volume PV 2 of the larger pores of 10 to 200 nm, or PVi/PV 2 , is maintained in the range of from 0.5 to 2.0. If the ratio is smaller than 0.5, specific surface area of the cobalt component decreases because of the increase of larger pores and, resultantly, activity may decrease. If it exceeds 2.0, the dispersion decreases because of the increase of smaller pores and, resultantly, activity may decrease.
  • a precious metal component may be used to improve reducing property of the cobalt active component and inhibit oxidation of the cobalt active component by water.
  • a precursor such as ruthenium, rhenium, platinum, etc., may be used in the form of nitrate salt, acetate salt or chloride salt.
  • the precious metal component is used in 0.05 to 1 wt% per 100 wt% of the zirconium precursor. If it is used less than 0.05 wt%, the effect is insignificant. If in excess of 1 wt%, the catalyst manufacture cost increases and selectivity for methane increases.
  • the support of the present invention facilitates the transfer of the compounds having a high boiling point produced during the reaction while further improving dispersion and reducing property of the cobalt and other active components. Consequently, it reduces the production of methane and improves the selectivity for liquid hydrocarbons via improved FT reactivity.
  • the present invention further provides a preparation method for liquid hydrocarbons using the catalyst from a syngas by the Fischer- Tropsch reaction.
  • the F-T reaction may be performed as commonly carried out in the art and is not particularly limited.
  • the F-T reaction is performed using the catalyst in a fixed bed, a fluidized bed or slurry reactor, in the temperature range of from 200 to 700 0 C, after reducing under hydrogen atmosphere.
  • F-T reaction is performed in a standard condition, specifically at a temperature of 300 to 500 0 C, at a pressure of 30 to 60 kg/cm 2 and at a space velocity of 1000 to 10000 h ⁇ although not limited thereto.
  • Such prepared catalyst provides an F-T reaction conversion of 10 to 50 mol% and a selectivity for hydrocarbons with five carbon atoms or more, specifically naphtha, diesel, middle distillate, heavy oil, wax, etc., of 83 mol% or higher.
  • the slurry solution was stirred and aged for about 3 hours at 70 0 C.
  • the precipitant was removed by washing with 1800 mL of deionized water and filtering.
  • a 5 wt% powdery zirconia- alumina support was prepared by baking for 5 hours under air atmosphere at 500 0 C.
  • the prepared support had pores of 10 nm or smaller only and the specific surface area was 299 m 2 /g and the pore volume was 0.47 cmVg.
  • the cobalt precursor aqueous solution, the potassium carbonate precursor aqueous solution and the 5 wt% zirconia- alumina support slurry were simultaneously added dropwise at a rate of 5 mL/min to a 2000 mL flask at 70 0 C, while stirring and maintaining pH at 7 to 8.
  • the slurry solution was stirred and aged for about 1 hour at 70 0 C.
  • the precipitant was removed by washing with 1800 mL of deionized water and filtering.
  • a 20 wt% Co/5 wt% ZrO 2 -Al 2 O 3 catalyst was prepared by baking for 5 hours under air atmosphere at 500 0 C.
  • ruthenium nitrosyl nitrate (Ru(NO) (NO 3 ) 3 ) was supported on the 20 wt% Co/5 wt% ZrO 2 -Al 2 O 3 catalyst.
  • a 0.5 wt% Ru/20 wt% Co/5 wt% ZrO 2 -Al 2 O 3 catalyst was prepared by baking at 400 0 C for 5 hours under oxygen atmosphere.
  • the prepared catalyst had a bimodal pore structure, the specific surface area being 245 m 2 /g and the pore volume being 0.80 cmVg, particularly the volume ratio of the smaller pores to the large pores PWPV 2 being 0.84.
  • the slurry solution was stirred and aged for about 3 hours at 70 0 C.
  • the precipitant was removed by washing with 1800 mL of deionized water and filtering to prepare a 5 wt% zirconia- alumina precipitate in the form of cake.
  • a cobalt precursor is dissolved in 300 mL of deionized water and a potassium carbonate precursor aqueous solution in which 10.8 g of potassium carbonate (K 2 CO 3 ), a precipitant, is dissolved in 300 rnL of deionized water were prepared.
  • the solutions were simultaneously added dropwise at a rate of 5 mL/min to a 2000 mL flask holding 200 mL of deionized water at 70 0 C, while stirring and maintaining pH at 7 to 8.
  • the slurry solution was stirred and aged for about 1 hour at 70 0 C.
  • the precipitant was removed by washing with 1800 mL of deionized water and filtering to obtain cobalt precipitate in the form of cake.
  • Each prepared zirconia- alumina precipitate and cobalt precipitate in the form of cake was stirred for over 1 hour in 200 mL of deionized water at room temperature to obtain a zirconia-alumina slurry containing cobalt. After filtering, the prepared slurry was dried in an oven at 100 0 C for over 12 hours and baked for 5 hours under air atmosphere at 500 0 C to prepare a 20 wt% Co/5 wt% ZrO 2 -Al 2 O 3 catalyst.
  • ruthenium nitrosyl nitrate (Ru(NO) (NO 3 ) 3 ) was supported on the 20 wt% Co/5 wt% ZrO 2 -Al 2 O 3 catalyst.
  • a 0.5 wt% Ru/20 wt% Co/5 wt% ZrO 2 -Al 2 O 3 catalyst was prepared by baking at 400 0 C for 5 hours under oxygen atmosphere.
  • the prepared catalyst had a bimodal pore structure, the specific surface area being 220 m 2 /g and the pore volume being 0.62 cmVg, particularly the volume ratio of the smaller pores to the large pores PVi/PV 2 being 1.27.
  • Example 2 except for excluding ruthenium.
  • the prepared catalyst had a bimodal pore structure, the specific surface area being 238 m 2 /g and the pore volume being 0.53 cm 3 / g, particularly the volume ratio of the smaller pores to the large pores PVi/PV 2 being 1.43.
  • a 0.5 wt% Ru/20 wt% Co/5 wt% ZrO 2 - Al 2 O 3 catalyst was prepared in the same manner as in Example 1.
  • the prepared catalyst was reduced with hydrogen at 400 0 C for 12 hours and introduced to a slurry reactor after sealing. 300 mL of squalane was added as solvent in the slurry reactor. After adding 5 g of the catalyst, another reduction was performed at 220 0 C for over 12 hours.
  • reaction temperature 220 0 C
  • reaction pressure 20 kg/cm 2
  • space velocity 2000 L/kg cat/hr
  • stirring rate 200 rpm.
  • the contents of the product of the Fischer-Tropsch reaction are summarized in Table 1. The steady-state condition was obtained after around 60 hour operation and the averaged values for 10 hours at the steady- state were taken.
  • Fischer-Tropsch reaction was performed in the same manner as in Example 4, except for changing the reaction temperature to 240 0 C.
  • the contents of the product of the Fischer-Tropsch reaction are summarized in Table 1.
  • the steady-state condition was obtained after around 60 hour operation and the averaged values for 10 hours at the steady-state were taken.
  • a 0.5 wt% Ru/20 wt% Co/5 wt% ZrO 2 -Al 2 O 3 catalyst was prepared in the same manner as in Example 1, except for using cobalt nitrate (Co(NO 3 ) 2 6H 2 O) as cobalt precursor.
  • a 0.5 wt% Ru/20 wt% Co/5 wt% ZrO 2 -Al 2 O 3 catalyst was prepared in the same manner as in Example 1, except for stirring and aging for about 5 hours in slurry phase at 70 0 C while co-precipitating the cobalt component to the support.
  • the prepared catalyst had a bimodal pore structure, the specific surface area being 256 m 2 /g and the pore volume being 0.85 cmVg, particularly the volume ratio of the smaller pores to the large pores PVi/PV 2 being 0.95.
  • a 0.5 wt% Ru/20 wt% Co/5 wt% ZrO 2 -Al 2 O 3 catalyst was prepared in the same manner as in Example 1, except for stirring and aging for about 10 hours in slurry phase at 70 0 C while co-precipitating the cobalt component to the support.
  • a 0.5 wt% Ru/20 wt% Co/2.5 wt% ZrO 2 -Al 2 O 3 catalyst was prepared in the same manner as in Example 1, except for using 5.4 g of zirconium nitrate (ZrO(NO 3 ) 2 2H 2 O; Kanto Chem.) as zirconium precursor.
  • zirconium nitrate ZrO(NO 3 ) 2 2H 2 O; Kanto Chem.
  • a 0.5 wt% Ru/20 wt% Co/10 wt% ZrO 2 -Al 2 O 3 catalyst was prepared in the same manner as in Example 1, except for using 21.6 g of zirconium nitrate (ZrO(NO 3 ) 2 2H 2 O; Kanto Chem.) as zirconium precursor.
  • the prepared catalyst had a unimodal pore structure, the specific surface area being 227 m 2 /g and the pore volume being 0.68 cmVg.
  • a 0.5 wt% Ru/20 wt% Co/5 wt% Zr/ Al 2 O 3 catalyst was prepared in the same manner as in Example 1, except for using zirconium oxychloride (ZrCl 2 O 8H 2 O), cobalt nitrate (Co(NO 3 ) 2 6H 2 O) and ruthenium nitrosyl nitrate (Ru(NO)(NO 3 ) 3 ) and supporting the components on an alumina support through impregnation.
  • the prepared catalyst had a unimodal pore structure, the specific surface area being 187 m 2 /g and the pore volume being 0.23 cm 3 /g.
  • a 0.5 wt% Ru/20 wt% Co/5 wt% Zr/ Al 2 O 3 catalyst was prepared in the same manner as in Example 1, except for using zirconium nitrate (Zr(NO 3 ) 2 2H 2 O), cobalt acetate (Co(CH 3 COOMH 2 O) and ruthenium nitrosyl nitrate (Ru(NO) (NO 3 ) 3 ) and supporting the components on an alumina support through impregnation.
  • the cobalt/zirconia-alumina catalysts prepared in accordance with the present invention have a bimodal pore structure of larger and small pores.
  • Example 1 the method of Example 1 by which the cobalt component is introduced to the support slurry by co-precipitation increases the specific surface area and improves the selectivity for liquid hydrocarbons than the method of Example 2 by which the catalyst prepared simply by co-precipitation is mixed in slurry phase.
  • Example 1 in which zirconia was further supported to improve dispersion and reducing property of cobalt, showed better activity than that of Example 3, in which the zirconia component was not added.
  • the catalytic performance resulting from the bimodal pore structure is more prominent in the slurry reactor, as seen in Examples 4 and 5, because the reactor type is more advantageous in matter- and heat transfer.
  • Figure 1 shows the conversion of carbon monoxide with reaction time after performing Fischer- Tropsch using the catalyst of the present invention (Example 1, 0.5 wt% Ru/20 wt% Co/5 wt% ZrO 2 -Al 2 O 3 ) and the catalyst prepared in Comparative Example 1 (20 wt% Co/80 wt% Al 2 O 3 ). It can be seen that initial conversion is superior and that, as also can be seen from Table 1, selectivity for liquid hydrocarbons is superior at similar conversion.
  • Figure 2 shows the pore distribution of the catalyst of the present invention (Example 1, 0.5 wt% Ru/20 wt% Co/5 wt% ZrO 2 -Al 2 O 3 ; Example 3, 20 wt% Co/5 wt% ZrO 2 -Al 2 O 3 ), as compared with those of Comparative Example 1 (20 wt% Co/Al 2 O 3 ) and Comparative Example 2 (0.5 wt% Ru/20 wt% Co/5 wt% Zr/Al 2 O 3 ).
  • the catalysts of the Examples have a bimodal pore structure and thus provide superior selectivity for liquid hydrocarbons because of superior thermal- and matter transfer performance.
  • Example 1 (Example 1, 0.5 wt% Ru/20 wt% Co/5 wt% ZrO 2 -Al 2 O 3 ). It can be seen that the nano- sized particulate cobalt component is uniformly distributed on the planar zirconia- alumina support.
  • the cobalt-supported zirconia- alumina catalyst having a bimodal pore structure provided by the present invention has improved the catalytic stability through improved transfer of compounds having a high boiling point and offers significantly improved Fischer- Tropsch reaction performance by minimizing transition to methane.
  • the catalyst of the present invention can be applied in any of the fixed bed reactor, fluidized bed reactor or slurry reactor to prepare liquid hydrocarbons from a syngas, the slurry reactor which is particularly advantageous in matter transfer offers the best result.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • General Chemical & Material Sciences (AREA)
  • Catalysts (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

La présente invention concerne un catalyseur à base de cobalt/zircone-aluminium dans lequel le cobalt est supporté sous forme d'un ingrédient actif sur le zircone-aluminium obtenu par co-précipitation, ce catalyseur ayant une structure de pores bimodale avec différentes grosseurs de pores et conservant un rapport volumique de pore spécifique. L'invention concerne également un procédé de préparation d'hydrocarbures liquides à rendement élevé à partir de la synthèse de Fischer-Tropsch d'un gaz synthétique (CO/H2/CO2 ) en présence du catalyseur de cobalt/zircone-aluminium.
PCT/KR2008/000547 2007-05-29 2008-01-30 Procédés de préparation d'hydrocarbures liquides à partir de gaz synthétique à l'aide de catalyseurs fischer-tropsch à base d'oxyde de zirconium et d'aluminium Ceased WO2008147013A2 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP08705003A EP2152413A2 (fr) 2007-05-29 2008-01-30 Procédés de préparation d'hydrocarbures liquides à partir de gaz synthétique à l'aide de catalyseurs fischer-tropsch à base d'oxyde de zirconium et d'aluminium

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR1020070052243A KR100837377B1 (ko) 2007-05-29 2007-05-29 지르코니아와 알루미나의 혼합담체를 이용한 피셔-트롭쉬 반응용 촉매 및 이를 이용한 합성가스로부터 액체탄화수소의 제조방법
KR10-2007-0052243 2007-05-29

Publications (2)

Publication Number Publication Date
WO2008147013A2 true WO2008147013A2 (fr) 2008-12-04
WO2008147013A3 WO2008147013A3 (fr) 2009-03-26

Family

ID=39771004

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/KR2008/000547 Ceased WO2008147013A2 (fr) 2007-05-29 2008-01-30 Procédés de préparation d'hydrocarbures liquides à partir de gaz synthétique à l'aide de catalyseurs fischer-tropsch à base d'oxyde de zirconium et d'aluminium

Country Status (3)

Country Link
EP (1) EP2152413A2 (fr)
KR (1) KR100837377B1 (fr)
WO (1) WO2008147013A2 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014534068A (ja) * 2011-11-24 2014-12-18 武▲漢凱▼迪工程技▲術▼研究▲総▼院有限公司 多孔質材料閉じ込め系のコバルト系フィッシャー・トロプシュ合成ナノ触媒とその調整方法
JP2017516734A (ja) * 2014-03-17 2017-06-22 Cqv株式会社Cqv Co., Ltd. 板状酸化アルミニウムおよびその製造方法
EP3456411A4 (fr) * 2016-05-12 2019-12-18 Fujian Institute Of Research On The Structure Of Matter, Chinese Academy Of Sciences Catalyseur, son procédé de préparation et son application dans la préparation de gaz de synthèse
CN116943662A (zh) * 2023-06-13 2023-10-27 北京海望氢能科技有限公司 一种非均相催化剂及其制备方法与应用

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101469183B1 (ko) * 2013-08-23 2014-12-10 한국화학연구원 촉매활성 성분이 지지체에 담지된 촉매의 제조방법
CN104226315B (zh) * 2014-09-30 2017-01-11 厦门大学 一氧化碳加氢制混合烃的Co基催化剂及其制备方法
CN113117683A (zh) * 2021-04-16 2021-07-16 郑州大学 负载型催化剂及其制备方法

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4619910A (en) * 1985-06-05 1986-10-28 Air Products And Chemicals, Inc. Catalyst for selective conversion of synthesis gas and method of making the catalyst
JP2859270B2 (ja) * 1987-06-11 1999-02-17 旭光学工業株式会社 カメラの視線方向検出装置
US4799077A (en) * 1987-11-23 1989-01-17 Polaroid Corporation Common drive for shutter blades and objective lens assembly
US7541310B2 (en) 2003-10-16 2009-06-02 Conocophillips Company Silica-alumina catalyst support, catalysts made therefrom and methods of making and using same

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014534068A (ja) * 2011-11-24 2014-12-18 武▲漢凱▼迪工程技▲術▼研究▲総▼院有限公司 多孔質材料閉じ込め系のコバルト系フィッシャー・トロプシュ合成ナノ触媒とその調整方法
JP2017516734A (ja) * 2014-03-17 2017-06-22 Cqv株式会社Cqv Co., Ltd. 板状酸化アルミニウムおよびその製造方法
EP3456411A4 (fr) * 2016-05-12 2019-12-18 Fujian Institute Of Research On The Structure Of Matter, Chinese Academy Of Sciences Catalyseur, son procédé de préparation et son application dans la préparation de gaz de synthèse
US11104575B2 (en) 2016-05-12 2021-08-31 Fujian Institute Of Research On The Structure Of Matter, Chinese Academy Of Science Nanocatalysts, preparation methods and applications for reforming carbon dioxide and methane to syngas
CN116943662A (zh) * 2023-06-13 2023-10-27 北京海望氢能科技有限公司 一种非均相催化剂及其制备方法与应用
CN116943662B (zh) * 2023-06-13 2024-02-20 北京海望氢能科技有限公司 一种非均相催化剂及其制备方法与应用

Also Published As

Publication number Publication date
KR100837377B1 (ko) 2008-06-12
WO2008147013A3 (fr) 2009-03-26
EP2152413A2 (fr) 2010-02-17

Similar Documents

Publication Publication Date Title
EP2173481B1 (fr) Catalyseurs à base de phosphore-oxyde d'aluminium/cobalt, leurs procédés de préparation et leur utilisation pour la synthèse de fischer-tropsch
EP2490989B1 (fr) Production d'oléfines inférieures à partir de gaz de synthèse
KR101026536B1 (ko) 피셔-트롭쉬 합성 반응용 철계열의 촉매와 이의 제조방법
AU2009229706B2 (en) Cobalt/zirconium-phosphorus/silica catalyst for Fischer-Tropsch synthesis and method of preparing the same
US8598066B2 (en) Preparing phosphorus containing alumina support by sol-gel method for fischer-tropsch synthesis and catalyst preparation thereof
EP2197816A2 (fr) Procédé de synthèse directe d'hydrocarbures légers à partir de gaz naturel
KR101829917B1 (ko) 피셔-트롭쉬 합성 반응용 메조 기공 구조의 주골격을 갖는 코발트계 촉매 및 이의 제조방법
EP2152413A2 (fr) Procédés de préparation d'hydrocarbures liquides à partir de gaz synthétique à l'aide de catalyseurs fischer-tropsch à base d'oxyde de zirconium et d'aluminium
KR100830719B1 (ko) 알루미나-실리카 담체와, 이를 함유한 촉매 및 상기 촉매를이용한 합성가스로부터 액체탄화수소 제조방법
CN101098752A (zh) 用于费托合成的钴基催化剂
AU2009297335B2 (en) Preparation methods for liquid hydrocarbons by Fischer-Tropsch synthesis through slurry reaction
CA2509230A1 (fr) Masse catalytique resistant a l'usure et ses procedes de fabrication et d'utilisation
KR102114538B1 (ko) 규칙적인 메조다공성의 주골격을 갖는 피셔-트롭쉬 합성 반응용 코발트-철 하이브리드 촉매, 이의 제조방법 및 이를 이용한 탄화수소의 제조방법
JP4118503B2 (ja) 二酸化炭素共存下の炭化水素類の製造方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 08705003

Country of ref document: EP

Kind code of ref document: A2

NENP Non-entry into the national phase

Ref country code: DE

WWE Wipo information: entry into national phase

Ref document number: 2008705003

Country of ref document: EP