WO2014007598A1 - Catalyseur hybride pour une réaction de synthèse de fischer-tropsch et procédé de synthèse de fischer-tropsch l'utilisant - Google Patents

Catalyseur hybride pour une réaction de synthèse de fischer-tropsch et procédé de synthèse de fischer-tropsch l'utilisant Download PDF

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WO2014007598A1
WO2014007598A1 PCT/KR2013/006067 KR2013006067W WO2014007598A1 WO 2014007598 A1 WO2014007598 A1 WO 2014007598A1 KR 2013006067 W KR2013006067 W KR 2013006067W WO 2014007598 A1 WO2014007598 A1 WO 2014007598A1
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synthesis
catalyst
zsm5
zeolite
coz
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Korean (ko)
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하경수
강석환
김진호
류재홍
전기원
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한국화학연구원
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • 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
    • B01J23/8933—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 also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/894—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 also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • 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
    • B01J37/031—Precipitation
    • B01J37/035—Precipitation on carriers
    • 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
    • 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
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/60—Synthesis on support
    • B01J2229/64—Synthesis on support in or on refractory materials
    • 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
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/60—Synthesis on support
    • B01J2229/66—Synthesis on support on metal supports

Definitions

  • the present invention relates to a Fischer-Tropsch synthesis hybrid catalyst for directly producing intermediate oils from syngas and a Fischer-Tropsch synthesis reaction process using the same.
  • zeolites collectively refer to crystalline aluminosilicate. Since the site of aluminum in the skeleton of the aluminosilicate is negatively charged, cations for the charge offset exist in the pores and the remaining space in the pores is usually filled with water molecules. The structure, shape, and size of the three-dimensional pores of the zeolite depend on the type of zeolite, but the diameter of the pores usually corresponds to the molecular size. Therefore, zeolites are also called molecular sieves because they have the size selectivity or shape selectivity of the molecules to be taken into the pores depending on the kind.
  • zeotype molecular sieves are known in which a part or all of silicon or aluminum is replaced by various other elements instead of silicon (Si) and aluminum (Al), which constitute the skeletal structure of the zeolite.
  • porous silica sicalite
  • AlPO 4 alpo
  • Ti, Mn, Co, Fe in the skeleton of such zeolite and pseudomolecular sieves
  • pseudomolecules obtained by partially substituting various metal elements such as Zn.
  • zeolites materials derived from zeolites and, according to their original mineralogy, do not belong to zeolites, but all of them are called zeolites in the art. Accordingly, the term zeolite in the present specification means a zeolite having a broad meaning including the above-described pseudomolecular body.
  • zeolites having an MFI structure are among the most actively used zeolites, and their kinds are as follows:
  • ZSM-5 A zeolite of MFI structure in which silicon and aluminum are formed in a constant ratio.
  • Silicalite-1 Zeolite having a structure composed only of silica.
  • TS-1 Zeolite of MFI structure with titanium (Ti) in some aluminum spots.
  • the MFI structure is shown in FIG.
  • a channel connected in a zigzag form with oval (0.51 x 0.55 nm) pores flows in the a-axis direction, and pores close to a circle (0.54 x 0.56 nm) form a straight line and extend in the b-axis direction to form a straight channel.
  • the channel is not open in the c-axis direction.
  • the shape, size and channel structure of the pores differ depending on the crystal direction.
  • GTL processes using natural gas, particularly stranded gases or associated gases, have recently attracted attention as another method for synthesizing clean fuels and compounds due to the rapid depletion of crude oil.
  • Conversion of syngas to synthetic fuel via FT synthesis is one of the most promising ways to solve this problem.
  • the main products of the FT synthesis reaction are clean diesel, gasoline, food grade paraffin, and special lubricants, which are continuous upgrade processes such as hydrocracking, hydrodewaxing, or isomerization. Can be obtained through.
  • the polymerisation mechanism represented by the Anderson-Schulz-Flory (ASF) distribution produces a wide range of hydrocarbons, from CH 4 to high molecular weight hydrocarbons.
  • product distribution is described by the possibility of chain growth, and chain growth mechanisms can be performed through various pathways such as CH 2 insertion or CO insertion.
  • the CH 2 insertion mechanism causes CC coupling by polymerisation of CH 2 intermediates on the catalyst surface to form higher molecular weight hydrocarbons. It is known that the selectivity of gasoline and heavy hydrocarbons is limited to a maximum of 48 mol%.
  • synthetic oils can be obtained through the Fischer-Tropsch reaction after converting the coal or biomass gas containing carbon containing a large amount of carbon or the reforming of natural gas into a synthesis gas containing mostly carbon monoxide and hydrogen. .
  • Fischer-Tropsch synthesis (FTS) reaction is a reaction for generating hydrocarbon compounds from syngas and is performed by the following main representative reactions on iron-based and cobalt-based catalysts.
  • Such a Fischer-Tropsch synthesis process can be produced with various products depending on the composition of the synthesis gas and the catalyst used.
  • a Fischer-Tropsch synthesis process is performed using a synthesis gas having a H 2 / CO ratio of 2 or more
  • Many hydrocarbons are produced and gasoline (C 5 -C 11 ), diesel (C 12 -C 18 ), wax (C 24 or more) and the like are produced using a synthesis gas having a H 2 / CO ratio of 2 or less.
  • reactors for Fischer-Tropsch synthesis there are three types of reactors for Fischer-Tropsch synthesis, a fixed bed reactor, a slurry bubble column reactor (SBCR), and a fluidized bed reactor.
  • Commercially available reactors are mainly composed of fixed bed reactors and slurry bubble column reactors.
  • FIG. 10 A typical process for preparing synthetic oil is shown in FIG. 10.
  • Coal or biomass (1) is reacted with oxygen (3) in the gasifier (2) to produce a synthesis gas mainly composed of carbon monoxide and hydrogen, dust collection (4), water gas conversion (5), removes carbon dioxide and sulfur compounds
  • Synthetic oil (9) is produced in the FT synthesis process (7) after the acid gas removal process (6).
  • This synthetic oil 9 is reformed and sold as a gaseous fuel / intermediate fraction 10 through the upgrading process 8.
  • Such a process is known as coal to liquids (CTL).
  • the natural gas 11 reacts with steam (H 2 O) or steam + carbon dioxide (H 2 O / CO 2 ) in the reforming reactor 12 after the odorant is removed, and produces a synthesis gas (FT synthesis process ( 7) produces a synthetic oil (9).
  • This synthetic oil 9 is reformed and sold as a gaseous fuel / intermediate fraction 10 through the upgrading process 8.
  • Such a process is known as gas to liquids (GTL).
  • Cracking catalyst unlike FT synthesis catalyst can be prepared by using the following support.
  • Amorphous oxide HFTreated Al 2 O 3 , SiO 2 -Al 2 O 3 , ZrO 2 / SO 4 2-
  • Zeolites Y, beta, mordenite, ZSM-5, ZSM-22
  • the cracking catalyst may be prepared by impregnating a metal such as Pt, Pd, and bimetallic systems (Ni / Co, Ni / W, Ni / Mo, W / Mo) on the support.
  • a metal such as Pt, Pd, and bimetallic systems (Ni / Co, Ni / W, Ni / Mo, W / Mo) on the support.
  • FT synthesis reaction of syngas is generally classified into 260 ⁇ 280 °C (LTFT) and 300 ⁇ 350 °C (HTFT) according to the operating temperature for iron catalyst above 20 atm pressure, and 220 ⁇ 240 for cobalt catalyst. It is operated at °C.
  • the wax produced is then converted to liquid fuel by a cracking catalyst under conditions such as 360 to 396 ° C. and ⁇ 69 atm (SRI report, 2006).
  • the FT synthesis reaction and cracking process are difficult to operate in a sequential continuous process because the operating temperature or pressure is different, and the preheating and supply system of the wax must be established to operate at a higher pressure than the FT synthesis process.
  • the inventors of the present invention have attempted to develop a hybrid catalyst for FT synthesis that can improve the productivity of the intermediate fraction, while simplifying the overall process in which the cracking process or the upgrading process is omitted.
  • Zeolite and Supported Cobalt System For catalyst structures of specific structure with catalyst, CH 4 Medium fraction (C 5 -C 22 The present invention was completed by confirming the effect of greatly improving the selectivity and / or yield of.
  • Another object of the present invention is to provide a method for producing an intermediate oil directly from syngas using the hybrid catalyst.
  • FT Fischer-Tropsch
  • the present invention provides a method for producing intermediate oil directly from syngas using the hybrid catalyst for FT synthesis according to the present invention.
  • the Fischer-Tropsch (FT) process currently has two major problems with gasoline production. First of all, the selectivity of gasoline (C 5 to C 11 ) is theoretically limited, with linear olefins and paraffins being inadequate for use as energy sources. Gasoline produced through the FT process can be converted to isoparaffins and aromatic compounds using acid and Pt catalysts by further processes to increase the octane number.
  • the giant paraffins produced by the FT process are modified using Pt-based catalysts.
  • Pt-based catalysts many metal catalysts such as Ni, Co, Fe, Zn, and La have been applied to isomerization by many research groups, the selectivity of isoparaffin and aromatic compounds of Pt catalyst is reported to be the best.
  • Pt is mainly used around 1% of zeolite or amorphous alumina. In this catalyst, hydrogenation ability, dehydrogenation ability of metal, acid number of carrier, pore size and geometrical form are also important factors.
  • Fe and Co-based catalysts exhibit high activity as catalysts used to directly produce high-octane gasoline by the FT process.
  • a catalyst for improving the octane number of gasoline Fe and Co series catalysts are hybridized with a zeolite (ZSM-5) catalyst having a strong Bronsted acid point to directly generate a high octane hydrocarbon compound from the synthesis gas.
  • ZSM-5 catalyst zeolite
  • hybrid catalyst it is meant that the catalysts are not physically produced by chemical bonding in the process of preparing the catalysts, but are simply physically mixed after each catalyst is prepared. In the case of the hybrid catalyst, the bifunctionality of the catalyst can be expected at the same time, and the process can be simplified in the production of gasoline of high octane number.
  • Catalyst performance could be altered primarily by varying the acidity and reducibility of cobalt oxides on ZSM5-modified Co / SiO 2 catalysts. This is because the degree of olefin cracking reaction is different when the degree of migration of cobalt oxide from SiO 2 to ZSM5 surface is different.
  • ZSM5-modified Co / SiO 2 catalysts with 25 wt% ZSM5 have high CO conversion and C 5 to C because they have a small cobalt crystal size with high reducibility and optimal acid site density. 22 shows the maximum selectivity for hydrocarbons.
  • the good catalytic performance on ZSM5-modified Co / SiO 2 catalysts is mainly due to the modification of the presence of ZSM5 particles adjacent to the Co / SiO 2 surface and the migration of cobalt species from SiO 2 to the ZSM5 surface during hydrothermal synthesis of ZSM5. It confirmed that it did.
  • the present invention is based on this.
  • the present invention relates to a hybrid catalyst for Fischer-Tropsch (FT) synthesis formed by hydrothermally synthesizing zeolite on a porous support loaded with cobalt oxide, wherein the porous support (weight ratio) of zeolite / cobalt oxide is 0.25 to 0.5. Is characteristic. At this time, the porous support (weight ratio) on which the zeolite / cobalt oxide is supported is preferably within a range of 0.25 ⁇ 0.1.
  • catalyst performance can be altered.
  • the Co / porous support surface is characterized in that it is not completely covered by zeolite. As the zeolite content increases, the mesopores of the Co / porous support catalyst are blocked by the zeolite particles, thereby reducing the surface area and pore volume of the catalyst.
  • the hybrid catalyst for FT synthesis according to the present invention may be one in which some or all of the cobalt oxide is transferred from the porous support to the zeolite surface during hydrothermal synthesis of the zeolite on the porous support (Co / porous support) on which the cobalt oxide is supported.
  • the cobalt oxide transferred to the zeolite surface on the porous support during hydrothermal synthesis is preferably exposed to the surface in contact with the zeolite particles (see FIG. 9).
  • the degree of cobalt oxide migration from the Co / porous support to the zeolite surface increases with increasing zeolite content.
  • the fine crystal size of Co 3 O 4 increases as the zeolite / (Co / porous support) ratio increases.
  • the cobalt crystal average particle diameter of the cobalt oxide migrated from the porous support to the zeolite surface during hydrothermal synthesis is preferably from 15 to 20 nm in order to exhibit high reducibility.
  • Hybrid catalysts for FT synthesis according to the present invention include those in which some or all of the cobalt oxide is reduced to cobalt metal. That is, the cobalt based catalyst may be cobalt metal or cobalt oxide.
  • the hybrid catalyst for FT synthesis according to the present invention can exhibit catalytic activity against FT synthesis reaction and olefin cracking reaction. Therefore, the hybrid catalyst for FT synthesis according to the present invention can omit the cracking process or the upgrading process and can greatly improve the selectivity and yield of the intermediate fractions (C 5 to C 22 ).
  • the catalyst according to the invention is well dispersed, with zeolite particles adjacent contacting cobalt oxide on the surface of the Co / porous support during in situ hydrothermal synthesis, the olefins of the FTS products on the zeolite surface even at low temperatures Cracking reactions can occur, which is advantageous for obtaining high selectivity for gasoline and middle distillate range hydrocarbons.
  • Cobalt catalysts are more expensive than iron catalysts and have a higher selectivity of methane at higher temperatures, but have the advantages of high activity, long lifetime, and little WGS (water gas shift reaction), resulting in low carbon dioxide generation.
  • a support having a high specific surface area may be selected or an accelerator may be used to increase dispersion of the active metal.
  • the size of the porous support is preferably a specific surface area of 100 to 400 m 2 / g.
  • Preferred examples of the porous support are porous silica (SiO 2 ) (silicalite).
  • Co is preferably 5 to 40 parts by weight based on 100 parts by weight of the porous support.
  • zeolite refers not only to (i) a generic term for minerals that are aluminum silicate hydrates of alkali or alkaline earth metals, but also to (ii) a variety of alternatives to silicon (Si) and aluminum (Al), It also includes zeotype molecular sieves that have replaced some or all of silicon or aluminum as an element, and in the larger sense includes all porous oxides or sulfides having hydroxyl groups on the surface.
  • zeolite or pseudomolecular sieves of MFI structure examples include ZSM-5, silicalite, TS-1, AZ-1, Bor-C, Boralite C, encilite, FZ-1, LZ-105, monoclinic H-ZSM -5, mutinite, NU-4, NU-5, TSZ, TSZ-III, TZ-01, USC-4, USI-108, ZBH, ZKQ-1B and the like.
  • the zeolite is preferably ZSM-5, ⁇ -zeolite, MCM, SBA, Morsenite, SAPO, Ferrierite, or the like.
  • a porous support on which cobalt oxide is supported may be prepared by impregnating a cobalt precursor in a porous support and then firing.
  • Co precursors are the metal itself, oxides (eg alumina), hydroxides (eg aluminum hydroxide), oxyhydroxides, nitrates, chlorides, carbonates, acetates, oxalates, citrates, or mixtures thereof.
  • the cobalt precursor may be selected from one or two or more selected from the group consisting of cobalt metal, cobalt nitrate, cobalt acetate, cobalt bromide, cobalt chloride, and cobalt iodide.
  • an initial wetness impregnation method may be used.
  • a synthetic gel a gel to which a structure directing agent or an organic template is added is usually used.
  • the structure inducing agent is a material that serves as a template of a specific crystalline structure, and the charge distribution, size, and geometric shape of the structure inducing agent provide structure directing properties.
  • the structural inducing agent may be an amine, an imine or a quaternary ammonium salt, preferably a quaternary ammonium hydroxide or an oligomer thereof.
  • structure inducing agents are tetraproplyammonium hydroxide (TPAOH), tetraethylammonium hydroxide (TEAOH), tetramethylammonium (TMA), tetrabutylammonium (TBA) or mixtures thereof.
  • the solvent of the gel for zeolite synthesis may be water or an organic solvent or a mixture thereof.
  • the gel for zeolite synthesis may include the following raw materials:
  • Aluminum (Al) as an raw material an organic-inorganic hybrid material in which an organic material is bonded to aluminum such as aluminum isopropoxide, a salt form material containing Al such as aluminum sulfate, or powder form of Al only Metallic material in the form of agglomerates and all materials of aluminum oxide such as alumina.
  • organic inorganic hybrid materials in which organic matter is bonded to silicon such as TEOS (tetraethyl orthosilicate), salt form material containing Si element such as sodium silicalite, powder form or lump form made of Si only Material with, all materials of silicon oxide such as glass powder, and quartz.
  • TEOS tetraethyl orthosilicate
  • salt form material containing Si element such as sodium silicalite
  • powder form or lump form made of Si only Material with, all materials of silicon oxide such as glass powder, and quartz.
  • F raw material such as HF, NH4F, NaF, KF, etc.
  • the gel formation temperature for zeolite synthesis is 50 degreeC or more.
  • the reaction temperature for the zeolite hydrothermal synthesis may vary from 50 °C to 250 °C depending on the composition of the synthetic gel used or the material to be made.
  • the reaction temperature is 80 degreeC-200 degreeC, More preferably, it is 120 degreeC-180 degreeC.
  • the reaction temperature is not always fixed, but may react with varying temperatures in several steps.
  • the reaction time can vary from 0.5 hours to 20 days.
  • the reaction time is preferably 2 hours to 15 days, more preferably 6 hours to 2 days, and most preferably 10 hours to 1 day.
  • the porous support on which cobalt oxide is supported further supports a metal selected from Ru, Pt, and La.
  • the at least one metal element selected from Ru, Pt, and La based on 100 parts by weight of the porous support is preferably 0.1 to 5 parts by weight.
  • the porous support on which the oxide of the metal element is supported may be prepared by impregnating the metal element-containing compound in the porous support and then firing.
  • metal element-containing compound selected from Ru, Pt and La include metals themselves, oxides (e.g., alumina), hydroxides (e.g., aluminum hydroxide), oxyhydroxides, nitrates, chlorides, carbonates, acetates, oxalates, citrates, Or mixtures thereof.
  • the present invention experiments, hydrothermal synthesis of zeolite particles, which are catalysts used in cracking or upgrading processes, on the surface of a cobalt-based catalyst for FT synthesis and a porous support on which oxides of metals selected from Ru, Pt, and La are supported.
  • zeolite particles which are catalysts used in cracking or upgrading processes
  • a porous support on which oxides of metals selected from Ru, Pt, and La are supported.
  • Unreacted CO not converted to CO can be recycled to participate in FT synthesis. 2 It is important to suppress the production of it.
  • the zeolite on the surface of the cobalt-based catalyst supported on the support When the particles are synthesized in a structure similar to that of ZSM-5, the product of the intrinsic fraction produced by the chain growth may simultaneously crack on the zeolite particles, thereby increasing the selectivity of the middle fraction.
  • the hybrid catalyst for FT synthesis according to the present invention may be used in a Fischer-Tropsch synthesis reaction process for directly producing intermediate oil in a synthesis gas, but is not limited thereto.
  • the synthesis gas (H 2 / CO) may be prepared through the gasification of turbidity or biomass or reformation of natural gas.
  • the hydrogen / carbon monoxide reaction ratio is preferably carried out while maintaining the molar ratio of 1-2.
  • the synthesis reaction using the hybrid catalyst for FT synthesis of the present invention can significantly improve the selectivity and yield of the intermediate fractions (C 5 to C 22 ) while maintaining high conversion of hydrogen gas and carbon monoxide gas.
  • the reaction for producing the intermediate oil directly from the synthesis gas using the hybrid catalyst for FT synthesis according to the present invention can be carried out in a fixed bed, fluidized bed or slurry reactor.
  • the hybrid catalyst for FT synthesis according to the present invention is preferably used in a catalytic reaction after reduction in a hydrogen atmosphere in the range of 200 to 700 ° C. When the reduction exceeds 700 °C sintering of the catalyst may proceed.
  • the reaction for producing the intermediate fraction directly from the synthesis gas using the hybrid catalyst for FT synthesis according to the present invention can be carried out under reaction conditions similar to the Fischer-Tropsch synthesis reaction.
  • the reaction temperature is 220 ⁇ 400 °C, preferably the reaction temperature lower than the temperature of the general single cracking process
  • the reaction pressure is preferably carried out at 5 ⁇ 60 kg / and the space velocity is 500 to 10000 h -1 , but It is not limited.
  • the hard hydrocarbons 14 in the C 1 to C 4 range of the final product may be recycled as shown in FIG. 12 and introduced into the reforming process 12 together with the natural gas 11 as a raw material.
  • FIG. 3 shows XPS analysis of Co2p 3/2 and Co2p 1/2 on unused ZSM5-modified Co / SiO 2 catalysts.
  • FIG. 4 shows TEM images of unused ZSM5-modified Co / SiO 2 catalysts ((a) CoZ (0.25), (b) CoZ (0.33), and (c) CoZ (0.50)].
  • FIG. 6 shows NH 3 -TPD profile of unused ZSM5-modified Co / SiO 2 catalysts.
  • FIG. 7 is a graph showing catalyst activity over time in ZSM5-modified Co / SiO 2 catalysts.
  • FIG. 8 is a graph showing catalytic performance (CO conversion and product distribution) with acid point density in ZSM5-modified Co / SiO 2 catalysts.
  • FIG. 10 is a simplified process diagram of a middle oil production process using a conventional Fischer-Tropsch synthesis reaction process.
  • FIG. 11 is a simplified process diagram of a middle oil production process using the Fischer-Tropsch synthesis reaction process according to the present invention.
  • FIG. 12 is an improvement of the process diagram of FIG. 11 to recycle C 1 -C 4 light hydrocarbons in the final product of the Fischer-Tropsch synthesis reaction to a natural gas reforming process.
  • FIG. 13 is a diagram schematically showing zeolite crystals of an MFI structure in which a structure inducing agent is inserted.
  • Co / SiO 2 and Co / ZSM5 catalysts were prepared by typical wet-impregnation using SiO 2 and ZSM5 (Si / Al ratio of 25) supports and aqueous cobalt nitrate precursors of the required composition.
  • SiO 2 Davissil grade 645, Aldrich
  • ZSM5 Zerolyst having a surface area of 350 m 2 / g were used as a support.
  • TEOS 10% aqueous TPAOH solution, ethanol, and additional water were thoroughly mixed in a 100 mL Teflon tube.
  • Al (NO 3 ) 3 .H 2 O was carefully added and stirred at 60 ° C. for 2 hours until a sol was formed according to previously known preparation methods.
  • a Co / SiO 2 catalyst was then added to the synthesized sol solution, the tube was capped, placed in a hydrothermal synthesis apparatus heated to 180 ° C. and vigorously stirred at 100 rpm for 12 hours to ensure crystallization.
  • ZSM5 was synthesized in situ on the Co / SiO 2 surface, with cobalt oxide in close contact.
  • the final ZSM5-modified Co / SiO 2 catalyst was separated from the solution and dried at 120 ° C. for 12 hours. It was then calcined at 500 ° C. for 5 hours at a heating rate of 10 ° C./min.
  • the weight ratio of ZSM5 / (Co / SiO 2 ) was varied.
  • ZSM5-modified Co / SiO 2 catalysts were denoted by CoZ (x), where Co means Co / SiO 2 and Z means ZSM5, and the different ZSM5 / (Co / SiO 2 ) weight ratios are x (e.g., 0.25, 0.33, and 0.50).
  • the final compositions of Co, SiO 2 , and ZSM5 in CoZ catalysts are listed in Table 1.
  • the surface area, pore volume, and average pore size and distribution of CoZ catalysts were measured by N 2 -adsorption using a Micromeritics ASAP 2400 apparatus at -196 ° C. Surface concentrations and oxidation states of cobalt oxide on new CoZ catalysts were characterized using XPS instrument (ESCALAB MK-II). AlK ⁇ monochromatic light (1486.6 eV) was employed during the experiment, and the vacuum level was maintained at about 10 ⁇ 7 Pa. The binding energy (BE) was corrected to the reference BE of C1s (284.4 eV).
  • Temperature reduced reduction was performed to measure the reducibility of cobalt oxides on CoZ catalysts. Prior to the TPR experiment, samples were pretreated with He fluid up to 400 ° C. and held for 2 hours to remove adsorbed water and other contaminants, then cooled to 50 ° C. A reducing gas containing a 5% H 2 / Ar mixed gas was passed through the sample at a fluid rate of 30 mL / min, heated to 800 ° C. at a heating rate of 10 ° C./min and held at 800 ° C. for 30 minutes. The acidity of the CoZ catalyst was determined by temperature-programmed desorption of ammonia (NH 3 -TPD).
  • Powder X-ray diffraction (XRD) patterns were obtained using a Rigaku diffractometer with Cu-K ⁇ radiation from which the crystalline phases and average size of cobalt oxide on the CoZ catalyst were identified.
  • Co 3 O 4 average crystallite size on the CoZ catalyst was calculated by X-ray line broadening with the aid of Scherrer's equation.
  • Table 1 relates to the physical properties of ZSM5-modified Co / SiO 2 catalysts and the microcrystalline size of Co 3 O 4 on the catalysts.
  • ZSM5 is widely used as a solid acid catalyst because of its adjustable acid site density and acid strength, and due to the regular pore structure of ZSM5, it can contribute to catalytic activity, especially for hydrocracking.
  • different ratios of ZSM 5 / (Co / SiO 2 ) on CoZ catalysts can significantly change physicochemical properties and acidity.
  • the properties of CoZ catalysts prepared by in situ hydrothermal synthesis of ZSM5 in the presence of Co / SiO 2 catalysts, such as surface area, pore volume, average pore diameter, are summarized in Table 1. These values of CoZ catalysts decreased compared to that of Co / SiO 2 catalyst.
  • the surface area of all CoZ is similar.
  • the increase in the ZSM5 content of CoZ catalysts showed a decrease in surface area (244-> 238 m 2 / g) and a decrease in pore volume (1.01-> 0.97 cm 3 / g), the average pore diameter was especially on CoZ (0.50) 8.8-> 6.0 nm. This shows that the mesopores of the Co / SiO 2 catalyst are blocked by the ZSM5 particles, thereby increasing the ZSM5 content in reducing the surface area and pore volume. As shown in FIG.
  • the pore size distribution of the CoZ catalysts shows that it is possible to block the mesopores of Co / SiO 2 during the hydrothermal synthesis of ZSM5.
  • the pore size in the 2-5 nm range on Co / ZSM5 does not change significantly with increasing Si / Al ratio, and we found that about 3 nm mesopores on CoZ catalyst are ZSM5 pores. It is believed to be related to (FIG. 1). This is also supported by a small reduction in the surface area on CoZ when compared to Co / ZSM5 having a surface area of 306 m 2 / g. Increasing the ZSM5 content decreased the average pore diameter in CoZ catalysts.
  • the decrease in surface area by increasing the ZSM5 content on the CoZ catalysts contributes to the formation of ZSM5 particles on the outer surface, as well as the formation of intergranular structures of ZSM5 with large pore sizes of 40 nm or more as well as pore blocking of Co / SiO 2 .
  • An increase may be the cause.
  • the reduction in surface area and average pore size on CoZ catalysts compared to Co / SiO 2 and Co / ZSM5 catalysts mainly results in the formation of two pore size distributions, resulting in the pore blocking of the Co / SiO 2 catalyst with ZSM5 particles.
  • the fine crystal size of Co 3 O 4 increased. That is, as summarized in Table 1, the cobalt fine crystal sizes in CoZ (0.25), CoZ (0.33), and CoZ (0.50) catalysts were 16.8, 19.2, and 23.5 nm, respectively. Interestingly, the cobalt microcrystalline size on CoZ catalysts is larger than Co / SiO 2 catalyst and smaller than Co / ZSM5 catalyst. In order to clarify the line magnification of the corresponding Co 3 O 4 peak, diffraction peaks in the range of 30 ⁇ 2 ⁇ ⁇ 45 in the CoZ catalyst are included in the insert of FIG. 2.
  • the ZSM5 particles are in adjacent contact on the Co / SiO 2 surface during in situ hydrothermal synthesis, the distribution of which may result in the olefin cracking reaction of FTS products on the ZSM5 surface even at low temperatures. This is advantageous for obtaining high selectivity for gasoline and middle distillate range hydrocarbons.
  • SEM-EDS analysis was performed on the CoZ catalysts, the results of which are summarized in Table 1. This shows the preferential presence of cobalt oxide on the CoZ catalyst surface and the content of cobalt oxide on the CoZ catalyst surface also decreases with increasing ZSM5 content (Co / Si atomic ratio changes from 0.855 to 0.128). .
  • TEM images of the CoZ catalyst support that ZSM5 lies adjacent on the Co / SiO 2 catalysts.
  • cobalt oxide was found to be about 20 nm. Dark black points correspond to cobalt oxide and gray points correspond to ZSM5 and SiO 2 supports.
  • TEM images show that ZSM5 particles are well dispersed on CoZ (0.25) with cobalt oxide in close contact on Co / SiO 2 , and that ZSM5 particles are isolated in separate phase on CoZ (0.50) catalyst. . These results support that ZSM5 is in contact with cobalt oxide at low ZSM5 content, such as CoZ (0.25) catalyst.
  • Table 2 relates to H 2 uptake measured by H 2 -TPR in ZSM 5 -modified Co / SiO 2 catalysts.
  • the reduction profile of the calcined CoZ catalysts is shown in FIG. 5, and the reduction degree was calculated by dividing the H 2 consumption from TPR to 400 ° C. by the total H 2 consumption, as summarized in Table 2.
  • the TPR profile on CoZ catalysts shows two distinct reduction peaks and was observed at better temperatures than that of Co / SiO 2 catalysts due to the possibility of cobalt oxide on SiO 2 migration to ZSM5.
  • the first reduction peak is usually by reduction of Co 3 O 4 to CoO and the second peak is by reduction of CoO to metal cobalt.
  • TPR profiles of all CoZ catalysts also show distinct shoulder peaks around 272-295 ° C., with a strong second peak at maximum temperature (T max ) near 325-341 ° C.
  • the second peak is due to the complete reduction of cobalt oxide to metal cobalt.
  • Small peak intensities in the high temperature range above 600 ° C. suggest that cobalt oxide can be converted to inert cobalt silicate on Co / SiO 2 catalysts.
  • the TPR peaks of the CoZ (0.25) catalyst appearing near 272 and 325 ° C. may be due to cobalt microcrystals that can be readily reduced to the metallic state at low temperatures. Cobalt species with a larger surface area and smaller microcrystal size were found to be characteristic of the CoZ (0.25) catalyst.
  • the fine crystal size and T max of cobalt oxide decreases from 341 ° C. to 325 ° C. as the ZSM5 content decreases in CoZ catalysts.
  • the ZSM5 support exhibits strong cobalt-supporter interaction at ZSM5 acid sites (a rather high reduction temperature near 383 ° C.). This phenomenon suggests that the cobalt oxide migration from SiO 2 to ZSM5 surface is not severe because of the low zeolite content in the CoZ (0.25) catalyst.
  • a higher reduction temperature peak near 380 ° C. in the Co / ZSM5 catalyst also supported the possibility of cobalt oxide migration from SiO 2 to the ZSM 5 surface.
  • the degree of reduction on CoZ catalysts was calculated from the H 2 consumption in TPR.
  • the total H 2 consumption (expressed as total H 2 consumption / g cat ) based on the weight of the CoZ catalyst was 2.12, 2.00, and 1.82 mmol H 2 in CoZ (0.25), CoZ (0.33), and CoZ (0.50), respectively. calculated with / g cat .
  • Co / ZSM5 as compared to (3.86 mmol H 2 / g) , and because it is of the H 2 consumption reduction for CoZ catalyst will decrease the absolute amount of the metal species, the total H 2 consumption is a ZSM5 content of at CoZ catalyst Decreased with increase.
  • This tendency is associated with an increase in the content of ion-exchanged Co 2+ species from Co / SiO 2 to ZSM5 surface or small cobalt microcrystals that are rarely reduced (even above 400 ° C.) during the hydrothermal synthesis step of the CoZ catalyst. .
  • These cobalt species can interact strongly in the backbone of the Al sites, with increasing ZSM5 / (Co / SiO 2 ), hydrogen consumption values from 7.3 to 19.9% above 400 ° C, as shown in Table 2. Increasing results and 30.6% in Co / ZSM5.
  • the H 2 consumption values (mmol H 2 / g Co ), recalculated based on cobalt weight below 400 ° C., are about the same in the range 12.1 to 14.6; However, above 400 ° C., the value gradually increases as the ZSM5 content increases. That is, 1.03, 2.85, and 3.62 mmol H 2 / g cat in CoZ (0.25), CoZ (0.33), and CoZ (0.50), respectively, and 5.91 mmol H 2 / g cat in Co / ZSM5. These observations also show the mobility of small sized cobalt species and ion exchange of cobalt species on the scattering points of the ZSM5 surface.
  • Table 3 relates to the surface acidity measured by NH3-TPD in ZSM5-modified Co / SiO 2 catalysts.
  • NH 3 -TPD experiments were performed to investigate the concentration and strength of acid sites in CoZ catalysts.
  • the acid point on the ZSM5 can act as an active site for the olefin cracking reaction of the FTS product even at low reaction temperatures.
  • the NH 3 -TPD pattern of CoZ catalysts is shown in FIG. 6. Three characteristic steps, peaks I, II and III, associated with NH 3 desorption were observed. Peak I is NH 3 desorption temperature, peak II of below 220 °C temperature of NH 3 desorption temperature, peak III at 220 ⁇ 500 °C corresponds to the NH 3 desorption temperature of at least 500 °C. Desorption peak III observed above 500 ° C.
  • the acid point density in CoZ catalysts as NH 3 / gcat as weak and strong acid points. Considering the first peak (weak acid point) and the second peak (strong acid point), which can be active sites for the olefin cracking reaction, we found that the acid point density is higher due to the increased ZSM5 content in the CoZ (0.50) catalyst. .
  • the total scattering density (sum of peaks I and II) varies in the order of CoZ (0.50)> CoZ (0.33)> CoZ (0.25).
  • the acid point density also increases proportionally.
  • the weak and strong acid point density for peaks I and II in NH 3 -TPD was significantly reduced by the addition of cobalt species by acid point blocking on ZSM5 (0.743 of bare ZSM5, 0.450 on Co / ZSM5 catalyst). mmol NH 3 / g).
  • Table 4 is the catalytic performance for the ZSM5-modified Co / SiO 2 catalyst.
  • CO conversion decreases proportionally with increasing ZSM5 / (Co / SiO 2 ) weight ratio, and the trend is related to the fine crystal size of cobalt oxide and its reducing capacity as shown in Table 1.
  • catalysts having a large surface area and large pore diameters are advantageous for obtaining small cobalt microcrystalline size and can easily transport heavy chain hydrocarbons formed during the FTS reaction. It has been suggested that the large pores on the FTS catalyst are linked to less coke or wax deposition.
  • the high content of weak acid sites is associated with high yields of C 5 to C 22 hydrocarbons due to the cracking of the polymer olefins at the acid sites of the zeolites.
  • a composite catalyst in which Co / SiO 2 and ZSM5 are physically mixed cannot be a good catalyst for improving C 5 to C 22 hydrocarbon selectivity.
  • the iron-based FTS catalyst physically mixed with ZSM5 showed high by-product selectivity and low selectivity of olefin hydrocarbons.
  • lower olefin production rates in cobalt based catalysts than iron based catalysts are associated with low cracking catalyst activity of the olefin components causing small changes in product distribution.
  • the CoZ catalyst showed safe catalytic activity at about 40 hours compared to Co / SiO 2 and Co / ZSM5, showing high selectivity for heavy hydrocarbons and low selectivity for CH 4 and CO 2 .
  • CO conversion from CoZ catalyst to heavy hydrocarbons is 82.8% for all FTS catalysts.
  • CO conversion to CO 2 is proportional to CO conversion by the water gas shift reaction. In addition, they decrease with decreasing Co / SiO 2 content in the CoZ catalyst.
  • TOF values are reported to range from 1.6 ⁇ 10 ⁇ 3 to 3.0 ⁇ 10 ⁇ 3 / s on cobalt nanofine crystal phases having approximately 10 nm size.
  • the CO conversion in the CoZ catalyst is somewhat lower than that of the Co / SiO 2 catalyst due to the blocking of active cobalt sites due to the deposition of ZSM5, the yields of C 5 to C 22 hydrocarbons in the CoZ catalyst change significantly and the low CH 4 selectivity Was observed.
  • CoZ (0.25) catalysts show high values of CO conversion and high yields of C 5 to C 22 hydrocarbons. Due to the low content of ZSM5, which indicates low acid density, the CoZ (0.25) catalyst shows low CH 4 selectivity of about 7.8% and C 2 -C 4 hydrocarbons of about 9.2%. The CoZ (0.25) C 5 ⁇ C 22 hydrocarbons, up to the selection of even lower olefin selected from the catalyst and from about 62.8% Fig. (C 5 ⁇ C 22 hydrocarbons yield 49.1%) was observed.
  • CoZ (0.50) catalysts show the highest CH 4 selectivity of 11.3% and C 2 -C 4 hydrocarbons of 13.4%. CH 4 and C 2 -C 4 selectivity increase with increasing ZSM5 content. This is because the acid point of ZSM5 plays an important role as a catalyst in cracking reaction from olefin hydrocarbon to light hydrocarbon even at low temperature.
  • the acid point of ZSM5 is also related to the content of aluminum forming the backbone, which is related to the high selectivity of the olefin hydrocarbons.
  • Cobalt oxide microcrystals or ion exchanged Co 2+ species on CoZ catalysts may also be due to strong interactions with aluminum forming the backbone. This is supported by the CoZ (0.50) catalyst showing high olefin selectivity (expressed as O / (O + P)) of about 32.1% at 240 ° C.
  • CoZ catalyst with an optimal content of ZSM 5 in close contact with cobalt on Co / SiO 2 phase, such as CoZ (0.25), is formed on the ZSM5 support. It is better to simply impregnate Co at.
  • Catalytic performance parameters such as CO conversion and product distribution for acid point density on CoZ catalysts are summarized in FIG. 8. CO conversion decreased with increasing ZSM5 content on the CoZ catalyst due to the low Co / SiO 2 content. High C 5 -C 22 hydrocarbon selectivity was observed in the CoZ (0.25) catalyst.
  • a schematic diagram of Co / SiO 2 modified with ZSM5 is shown in FIG. 9.
  • CoZ (0.25) catalysts allows cobalt microcrystals to migrate from Co / SiO 2 to the acidic point of ZSM5 during hydrothermal synthesis, resulting in small microcrystalline size in close contact with the weak acidic points of ZSM5 on the Co / SiO 2 surface. Mainly related to the formation of cobalt oxide.
  • ZSM5 particles in close contact with the cobalt oxide can also improve the degree of olefin cracking reaction of the FTS product, which enhances the C 5 -C 22 hydrocarbon selectivity in the CoZ (0.25) catalyst.
  • the catalyst was prepared by hydrothermal synthesis of ZSM5 in-situ in a solution containing pre-prepared Co / SiO 2 catalyst. As a result, a maximum yield of C 5 to C 22 hydrocarbons was obtained in ZSM5-modified CoZ (0.25), which is better than Co / SiO 2 and Co / ZSM5.
  • the crystal size of the increased cobalt oxide is due to the cobalt movement to the ZSM5 surface.
  • the adjacent contact of cobalt oxide with ZSM5 is responsible for high catalytic performance. Modification of Co / SiO 2 with ZSM 5 particles during ZSM 5 hydrothermal synthesis can increase the selectivity of C 5 to C 22 hydrocarbons while minimizing C 1 to C 4 hydrocarbons.
  • the solution was dried with a commercially available silica support by stirring using a magnetic bar to mix 20 wt% of cobalt nitrate (Co (NO 3 ) 2 .6H 2 O) aqueous solution. After calcining at 500 ° C. for 5 hours, a 20 wt% Co / silica catalyst was prepared. The prepared catalyst was filtered by 20 to 40 Mesh.
  • Hybrid catalyst for Fischer-Tropsch (FT) synthesis formed by hydrothermal synthesis of zeolite on a porous support loaded with cobalt oxide
  • TPAOH tetrapropyl ammonium hydroxide solution
  • Al (NO 3 ) 3 ⁇ H 2 O (99.5%) and TEOS tetraethyl ortho silicate
  • the gel-forming composition for zeolite synthesis was prepared by sol at 50 ° C. and then mixed with 4 g of the prepared Fischer-Tropsch synthesis catalyst (Co / SiO 2 , Co-Ru / SiO 2 , Co-Pt / SiO 2 ,) 180 Hydrothermal synthesis for 10 hours at °C.
  • Example 1 Zeolite / (Co / SiO 2 ) 88.3 17.2 17.0 / 16.3 / 13.7 / 53.0 66.7 47.4 240
  • Example 2 Zeolite / (Co-Ru / SiO 2 ) a) 38.7 3.1 17.1 / 10.2 / 20.4 / 56.1 76.5 25.9 240
  • Example 3 Zeolite / (Co-Pt / SiO 2 ) b) 49.7 3.0 25.9 / 17.4 / 28.6 / 28.1 56.7 26.5 260 Comparative Example 1 Co / SiO 2 26.8 0.6 6.8 / 10.9 / 10.4 / 71.9 82.3 21.6 220 Comparative Example 2

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Abstract

La présente invention concerne un catalyseur hybride pour une synthèse de Fischer-Tropsch (FT), formé par la synthèse de façon hydrothermale de zéolites sur un échafaudage poreux à support en oxyde de cobalt, dans lequel la zéolite/échafaudage poreux à support en sur oxyde de cobalt (rapport en poids) = 0,25 à 0,5. La présente invention concerne également un procédé de préparation du catalyseur hybride. De plus, la présente invention concerne un procédé de fabrication de distillats moyens directement à partir de gaz de synthèse à l'aide du catalyseur hybride pour la synthèse FT selon la présente invention. Avec le catalyseur hybride pour une réaction de synthèse de Fischer-Tropsch selon la présente invention, des distillats moyens peuvent être directement obtenus à partir de gaz de synthèse sans un procédé de craquage ou un procédé de valorisation, et CH4 peut être sélectivement maintenu à un faible niveau et la sélectivité et le rendement des distillats moyens peuvent être améliorés.
PCT/KR2013/006067 2012-07-06 2013-07-08 Catalyseur hybride pour une réaction de synthèse de fischer-tropsch et procédé de synthèse de fischer-tropsch l'utilisant WO2014007598A1 (fr)

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KR101970811B1 (ko) * 2017-05-12 2019-04-22 한국화학연구원 메조기공 제올라이트에 담지된 피셔-트롭시 공정용 코발트 촉매 및 이를 이용한 합성액체연료 제조 방법
KR102073959B1 (ko) * 2017-12-27 2020-02-05 고등기술연구원연구조합 고발열량의 합성천연가스 합성용 촉매 및 이를 이용한 합성천연가스의 제조방법

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