WO2014119870A1 - Fischer-tropsch synthesis catalyst comprising coo phase particles and method for preparing liquid hydrocarbon from natural gas using same - Google Patents
Fischer-tropsch synthesis catalyst comprising coo phase particles and method for preparing liquid hydrocarbon from natural gas using same Download PDFInfo
- Publication number
- WO2014119870A1 WO2014119870A1 PCT/KR2014/000647 KR2014000647W WO2014119870A1 WO 2014119870 A1 WO2014119870 A1 WO 2014119870A1 KR 2014000647 W KR2014000647 W KR 2014000647W WO 2014119870 A1 WO2014119870 A1 WO 2014119870A1
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- WO
- WIPO (PCT)
- Prior art keywords
- catalyst
- fischer
- tropsch synthesis
- cobalt
- coo
- Prior art date
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- 239000003054 catalyst Substances 0.000 title claims abstract description 191
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 66
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- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
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- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
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- 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
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- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
- C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
- C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
- C10G2/33—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used
- C10G2/331—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals
- 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
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1025—Natural gas
Definitions
- the present invention relates to a separated Fischer-Tropsch (F-T) catalyst comprising CoO phase particles, a method for preparing the same, and a method for producing a liquid hydrocarbon from natural gas using the same.
- F-T Fischer-Tropsch
- the improvement of the catalyst for FT synthesis is directly connected to the improvement of the competitiveness of the GTL technology.
- the thermal efficiency and carbon utilization efficiency of the GTL process can be improved, and the FT reaction process can be optimized and designed.
- Iron and cobalt-based catalysts are mainly used for the FT reaction, but the characteristics of the cobalt-based catalysts are expensive, but they have high activity, long lifespan, and low production of CO 2 while producing low yields of liquid paraffinic hydrocarbons. It has a high advantage.
- the GTL process consists of three main processes: reforming reaction of natural gas, FT synthesis reaction of synthesis gas, and reforming reaction of product. Among them, iron and cobalt are used as catalysts, and the temperature is 200 ° C to 350 ° C.
- the reaction temperature of and the FT reaction carried out at a pressure of 10 to 30 atm can be described as four main reactions as follows.
- the catalyst for F-T synthesis is an oxide catalyst. Therefore, the reduction properties of the catalyst for F-T synthesis are one of the very important factors in determining the catalytic reaction.
- the prepared cobalt catalyst has a Co 3 O 4 phase, and undergoes a step of reducing cobalt oxide at a temperature of 300 to 500 ° C. using hydrogen before performing the FT reaction.
- the reduction process of cobalt oxide can be represented by the following two steps.
- Step 1 Co 3 O 4 + 4H 2 ⁇ 3CoO + 4H 2 0
- the catalyst produced by the above method is a catalyst oxide is formed through the calcination process. That is, it has a Co 3 O 4 phase and the catalyst has a high reduction temperature of cobalt oxide because the catalyst has a strong interaction with the support.
- Korean Patent No. 10-1015492 proposed a catalyst production method different from the existing catalyst production method. It is described that the selectivity of carbon monoxide can be controlled by controlling the size of the active ingredient particles while reducing the interaction of the support with the active material.
- the catalyst prepared by the method proposed in the patent also consists of a Co 3 O 4 phase, there was a limit to go through a two-stage reduction reaction before being used for the FT reaction.
- Important factors that determine the activity of the F-T catalyst are dispersion and reduction rate.
- the particle size is small and the dispersion degree is high, there is a problem that the stability of the F-T catalyst is low, the catalytic activity is low, and the methane production is increased.
- the particle size is too large and the reduction rate is high, the degree of dispersion is low and the activity of the catalyst is inhibited. Therefore, a catalyst having an appropriate particle size and high dispersibility and reduction rate can be said to be an excellent catalyst.
- the present inventors devised a method for preparing cobalt nanoparticles containing a CoO phase, while studying the cobalt-based catalysts with optimized activity and selectivity of liquid hydrocarbons, and supported them on a catalyst support for Fischer-Tropsch synthesis.
- the present invention exhibited excellent reduction activity and excellent dispersibility at low temperature, and showed excellent catalytic activity compared to the conventional production method, thus completing the present invention.
- the present invention is based on this.
- a method for preparing a Fischer-Tropsch synthesis catalyst including CoO phase particles comprising: reacting a cobalt feed precursor aqueous solution with an aqueous basic compound solution to form a precipitate; A second step of heating the precipitate by mixing with a capping molecule and a nonpolar organic solvent; And a third step of recovering the organic solvent layer in the mixture and heating at 230 ° C. to 350 ° C. to form CoO phase particles.
- the method may further include a fourth step of supporting the cobalt oxide particles including some or all of the CoO phase particles prepared in the previous step on the support.
- the second aspect of the present invention provides a catalyst for separated Fischer-Tropsch synthesis, which is prepared by the first aspect of the present invention, comprising CoO phase particles.
- a method for producing a liquid hydrocarbon from natural gas using a Fischer-Tropsch synthesis reaction wherein the Fischer-Tropsch synthesis catalyst prepared by the first aspect of the present invention A) applying to a synthetic reactor; B) reducing the separated Fischer-Tropsch synthesis catalyst comprising CoO phase particles to activate the Fischer-Tropsch synthesis catalyst; And c) performing Fischer-Tropsch synthesis by the activated Fischer-Tropsch synthesis catalyst.
- the existing cobalt catalyst is prepared in Co 3 O 4 phase, it must be activated to cobalt metal (Co) by reduction under high temperature hydrogen atmosphere of 300-500 ° C. after being applied to the FT reactor and before performing the FT reaction. do.
- the cobalt catalyst containing CoO phase particles can be prepared when the capped cobalt-containing organic solvent layer is heated at 230 ° C. to 350 ° C. in the preparation of cobalt oxide, and the present invention is based on this.
- Example 1-1 When the capped cobalt-containing organic solvent layer was heated at 300 ° C. (Example 1-1), all of the formed cobalt oxide nanoparticles consisted of only CoO phase. Meanwhile, when the capped cobalt-containing organic solvent layer was heated at 270 ° C. (Example 2), the content of CoO phase in the cobalt oxide nanoparticles was 70%, and when heated at 230 ° C. (Example 3), the content of CoO phase This was 30%, and when heated at 200 ° C. (Comparative Example 1), the cobalt oxide nanoparticles were all composed of Co 3 O 4 phase only.
- the present invention is characterized in that, before being applied to the F-T reactor, the catalyst active ingredient supported on the Fischer-Tropsch synthesis catalyst and / or the support is cobalt oxide particles containing some or all of CoO phase particles. Therefore, the catalyst prepared according to the present invention can be reduced and activated with hydrogen without a separate firing process. The reduction may be carried out in a hydrogen atmosphere in the temperature range of 100 °C to 500 °C after applying the catalyst to a fixed bed, fluidized bed or slurry reactor.
- the Fischer-Tropsch synthesis catalyst prepared according to the present invention exhibits high activity even at low reduction temperatures, and can suppress high conversion of carbon monoxide, stable selectivity to liquid hydrocarbons, and deactivation of the catalyst.
- "separate Fischer-Tropsch synthesis catalyst” refers to a catalyst state that can be directly synthesized and transported and / or distributed before being applied to the Fischer-Tropsch synthesis reactor, and according to the Fischer- The catalyst for Tropsch synthesis is synthesized in a CoO phase prior to application to the Fischer-Tropsch synthesis reactor, and then applied to the Fischer-Tropsch synthesis reactor, and then the precursor of CoO is fischer-Tropsch by Co reduction. It becomes a catalyst for synthesis.
- the present invention can prepare the cobalt-based catalyst component in the optimum size before the application to the FT reactor, and can be prepared by the nanoparticles containing the CoO phase and supported on the catalyst support, high dispersion degree and reduced at low temperature You can make this happen easily.
- a method for preparing a catalyst for Fischer-Tropsch synthesis including CoO phase particles may include a first step of forming a precipitate by reacting an aqueous solution of a cobalt feed precursor and an aqueous solution of a basic compound; A second step of heating the precipitate by mixing with a capping molecule and a nonpolar organic solvent; And a third step of recovering the organic solvent layer in the mixture and heating at 230 ° C. to 350 ° C. to form CoO phase particles.
- the cobalt-containing precipitate slurry obtained by washing with deionized water is mixed with a capping molecule and a non-polar organic solvent and heated to form an inorganic catalyst component. It is dissolved in an organic solvent and separated from the aqueous layer. Subsequently, the organic solvent layer may be recovered and heated at 230 ° C. to 350 ° C. to form particles containing a CoO phase. In addition, the particle size can be adjusted to the desired size at this time.
- Non-limiting examples of cobalt feed precursors in the first step include cobalt nitrate (Co (NO 3 ) 2 H 2 O), cobalt chloride (CoCl 2 H 2 O), cobalt sulfate (CoSO 4 ), cobalt acetate (Co (AC) 2 ) and mixtures thereof.
- Non-limiting examples of basic compounds in the first step include ammonia, sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide, ammonium hydroxide, ammonium carbonate, ammonium bicarbonate, sodium carbonate, sodium bicarbonate, potassium carbonate, potassium hydrogen carbonate and mixtures thereof Can be.
- Non-limiting examples of capping molecules in the second step can be saturated or unsaturated C 6 -C 30 organic acids or fatty acids. More specifically, 2-ethylhexanoic acid, stearic acid, lauric acid, linoleic acid, palmitic acid, oleic acid, multiple Acids (polyacids), derivatives thereof and the like may be used alone or in combination of two or more thereof.
- the capping molecule in the second step is preferably used in a molar ratio of 0.1 to 2.5 with respect to 1 mole of cobalt feed precursor. If it is less than 0.1 molar ratio, complete capping will not be achieved, resulting in poor dispersibility, and loss of catalyst components may remain in the aqueous solution. On the other hand, when it exceeds 2.5 molar ratio, the fluidity of the colloidal solution of the capped catalyst component may be inferior.
- the nonpolar organic solvent preferably has a melting point of less than 30 ° C. and a boiling point of 70 ° C. or more. This is to maintain a reaction temperature suitable for surface treatment.
- nonpolar organic solvents may be toluene, xylene, paraffin, 1-hexadecane and common petroleum solvents such as kerosene, light oil or heavy oil and the like.
- Preferred capping reaction temperature of the second step is preferably 40 to 110 °C. If the temperature is less than 40 ° C, the catalyst component is not completely capped, so that the catalyst component does not effectively separate from the aqueous solution layer into the organic solvent layer. If the temperature exceeds 110 ° C, the reaction temperature is higher than the boiling point of the solution, making manufacturing difficult. do.
- the preferred heating temperature range in the third step is 230 ° C to 350 ° C, more preferably 230 ° C to 300 ° C. If it is less than 230 ° C, there is a problem in that CoO is not formed and the crystallization reaction is weak so that the size of crystals produced is too small. In addition, when the temperature exceeds 350 ° C., the size of the crystal may be too large to be suitable as a nanocatalyst.
- the solution containing the CoO phase particles formed may be mixed with a polar organic solvent to precipitate and capped particles, and then redispersed to obtain cobalt oxide (CoO) particles dispersed in the organic solvent.
- a polar organic solvent used as the extraction solvent may be methanol, ethanol, acetone, acetonitrile or mixtures thereof.
- the average diameter of the CoO phase particles which may be formed according to the preparation method of the present invention may be 5 to 50 nm, more preferably 10 to 20 nm range. If it is less than 10 nm, it becomes difficult to reduce to the metal which is Fischer-Tropsch reaction active point by interaction with a catalyst support. Thus, the activity is lowered as a catalyst, while the selectivity to liquid hydrocarbons is reduced while the production of by-product methane is increased. On the other hand, when it exceeds 20 nm, since the bulk volume is larger than the surface area of the catalyst, there is a problem in that the surface area, which is the catalytic action point, is relatively small and the activity of the catalyst is reduced.
- the content of CoO phase particles in the catalyst component that may be formed according to the preparation method of the present invention may be 10 parts by weight to 100 parts by weight based on 100 parts by weight of cobalt oxide as a catalyst component.
- the method for preparing a catalyst for Fischer-Tropsch synthesis according to the present invention may further include a fourth step of supporting cobalt oxide particles including some or all of the CoO phase particles prepared in the previous step on a support. Can be.
- the content of the catalyst component including the CoO phase particles supported on the support may be 3 parts by weight to 40 parts by weight, more preferably 5 parts by weight to 35 parts by weight based on 100 parts by weight of the support. If it is less than 3 parts by weight, there is a problem that the reactivity decreases because there is not enough active ingredient to exhibit reactivity in Fischer Trop. On the other hand, if it exceeds 40 parts by weight, the catalyst manufacturing cost is increased and the economical efficiency is lowered, the particle size of the catalyst is increased and the specific surface area of the catalyst is reduced, there is a problem that the activity of Fischer Trop drop.
- the support may be gamma-alumina, silica, titania, modified gamma-alumina, modified silica, modified titania, or mixtures thereof.
- the modified support has the effect of improving the physico-chemical performance of the support or improving the dispersion of the catalyst and enhancing the catalyst stability.
- the catalytic activity is greatly enhanced by treating zirconia on silica or alumina support.
- the cobalt particles may be redispersed in a nonpolar solvent and then impregnated into the support.
- a solvent having a low boiling point as the nonpolar solvent.
- the non-polar solvent may be removed at a temperature of from room temperature to 70 ° C., and the supported catalyst may be dried at a temperature of 80 to 200 ° C. to finally prepare a Fischer-Tropsch synthesis catalyst supported on a support.
- Fischer-Tropsch synthesis catalyst prepared according to the present invention may further comprise a precious metal selected from the group consisting of platinum, ruthenium, rhenium or mixtures thereof.
- the noble metal acts as a promoter to improve the activity of the catalyst.
- the content of the noble metal is preferably 0.01 parts by weight to 1 part by weight based on 100 parts by weight of the catalyst.
- the process for producing liquid hydrocarbons from natural gas using the Fischer-Tropsch synthesis reaction according to the invention comprises the steps of: a) applying the Fischer-Tropsch synthesis catalyst prepared according to the invention to a Fischer-Tropsch synthesis reactor ; B) reducing the separated Fischer-Tropsch synthesis catalyst comprising CoO phase particles to activate the Fischer-Tropsch synthesis catalyst; And c) performing a Fischer-Tropsch synthesis reaction by the activated Fischer-Tropsch synthesis catalyst.
- natural gas may be reformed to prepare syngas (CO / H 2 ).
- the Fischer-Tropsch synthesis reactor may be a fixed bed, fluidized bed, or slurry reactor.
- step b) may be performed by reducing the Fischer-Tropsch synthesis catalyst under a hydrogen atmosphere without a separate firing process. Can be.
- Step b) is preferably carried out in a hydrogen atmosphere of 100 °C to 500 °C.
- step c) corresponding to the Fischer Tropsch synthesis reaction may be performed at 200 ° C. to 350 ° C., a reaction pressure of 5 to 30 kg / cm 3 , and a space velocity of 1000 to 10000 h ⁇ 1 , but is not limited thereto.
- Fischer Tropsch synthesis reaction is preferably carried out while maintaining the hydrogen / carbon monoxide reaction ratio of 1 to 25 molar ratio.
- the method for producing a liquid hydrocarbon according to the present invention may further include a step of reforming the Fischer Tropsch synthesis reaction product after step c).
- the Fischer-Tropsch synthesis catalyst prepared according to the present invention exhibits high activity even at low reduction temperatures, and can suppress high conversion of carbon monoxide, stable selectivity to liquid hydrocarbons, and deactivation of the catalyst.
- liquid hydrocarbons were prepared through Fischer-Tropsch synthesis, resulting in improved cobalt oxide reduction and CO selectivity in Fischer-Tropsch synthesis, and increased C5 + carbon selectivity.
- the separated Fischer-Tropsch synthesis catalyst comprising CoO phase particles prepared according to the present invention exhibits high activity even at low reduction temperatures because of its high dispersion and easy reduction.
- the catalyst When the catalyst is applied to the Fischer Tropsch synthesis reaction, it exhibits high conversion of carbon monoxide and stable selectivity of liquid hydrocarbon, and can inhibit the deactivation of the catalyst, thereby enabling the development of a competitive GTL process.
- Example 1 is a transmission electron microscope (TEM) photograph of cobalt oxide nanoparticles prepared in each of Examples and Comparative Examples (a: Example 1, b: Example 2, c: Example 3, d: Comparative Example 1) .
- TEM transmission electron microscope
- Figure 2 shows the X-ray diffraction pattern (XRD) of the nanoparticles prepared in each Example and Comparative Example (a: Example 1, b: Example 2, c: Example 3, d: Comparative Example 1) .
- XRD X-ray diffraction pattern
- Example 3 is a transmission electron micrograph of a catalyst in which cobalt oxide nanoparticles prepared in Examples and Comparative Examples are supported on a gamma-alumina support (a: Example 1, b: Example 2, c: Example 3, d: comparative example 1).
- FIG. 4 shows X-ray diffraction patterns (XRD) of a catalyst in which cobalt oxide nanoparticles prepared in each example and a comparative example are supported on a gamma-alumina support (a: Example 1, b: Example 2, c Example 3, d: Comparative Example 1).
- XRD X-ray diffraction patterns
- Example 1 Preparation of CoO the cobalt catalyst consisting of 100% (5% Co / Al 2 O 3 - CoO 100%)
- FIG. 3 (a) A TEM image of the catalyst supported on the support is shown in FIG. 3 (a), and an XRD pattern is shown in FIG. 4 (a). 3 (a) it was confirmed that the cobalt oxide nanoparticles are evenly supported on the support.
- Example 2 a 70% CoO and Co 3 O 4 phase producing a cobalt catalyst consisting of 30% (5% Co / Al 2 O 3 - CoO 70%)
- Cobalt nanoparticles were prepared in the same manner as in Example 1, except that the capped cobalt-containing oil layer of Example 1 was heated to 270 ° C. for 3 hours.
- FIG. 1 (b) A transmission electron microscope (TEM) photograph of the prepared cobalt oxide nanoparticles is shown in FIG. 1 (b). From the TEM photograph of FIG. 1 (b), it could be confirmed that the average size of the prepared cobalt oxide particles was 14.2 nm. In addition, the average size of cobalt oxide was calculated using the Debye-Scherrer equation, which was found to be 15.2 nm, similar to the TEM result.
- Example 2 Support of the prepared cobalt nanoparticles was also carried out in the same manner as in Example 1.
- TEM images and X-ray diffraction images of the supported cobalt nanoparticles are shown in FIGS. 3 (b) and 4 (b), respectively.
- Example 3 a 30% CoO and Co 3 O 4 phase producing a cobalt catalyst consisting of 70% (5% Co / Al 2 O 3 - CoO 30%)
- Cobalt nanoparticles were prepared in the same manner as in Example 1, except that the capped cobalt-containing oil layer of Example 1 was heated to 230 ° C. for 3 hours.
- FIG. 1 (c) A transmission electron microscope (TEM) photograph of the prepared cobalt oxide nanoparticles is shown in FIG. 1 (c). From the TEM photograph of FIG. 1 (c), it could be confirmed that the average size of the prepared cobalt oxide particles was 14.5 nm. In addition, the average size of cobalt oxide was calculated using the Debye-Scherrer equation, which was found to be 15.2 nm, similar to the TEM result.
- Example 2 Support of the prepared cobalt nanoparticles was also carried out in the same manner as in Example 1. TEM images and X-ray diffraction images of the supported cobalt nanoparticles are shown in FIGS. 3 (c) and 4 (c), respectively.
- Cobalt nanoparticles were prepared in the same manner as in Example 1, except that the capped cobalt-containing oil layer of Example 1 was heated to 200 ° C. for 3 hours.
- FIG. 1 (d) A transmission electron microscope (TEM) photograph of the prepared cobalt oxide nanoparticles is shown in FIG. 1 (d).
- TEM transmission electron microscope
- the average size of the prepared cobalt oxide particles was 14.8 nm.
- the average size of cobalt oxide was calculated using the Debye-Scherrer equation, which was found to be 15.7 nm, similar to the TEM result.
- a solution containing 20 mL of tertiary distilled water and 2.9 g of 28% ammonium hydroxide (NH 4 OH) was prepared.
- a slurry of 7 g of cobalt nitrate (Co (NO 3 ) 2 .6H 2 O) and 26.9 g of gamma-alumina in 50 mL of tertiary distilled water the solution was added under vigorous stirring.
- the slurry was dried at 100 ° C. for at least 12 hours, and then calcined at 500 ° C. for 5 hours to prepare a 5% cobalt / alumina catalyst.
- Fischer-Tropsch reaction was performed using the catalysts prepared in Examples 1 to 3 and Comparative Examples 1 to 3, and the activity of each catalyst was compared and analyzed.
- Example 1 Example 2> Example Example 3).
- Examples 1 to 3 containing the CoO phase is similar to the C5 + carbon selectivity compared to Comparative Examples 1 to 3 consisting of only the Co 3 O 4 phase, but the hydrogen adsorption amount and CO conversion rate is much better Showed results.
- Fischer-Tropsch catalyst prepared according to the production method of the present invention CoO phase was confirmed that the hydrogen adsorption amount and CO conversion rate is remarkable compared to the existing catalyst.
- Example 4 CoO phase of 100% cobalt nanoparticles gamma-manufacture of the supported catalyst in 10% aluminum chair support (10% Co / Al 2 O 3 - CoO 100%)
- Cobalt nanoparticles were prepared in the same manner as in Example 1.
- the supported catalyst was prepared in the same manner as in Example 1 except that 20 g of nanocobalt oxide solution was taken and impregnated in 10 g of gamma-alumina.
- Example 5 CoO phase of 100% cobalt nanoparticles gamma-manufacture of the supported catalyst in 20% aluminum chair support (20% Co / Al 2 O 3 - CoO 100%)
- Cobalt nanoparticles were prepared in the same manner as in Example 1.
- the supported catalyst was prepared in the same manner as in Example 1 except that 40 g of nanocobalt oxide solution was taken and impregnated into 10 g of gamma-alumina.
- Example 6 100% CoO phase of the cobalt nanoparticles gamma-manufacture of the supported catalyst in 30% aluminum chair support (30% Co / Al 2 O 3 - CoO 100%)
- Cobalt nanoparticles were prepared in the same manner as in Example 1.
- the supported catalyst was prepared in the same manner as in Example 1 except that 60 g of nanocobalt oxide solution was taken and impregnated in 10 g of gamma-alumina.
- Comparative Example 4 100% of CoO phase cobalt nanoparticles are gamma-manufacture of the supported 2% aluminum chair support catalyst (2% Co / Al 2 O 3 - CoO 100%)
- Cobalt nanoparticles were prepared in the same manner as in Example 1.
- the supported catalyst was prepared in the same manner as in Example 1 except that 4 g of the nanocobalt oxide solution and 10 g of hexane were mixed and impregnated in 10 g of gamma-alumina.
- Comparative Example 5 100% of CoO phase cobalt nanoparticles are gamma-manufacture of the supported catalyst in 50% aluminum chair support (50% Co / Al 2 O 3 - CoO 100%)
- Cobalt nanoparticles were prepared in the same manner as in Example 1.
- the supported catalyst was prepared in the same manner as in Example 1 except that 100 g of nanocobalt oxide solution was taken and impregnated in 10 g of gamma-alumina.
- Fischer-Tropsch reaction was performed in the same manner as in Experimental Example 1, except that the catalysts prepared in Examples 4 to 6 and Comparative Examples 4 to 5 were used. The results are shown in Table 2.
- the cobalt oxide reduction and CO conversion were excellent when the supported amount of cobalt nanoparticles was between 10% and 30%.
- the catalytic activity and C5 + selectivity increased.
- the supported amount of cobalt nanoparticles was too small (2%, Comparative Example 4)
- the catalytic activity and selectivity decreased, and even when the supported amount of cobalt nanoparticles was large (50%, Comparative Example 5)
- the CO conversion rate is low. That is, it was confirmed that the supported amount of the cobalt nanoparticles is 10% to 30%.
- Example 7 Preparation of a Catalyst in which 10% of Cobalt Nanoparticles on CoO Supported on a Silica Support 10% (10% Co / SiO 2 -CoO 100%)
- a catalyst was prepared in the same manner as in Example 4, except that silica (SiO 2, specific surface area of 260 m 2 / g, average pore diameter of 10 nm) was used as the catalyst support.
- silica SiO 2, specific surface area of 260 m 2 / g, average pore diameter of 10 nm
- a catalyst was prepared in the same manner as in Example 4, except that titania (TiO 2, specific surface area of 120 m 2 / g, average pore diameter of 12 nm) was used as the catalyst support.
- titania TiO 2, specific surface area of 120 m 2 / g, average pore diameter of 12 nm
- Example 9 Preparation of a Catalyst in which 100% of Cobalt Nanoparticles on CoO Are 10% Supported on a Gamma-Alumina Support Modified with SiO 2 (10% Co / 3% SiO 2 / Al 2 O 3 -CoO 100%)
- TEOS tetraethyl orthosilicate
- a catalyst was prepared in the same manner as in Example 4, except that 3% SiO 2 / Al 2 O 3 was used as the catalyst support.
- the catalyst was prepared by further dissolving 0.02 g of tetraamineplatinum (II) nitrate, a platinum precursor, in 6 g of distilled water in the catalyst prepared in Example 4 (Example 10).
- Fischer-Tropsch reaction was performed in the same manner as in Experiment 1, except that the catalyst containing the platinum promoter prepared in Example 10 was used. The results are shown in Table 4 below.
- Fischer-Tropsch reaction was performed in the same manner as in Experiment 1, except that the catalysts prepared in Comparative Examples 6 to 9 were used. The results are shown in Table 5.
Abstract
The present invention relates to an isolated Fischer-Tropsch synthesis catalyst comprising CoO phase particles, a method for preparing the same, and a method for preparing liquid hydrocarbon from natural gas using the same. The isolated Fischer-Tropsch synthesis catalyst comprising CoO phase particles prepared according to the present invention has a high degree of dispersion and is readily reducible, and thus exhibits high activity even at low reduction temperatures. The application of the catalyst to a Fischer-Tropsch synthesis reaction can exhibit a high conversion ratio of carbon monoxide and stable selectivity to liquid hydrocarbon and suppress deactivation of the catalyst, so that competitive GTL processes can be developed.
Description
본 발명은 CoO 상(phase) 입자를 포함하는 분리된 피셔-트롭시 (Fischer-Tropsch, F-T) 합성용 촉매, 이의 제조방법 및 이를 이용하여 천연가스로부터 액체 탄화수소를 제조하는 방법에 관한 것이다.The present invention relates to a separated Fischer-Tropsch (F-T) catalyst comprising CoO phase particles, a method for preparing the same, and a method for producing a liquid hydrocarbon from natural gas using the same.
최근의 급변하는 유가 상승 문제에 대처하기 위한 대안책으로서 각광받고 있는 GTL 기술의 개발에 있어서 F-T 합성용 촉매의 개선은 GTL 기술의 경쟁력 향상과 직결되고 있다. 특히, F-T 반응용 촉매의 개선에 따라서 GTL 공정의 열효율 및 카본 활용 효율을 향상할 수 있으며 F-T 반응 공정을 최적화하여 설계할 수도 있게 된다. 이와 같은 F-T 반응을 위해서는 철 및 코발트 계열 등의 촉매가 주로 사용되는데, 코발트 계열 촉매의 특징은 고가인 단점이 있으나, 높은 활성과 긴 수명 그리고 CO2 생성이 낮으면서 액체 파라핀계 탄화수소의 생성 수율이 높은 장점을 지니고 있다. 또한, 고온에서는 CH4을 다량 생산하는 문제가 있어 저온 촉매로만 사용이 가능하며, 고가의 코발트를 사용하기 때문에 알루미나, 실리카, 티타니아 등의 고표면적의 안정적인 지지체 위에 잘 분산시켜야 하며 소량의 Pt, Ru, Re 등의 귀금속 조촉매가 추가로 첨가된 형태로 사용되고 있는 실정이다.In the development of GTL technology, which is in the spotlight as an alternative to cope with the recent rapidly rising oil price problem, the improvement of the catalyst for FT synthesis is directly connected to the improvement of the competitiveness of the GTL technology. In particular, according to the improvement of the catalyst for FT reaction, the thermal efficiency and carbon utilization efficiency of the GTL process can be improved, and the FT reaction process can be optimized and designed. Iron and cobalt-based catalysts are mainly used for the FT reaction, but the characteristics of the cobalt-based catalysts are expensive, but they have high activity, long lifespan, and low production of CO 2 while producing low yields of liquid paraffinic hydrocarbons. It has a high advantage. In addition, there is a problem of producing a large amount of CH 4 at high temperatures, it can be used only as a low-temperature catalyst, and because expensive cobalt is used, it must be well dispersed on a high surface area stable support such as alumina, silica, titania, and a small amount of Pt, Ru It is a situation that is used in the form of addition of a noble metal promoter, such as, Re.
GTL 공정은 천연가스의 개질(reforming) 반응, 합성가스의 F-T 합성반응 및 생성물의 개질 반응과 같이 3단계의 주요 공정으로 구성되어 있으며, 이 중에서 철 및 코발트를 촉매로 사용하여 200℃ 내지 350℃의 반응 온도와 10기압 내지 30기압의 압력에서 수행되는 F-T 반응은 다음과 같이 4개의 주요 반응으로 설명될 수 있다.The GTL process consists of three main processes: reforming reaction of natural gas, FT synthesis reaction of synthesis gas, and reforming reaction of product. Among them, iron and cobalt are used as catalysts, and the temperature is 200 ° C to 350 ° C. The reaction temperature of and the FT reaction carried out at a pressure of 10 to 30 atm can be described as four main reactions as follows.
(a) 사슬성장 F-T 합성(Chain growth in F-T synthesis)(a) Chain growth in F-T synthesis
CO + 2H2 → -CH2- + H2O △H(227 ℃) = -165 kJ/molCO + 2H 2 → -CH 2- + H 2 O ΔH (227 ° C) = -165 kJ / mol
(b) 메탄화(Methanation)(b) Methanation
CO + 3H2 → CH4 + H2O △H(227 ℃) = -215 kJ/molCO + 3H 2 → CH 4 + H 2 O ΔH (227 ° C) = -215 kJ / mol
(c) 수성가스 전환반응(Water gas shiF-T reaction)(c) Water gas shiF-T reaction
CO + H2O → CO2 + H2 △H(227 ℃) = -40 kJ/molCO + H 2 O → CO 2 + H 2 ΔH (227 ° C) = -40 kJ / mol
(d) 부다 반응(Boudouard reaction)(d) Boudouard reaction
2CO → C + CO2 △H(227 ℃) = -134 kJ/mol2CO → C + CO 2 ΔH (227 ° C.) = − 134 kJ / mol
일반적으로 F-T 합성용 촉매는 산화물 촉매이다. 따라서, F-T 합성용 촉매의 환원 특성은 촉매 반응을 결정하는 매우 중요한 요소 중 하나이다.Generally, the catalyst for F-T synthesis is an oxide catalyst. Therefore, the reduction properties of the catalyst for F-T synthesis are one of the very important factors in determining the catalytic reaction.
일반적으로 제조된 코발트 촉매는 Co3O4상을 가지고 있으며, F-T 반응을 수행하기 앞서 수소를 이용하여 300 - 500℃의 온도에서 산화코발트를 환원시키는 단계를 거치게 된다. 산화코발트의 환원 과정은 다음 2 단계로 나타낼 수 있다. In general, the prepared cobalt catalyst has a Co 3 O 4 phase, and undergoes a step of reducing cobalt oxide at a temperature of 300 to 500 ° C. using hydrogen before performing the FT reaction. The reduction process of cobalt oxide can be represented by the following two steps.
1단계: Co3O4 ＋ 4H2 → 3CoO ＋ 4H20Step 1: Co 3 O 4 + 4H 2 → 3CoO + 4H 2 0
2단계: CoO ＋ H2 → Co ＋ H2O Step 2: CoO + H 2 → Co + H 2 O
기존 코발트계 F-T 합성용 촉매의 제조방법으로는 함침법 또는 공침법이 있으며, 상기 방법으로 제조된 촉매의 경우는 소성과정을 통해 촉매 산화물이 형성된다. 즉, Co3O4상을 가지게 되며 상기 촉매는 지지체와의 강한 상호작용을 하기 때문에 산화 코발트의 환원온도가 높다. Existing cobalt-based FT synthesis of the catalyst is a method of impregnation or coprecipitation method, the catalyst produced by the above method is a catalyst oxide is formed through the calcination process. That is, it has a Co 3 O 4 phase and the catalyst has a high reduction temperature of cobalt oxide because the catalyst has a strong interaction with the support.
한국 등록특허 제10-1015492호는 기존 촉매 제조방법과 상이한 촉매 제조방법을 제시하였다. 이는 지지체와 활성 물질과의 상호작용을 적게 하는 동시에 활성 성분 입자의 크기를 조절함으로써, 일산화탄소의 선택도를 조절할 수 있다고 기재되어 있다. 그러나, 상기 특허에서 제시된 방법으로 제조된 촉매 역시 Co3O4상으로 이루어져, F-T 반응에 사용되기 전 두 단계 환원 반응을 거쳐야 하는 한계가 있었다. Korean Patent No. 10-1015492 proposed a catalyst production method different from the existing catalyst production method. It is described that the selectivity of carbon monoxide can be controlled by controlling the size of the active ingredient particles while reducing the interaction of the support with the active material. However, the catalyst prepared by the method proposed in the patent also consists of a Co 3 O 4 phase, there was a limit to go through a two-stage reduction reaction before being used for the FT reaction.
F-T 촉매의 활성을 결정하는 중요한 요인은 분산도와 환원율이다. 입자의 크기가 작아서 분산도가 높은 경우에는, F-T 촉매의 안정성이 낮아지며 촉매활성이 낮고 메탄 생성이 많아지는 문제점이 있다. 또한 입자의 크기가 너무 커서 환원율이 높은 경우에는 분산도가 낮아 촉매의 활성이 저해된다. 따라서, 적절한 입자크기를 가지며 분산도와 환원율이 높은 촉매가 우수한 촉매라고 할 수 있다.Important factors that determine the activity of the F-T catalyst are dispersion and reduction rate. When the particle size is small and the dispersion degree is high, there is a problem that the stability of the F-T catalyst is low, the catalytic activity is low, and the methane production is increased. In addition, when the particle size is too large and the reduction rate is high, the degree of dispersion is low and the activity of the catalyst is inhibited. Therefore, a catalyst having an appropriate particle size and high dispersibility and reduction rate can be said to be an excellent catalyst.
이에, 본 발명자들은 활성 및 액체탄화수소의 선택도가 최적화된 코발트계 촉매에 대해 연구하던 중, CoO상이 포함된 코발트 나노입자를 제조하는 방법을 고안하였으며, 이를 촉매 지지체에 담지하여 피셔-트롭시 합성용 촉매를 제조하는 경우, 낮은 온도에서 높은 환원 특성과 우수한 분산도를 나타내어, 기존 제조방법에 비해 뛰어난 촉매 활성을 보이는 것을 확인하고 본 발명을 완성하였다. 본 발명은 이에 기초한 것이다.Accordingly, the present inventors devised a method for preparing cobalt nanoparticles containing a CoO phase, while studying the cobalt-based catalysts with optimized activity and selectivity of liquid hydrocarbons, and supported them on a catalyst support for Fischer-Tropsch synthesis. In the case of preparing a catalyst for the catalyst, the present invention exhibited excellent reduction activity and excellent dispersibility at low temperature, and showed excellent catalytic activity compared to the conventional production method, thus completing the present invention. The present invention is based on this.
본 발명의 제1양태는 CoO 상(phase) 입자를 포함하는 피셔-트롭시 합성용 촉매의 제조방법에 있어서, 코발트 공급 전구체 수용액과 염기성 화합물 수용액을 반응시켜 침전물을 형성하는 제1 단계; 상기 침전물을 캡핑(capping) 분자 및 비극성 유기 용매와 혼합하여 가열하는 제2 단계; 및 상기 혼합물 중 유기 용매층을 회수하고 CoO 상 입자들을 형성하도록 230℃ 내지 350℃에서 가열하는 제3 단계;를 포함하는 것이 특징인 제조방법을 제공한다. According to a first aspect of the present invention, there is provided a method for preparing a Fischer-Tropsch synthesis catalyst including CoO phase particles, the method comprising: reacting a cobalt feed precursor aqueous solution with an aqueous basic compound solution to form a precipitate; A second step of heating the precipitate by mixing with a capping molecule and a nonpolar organic solvent; And a third step of recovering the organic solvent layer in the mixture and heating at 230 ° C. to 350 ° C. to form CoO phase particles.
바람직하게는, 이전 단계에서 제조된 CoO 상(phase) 입자들을 일부 또는 전부 포함하는 코발트 산화물 입자들을 지지체에 담지하는 제4단계를 추가로 더 포함할 수 있다.Preferably, the method may further include a fourth step of supporting the cobalt oxide particles including some or all of the CoO phase particles prepared in the previous step on the support.
본 발명의 제2양태는 본 발명의 제1양태에 의해 제조된 것으로, CoO 상(phase) 입자를 포함하는 분리된 피셔-트롭시 합성용 촉매를 제공한다. The second aspect of the present invention provides a catalyst for separated Fischer-Tropsch synthesis, which is prepared by the first aspect of the present invention, comprising CoO phase particles.
본 발명의 제3양태는 피셔-트롭시 합성반응을 이용하여 천연가스로부터 액체 탄화수소를 제조하는 방법에 있어서, 본 발명의 제1양태에 의해 제조된 피셔-트롭시 합성용 촉매를 피셔-트롭시 합성반응기에 적용하는 a) 단계; CoO 상(phase) 입자를 포함하는 분리된 피셔-트롭시 합성용 촉매를 환원시켜 피셔-트롭시 합성용 촉매로 활성화시키는 b) 단계; 및 상기 활성화된 피셔-트롭시 합성용 촉매에 의해 피셔-트롭시 합성반응을 수행하는 c) 단계를 포함하는 것이 특징인 제조방법을 제공한다.According to a third aspect of the present invention, there is provided a method for producing a liquid hydrocarbon from natural gas using a Fischer-Tropsch synthesis reaction, wherein the Fischer-Tropsch synthesis catalyst prepared by the first aspect of the present invention A) applying to a synthetic reactor; B) reducing the separated Fischer-Tropsch synthesis catalyst comprising CoO phase particles to activate the Fischer-Tropsch synthesis catalyst; And c) performing Fischer-Tropsch synthesis by the activated Fischer-Tropsch synthesis catalyst.
이하 본 발명을 자세히 설명한다. Hereinafter, the present invention will be described in detail.
일반적으로 기존 코발트 촉매는 Co3O4 상으로 제조되기 때문에, F-T 반응기에 적용된 후, F-T 반응을 수행하기 전, 300 - 500℃의 고온의 수소분위기 하에서 환원에 의해 코발트 금속(Co)으로 활성화되어야 한다. In general, since the existing cobalt catalyst is prepared in Co 3 O 4 phase, it must be activated to cobalt metal (Co) by reduction under high temperature hydrogen atmosphere of 300-500 ° C. after being applied to the FT reactor and before performing the FT reaction. do.
코발트 산화물 제조시 캡핑된 코발트가 함유된 유기용매층을 230℃ 내지 350℃에서 가열하는 경우 CoO 상 입자를 함유하는 코발트 촉매를 제조할 수 있다는 것을 발견하였으며, 본 발명은 이에 기초한 것이다. It has been found that the cobalt catalyst containing CoO phase particles can be prepared when the capped cobalt-containing organic solvent layer is heated at 230 ° C. to 350 ° C. in the preparation of cobalt oxide, and the present invention is based on this.
캡핑된 코발트가 함유된 유기용매층을 300℃에서 가열하는 경우(실시예 1-1) 형성된 코발트 산화물 나노입자가 모두 CoO 상으로만 이루어졌다. 한편, 캡핑된 코발트가 함유된 유기용매층을 270℃에서 가열하는 경우(실시예 2) 코발트 산화물 나노입자 중 CoO 상의 함량이 70%이었고, 230℃에서 가열하는 경우(실시예 3) CoO 상의 함량이 30%이었으며, 200℃에서 가열하는 경우(비교예 1) 코발트 산화물 나노입자는 모두 Co3O4 상으로만 이루어졌다. 즉, 캡핑된 코발트가 함유된 유기용매층의 가열 온도가 270℃ 이하로 낮아질수록 CoO 상의 함량이 낮아지고 Co3O4 상의 함량이 높아졌다. 또한, 코발트 산화물 나노 입자 중 CoO 상이 존재하는 실시예 1 내지 4의 촉매를 400℃에서 소성한 결과(비교예 6 내지 9) 모두 Co3O4상이 100% 인 촉매로 되었다.When the capped cobalt-containing organic solvent layer was heated at 300 ° C. (Example 1-1), all of the formed cobalt oxide nanoparticles consisted of only CoO phase. Meanwhile, when the capped cobalt-containing organic solvent layer was heated at 270 ° C. (Example 2), the content of CoO phase in the cobalt oxide nanoparticles was 70%, and when heated at 230 ° C. (Example 3), the content of CoO phase This was 30%, and when heated at 200 ° C. (Comparative Example 1), the cobalt oxide nanoparticles were all composed of Co 3 O 4 phase only. That is, as the heating temperature of the capped cobalt-containing organic solvent layer was lowered below 270 ° C, the content of CoO phase was lowered and the content of Co 3 O 4 phase was higher. In addition, as a result of calcining the catalysts of Examples 1 to 4 in which the CoO phase is present in the cobalt oxide nanoparticles at 400 ° C. (Comparative Examples 6 to 9), the catalysts were 100% of the Co 3 O 4 phase.
따라서, 본 발명은 F-T 반응기에 적용되기 전, 피셔-트롭시 합성용 촉매 및/또는 지지체에 담지하는 촉매 유효성분이, CoO 상(phase) 입자들을 일부 또는 전부 포함하는 코발트 산화물 입자들인 것이 특징이다. 따라서, 본 발명에 따라 제조된 촉매는 별도의 소성과정 없이 수소로 환원되어 활성화될 수 있다. 상기 환원은 촉매를 고정층, 유동층 또는 슬러리 반응기에 적용시킨 후 100℃ 내지 500℃의 온도 범위의 수소 분위기하에서 이루어질 수 있다. 또한, 본 발명에 따라 제조된 피셔-트롭시 합성용 촉매는 낮은 환원 온도에서도 높은 활성을 나타내고, 일산화탄소의 높은 전환율과 액체탄화수소로의 안정적인 선택성 및 촉매의 비활성화를 억제할 수 있다.Accordingly, the present invention is characterized in that, before being applied to the F-T reactor, the catalyst active ingredient supported on the Fischer-Tropsch synthesis catalyst and / or the support is cobalt oxide particles containing some or all of CoO phase particles. Therefore, the catalyst prepared according to the present invention can be reduced and activated with hydrogen without a separate firing process. The reduction may be carried out in a hydrogen atmosphere in the temperature range of 100 ℃ to 500 ℃ after applying the catalyst to a fixed bed, fluidized bed or slurry reactor. In addition, the Fischer-Tropsch synthesis catalyst prepared according to the present invention exhibits high activity even at low reduction temperatures, and can suppress high conversion of carbon monoxide, stable selectivity to liquid hydrocarbons, and deactivation of the catalyst.
본 발명에서, "분리된 피셔-트롭시 합성용 촉매"는 피셔-트롭시 합성용 반응기에 적용 전 직접 합성하여 운반 및/또는 유통될 수 있는 촉매 상태를 의미하는 것으로, 본 발명에 따른 피셔-트롭시 합성용 촉매는 피셔-트롭시 합성용 반응기에 적용 전 CoO 상(phase) 으로 합성되고 나서, 피셔-트롭시 합성용 반응기에 적용된 후 환원반응에 의해 CoO 상의 전구체가 Co 상의 피셔-트롭시 합성용 촉매가 된다. In the present invention, "separate Fischer-Tropsch synthesis catalyst" refers to a catalyst state that can be directly synthesized and transported and / or distributed before being applied to the Fischer-Tropsch synthesis reactor, and according to the Fischer- The catalyst for Tropsch synthesis is synthesized in a CoO phase prior to application to the Fischer-Tropsch synthesis reactor, and then applied to the Fischer-Tropsch synthesis reactor, and then the precursor of CoO is fischer-Tropsch by Co reduction. It becomes a catalyst for synthesis.
또한, 본 발명은 F-T 반응기에 적용되기 전 미리 코발트계 촉매 성분을 최적의 크기로 제조하고 CoO 상을 포함하는 나노입자로 제조하여 이를 촉매 지지체에 담지할 수 있으므로, 분산도가 높고 낮은 온도에서 환원이 쉽게 일어나게 할 수 있다. In addition, the present invention can prepare the cobalt-based catalyst component in the optimum size before the application to the FT reactor, and can be prepared by the nanoparticles containing the CoO phase and supported on the catalyst support, high dispersion degree and reduced at low temperature You can make this happen easily.
본 발명에 따라 CoO 상(phase) 입자를 포함하는 피셔-트롭시 합성용 촉매의 제조방법은 코발트 공급 전구체 수용액과 염기성 화합물 수용액을 반응시켜 침전물을 형성하는 제1 단계; 상기 침전물을 캡핑(capping) 분자 및 비극성 유기 용매와 혼합하여 가열하는 제2 단계; 및 상기 혼합물 중 유기 용매층을 회수하고 CoO 상 입자들을 형성하도록 230℃ 내지 350℃에서 가열하는 제3 단계를 포함한다. According to the present invention, a method for preparing a catalyst for Fischer-Tropsch synthesis including CoO phase particles may include a first step of forming a precipitate by reacting an aqueous solution of a cobalt feed precursor and an aqueous solution of a basic compound; A second step of heating the precipitate by mixing with a capping molecule and a nonpolar organic solvent; And a third step of recovering the organic solvent layer in the mixture and heating at 230 ° C. to 350 ° C. to form CoO phase particles.
구체적으로는, 코발트 공급 전구체 수용액과 염기성 화합물 수용액을 반응시키면 코발트 함유 침전물이 형성되고, 이를 탈이온수로 세척하여 얻은 코발트 함유 침전물 슬러리를 캡핑 분자 및 비극성 유기 용매와 혼합하여 가열하면, 무기물 촉매성분이 유기 용매로 녹아들어 수용액층과 분리된다. 이어서, 유기 용매층을 회수하고 230℃ 내지 350℃에서 가열하면 CoO 상이 포함된 입자들을 형성할 수 있다. 또한, 이때 원하는 크기로 입자크기를 조절할 수 있다.Specifically, when the aqueous cobalt feed precursor solution and the basic compound aqueous solution are reacted to form a cobalt-containing precipitate, the cobalt-containing precipitate slurry obtained by washing with deionized water is mixed with a capping molecule and a non-polar organic solvent and heated to form an inorganic catalyst component. It is dissolved in an organic solvent and separated from the aqueous layer. Subsequently, the organic solvent layer may be recovered and heated at 230 ° C. to 350 ° C. to form particles containing a CoO phase. In addition, the particle size can be adjusted to the desired size at this time.
제1 단계에서 코발트 공급 전구체의 비제한적인 예는 질산코발트(Co(NO3)2·H2O), 염화코발트(CoCl2·H2O), 황산코발트(CoSO4), 초산코발트(Co(AC)2) 및 이의 혼합물일 수 있다.Non-limiting examples of cobalt feed precursors in the first step include cobalt nitrate (Co (NO 3 ) 2 H 2 O), cobalt chloride (CoCl 2 H 2 O), cobalt sulfate (CoSO 4 ), cobalt acetate (Co (AC) 2 ) and mixtures thereof.
제1 단계에서 염기성 화합물의 비제한적인 예는 암모니아, 수산화나트륨, 수산화칼륨, 수산화마그네슘, 수산화칼슘, 수산화암모늄, 탄산암모늄, 탄산수소암모늄, 탄산나트륨, 탄산수소나트륨, 탄산칼륨, 탄산수소칼륨 및 이의 혼합물일 수 있다. Non-limiting examples of basic compounds in the first step include ammonia, sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide, ammonium hydroxide, ammonium carbonate, ammonium bicarbonate, sodium carbonate, sodium bicarbonate, potassium carbonate, potassium hydrogen carbonate and mixtures thereof Can be.
제2 단계에서 캡핑 분자의 비제한적인 예는 포화 또는 불포화 C6 -C30 유기산 또는 지방산일 수 있다. 보다 구체적으로는 2-에틸헥사노익산(2-ethylhexanoic acid), 스테아린산(stearic acid), 라우린산(lauric acid), 리놀레산(linoleic acid), 팔미틴산(palmitic acid), 올레산(oleic acid), 다중산(polyacid), 이들의 유도체 등을 단독 또는 2종 이상을 혼합하여 사용할 수 있다. Non-limiting examples of capping molecules in the second step can be saturated or unsaturated C 6 -C 30 organic acids or fatty acids. More specifically, 2-ethylhexanoic acid, stearic acid, lauric acid, linoleic acid, palmitic acid, oleic acid, multiple Acids (polyacids), derivatives thereof and the like may be used alone or in combination of two or more thereof.
제2 단계에서 캡핑 분자는 코발트 공급 전구체 1몰에 대하여 0.1 내지 2.5의 몰비로 사용되는 것이 바람직하다. 0.1 몰비 미만이면 완전한 캡핑이 이루어지지 않아 분산성이 떨어지고, 수용액 중에 촉매 성분이 남아 손실이 발생할 수 있다. 반면, 2.5 몰비를 초과하는 경우에는 캡핑된 촉매성분의 콜로이드 용액의 유동성이 떨어질 수 있다.The capping molecule in the second step is preferably used in a molar ratio of 0.1 to 2.5 with respect to 1 mole of cobalt feed precursor. If it is less than 0.1 molar ratio, complete capping will not be achieved, resulting in poor dispersibility, and loss of catalyst components may remain in the aqueous solution. On the other hand, when it exceeds 2.5 molar ratio, the fluidity of the colloidal solution of the capped catalyst component may be inferior.
제2 단계에서 비극성 유기 용매는 녹는점이 30℃ 미만, 끓는점이 70℃ 이상인 것이 바람직하다. 이는 표면처리에 적합한 반응온도를 유지하기 위해서이다. 비극성 유기 용매의 비제한적인 예는 톨루엔, 자일렌, 파라핀, 1-헥사데칸 및 등유, 경유 또는 중유와 같은 일반적인 석유계 용제 등일 수 있다. In the second step, the nonpolar organic solvent preferably has a melting point of less than 30 ° C. and a boiling point of 70 ° C. or more. This is to maintain a reaction temperature suitable for surface treatment. Non-limiting examples of nonpolar organic solvents may be toluene, xylene, paraffin, 1-hexadecane and common petroleum solvents such as kerosene, light oil or heavy oil and the like.
제2단계의 바람직한 캡핑 반응온도는 40 내지 110℃인 것이 바람직하다. 40℃ 미만이면 촉매성분의 캡핑이 완전히 이루어지지 않아서 촉매성분이 수용액층에서 유기용매층으로 분리가 효과적으로 일어나지 않고, 110℃를 초과하는 경우에는 반응온도가 용액의 끓는점보다 높아 제조가 어려운 문제가 발생한다.Preferred capping reaction temperature of the second step is preferably 40 to 110 ℃. If the temperature is less than 40 ° C, the catalyst component is not completely capped, so that the catalyst component does not effectively separate from the aqueous solution layer into the organic solvent layer. If the temperature exceeds 110 ° C, the reaction temperature is higher than the boiling point of the solution, making manufacturing difficult. do.
제3 단계에서 바람직한 가열 온도 범위는 230℃ 내지 350℃이며, 보다 바람직하게는 230℃ 내지 300℃이다. 230℃ 미만이면 CoO가 형성되지 않고 결정화 반응이 약해 생성되는 결정의 크기가 너무 작아지는 문제점이 있다. 또한 350℃를 초과하는 경우 결정의 크기가 너무 커져 나노촉매로 적합하지 않을 수 있다. The preferred heating temperature range in the third step is 230 ° C to 350 ° C, more preferably 230 ° C to 300 ° C. If it is less than 230 ° C, there is a problem in that CoO is not formed and the crystallization reaction is weak so that the size of crystals produced is too small. In addition, when the temperature exceeds 350 ° C., the size of the crystal may be too large to be suitable as a nanocatalyst.
추가로, 형성된 CoO 상 입자들이 포함된 용액은, 극성 유기용매와 혼합시켜 캡핑된 입자를 침전시켜 추출한 후, 이를 재분산하여 유기용매에 분산된 코발트 산화물(CoO) 입자를 수득할 수 있다. 상기 추출 용매로 사용되는 극성 유기 용매의 비제한적인 예는, 메탄올, 에탄올, 아세톤, 아세토나이트릴 또는 이의 혼합물일 수 있다. In addition, the solution containing the CoO phase particles formed may be mixed with a polar organic solvent to precipitate and capped particles, and then redispersed to obtain cobalt oxide (CoO) particles dispersed in the organic solvent. Non-limiting examples of the polar organic solvent used as the extraction solvent may be methanol, ethanol, acetone, acetonitrile or mixtures thereof.
본 발명의 제조방법에 따라 형성될 수 있는 CoO 상 입자들의 평균직경은 5 내지 50 nm일 수 있으며, 보다 바람직하게는 10 내지 20 nm 범위일 수 있다. 10 nm 미만이면 촉매 지지체와 상호작용에 의해 피셔-트롭시 반응 활성점인 금속으로의 환원이 어려워진다. 따라서, 촉매로서 활성이 낮아지며, 액체탄화수소로의 선택도가 감소하는 반면 부산물인 메탄의 생성이 많아진다. 반면, 20 nm를 초과하는 경우 촉매 표면적에 비해 벌크 부피가 커지므로, 촉매 작용점인 표면적이 상대적으로 작아지고, 촉매의 활성이 줄어드는 문제점이 있다. The average diameter of the CoO phase particles which may be formed according to the preparation method of the present invention may be 5 to 50 nm, more preferably 10 to 20 nm range. If it is less than 10 nm, it becomes difficult to reduce to the metal which is Fischer-Tropsch reaction active point by interaction with a catalyst support. Thus, the activity is lowered as a catalyst, while the selectivity to liquid hydrocarbons is reduced while the production of by-product methane is increased. On the other hand, when it exceeds 20 nm, since the bulk volume is larger than the surface area of the catalyst, there is a problem in that the surface area, which is the catalytic action point, is relatively small and the activity of the catalyst is reduced.
본 발명의 제조방법에 따라 형성될 수 있는 촉매 성분 내 CoO 상 입자들의 함량은 촉매 성분인 코발트 산화물 100중량부를 기준으로 10중량부 내지 100중량부일 수 있다. The content of CoO phase particles in the catalyst component that may be formed according to the preparation method of the present invention may be 10 parts by weight to 100 parts by weight based on 100 parts by weight of cobalt oxide as a catalyst component.
본 발명에 따른 피셔-트롭시 합성용 촉매의 제조방법은, 이전 단계에서 제조된 CoO 상(phase) 입자들을 일부 또는 전부 포함하는 코발트 산화물 입자들을 지지체에 담지하는 제4단계를 추가로 더 포함할 수 있다.The method for preparing a catalyst for Fischer-Tropsch synthesis according to the present invention may further include a fourth step of supporting cobalt oxide particles including some or all of the CoO phase particles prepared in the previous step on a support. Can be.
상기 지지체에 담지된 CoO 상 입자를 포함하는 촉매 성분 함량은 바람직하게는 지지체 100중량부를 기준으로 3중량부 내지 40중량부, 보다 바람직하게는 5중량부 내지 35중량부일 수 있다. 3중량부 미만이면 피셔 트롭시 반응성을 나타내기에 충분한 활성 성분이 존재하지 않아 반응성이 감소하는 문제가 있다. 반면 40중량부를 초과하는 경우, 촉매 제조비용이 증가하여 경제성이 떨어지며, 촉매의 입자크기가 증가하고 촉매의 비표면적이 감소함으로써 피셔 트롭시 활성이 떨어지는 문제점이 있다.The content of the catalyst component including the CoO phase particles supported on the support may be 3 parts by weight to 40 parts by weight, more preferably 5 parts by weight to 35 parts by weight based on 100 parts by weight of the support. If it is less than 3 parts by weight, there is a problem that the reactivity decreases because there is not enough active ingredient to exhibit reactivity in Fischer Trop. On the other hand, if it exceeds 40 parts by weight, the catalyst manufacturing cost is increased and the economical efficiency is lowered, the particle size of the catalyst is increased and the specific surface area of the catalyst is reduced, there is a problem that the activity of Fischer Trop drop.
상기 지지체는 감마-알루미나, 실리카, 티타니아, 개질된 감마-알루미나, 개질된 실리카, 개질된 티타니아, 또는 이의 혼합물일 수 있다. 개질된 지지체는 지지체의 물리-화학적 성능을 개선하거나 촉매의 분산도를 개선하고 촉매 안정성을 증진하는 효과를 나타내며, 예를 들면 실리카나 알루미나 지지체에 지르코니아를 처리함으로서 촉매활성이 크게 증진된다.The support may be gamma-alumina, silica, titania, modified gamma-alumina, modified silica, modified titania, or mixtures thereof. The modified support has the effect of improving the physico-chemical performance of the support or improving the dispersion of the catalyst and enhancing the catalyst stability. For example, the catalytic activity is greatly enhanced by treating zirconia on silica or alumina support.
CoO 상(phase) 입자들을 일부 또는 전부 포함하는 코발트 입자들을 지지체에 담지하기 위해, 상기 코발트 입자들을 비극성 용매에 재분산한 후, 지지체에 함침시킬 수 있다. 이때 비극성 용매는 끓는점이 낮은 용매를 사용하는 것이 바람직하다. 상기 비극성 용매를 상온 내지 70℃의 온도에서 제거하고, 담지된 촉매를 80 내지 200℃의 온도에서 건조하여 최종적으로 지지체에 담지된 피셔-트롭시 합성용 촉매를 제조할 수 있다. In order to support the cobalt particles containing some or all of the CoO phase particles on the support, the cobalt particles may be redispersed in a nonpolar solvent and then impregnated into the support. In this case, it is preferable to use a solvent having a low boiling point as the nonpolar solvent. The non-polar solvent may be removed at a temperature of from room temperature to 70 ° C., and the supported catalyst may be dried at a temperature of 80 to 200 ° C. to finally prepare a Fischer-Tropsch synthesis catalyst supported on a support.
본 발명에 따라 제조된 피셔-트롭시 합성용 촉매는 백금, 루테늄, 레늄 또는 이의 혼합물로 이루어진 군에서 선택되는 귀금속을 추가로 더 포함할 수 있다. 상기 귀금속은 조촉매로서 작용하여 촉매의 활성을 개선한다. 상기 귀금속의 함량은 촉매 100중량부를 기준으로 0.01중량부 내지 1중량부인 것이 바람직하다.Fischer-Tropsch synthesis catalyst prepared according to the present invention may further comprise a precious metal selected from the group consisting of platinum, ruthenium, rhenium or mixtures thereof. The noble metal acts as a promoter to improve the activity of the catalyst. The content of the noble metal is preferably 0.01 parts by weight to 1 part by weight based on 100 parts by weight of the catalyst.
본 발명에 따라 피셔-트롭시 합성반응을 이용하여 천연가스로부터 액체 탄화수소를 제조하는 방법은, 본 발명에 따라 제조된 피셔-트롭시 합성용 촉매를 피셔-트롭시 합성반응기에 적용하는 a) 단계; CoO 상(phase) 입자를 포함하는 분리된 피셔-트롭시 합성용 촉매를 환원시켜 피셔-트롭시 합성용 촉매로 활성화시키는 b) 단계; 및 상기 활성화된 피셔-트롭시 합성용 촉매에 의해 피셔-트롭시 합성반응을 수행하는 c) 단계를 포함한다. The process for producing liquid hydrocarbons from natural gas using the Fischer-Tropsch synthesis reaction according to the invention comprises the steps of: a) applying the Fischer-Tropsch synthesis catalyst prepared according to the invention to a Fischer-Tropsch synthesis reactor ; B) reducing the separated Fischer-Tropsch synthesis catalyst comprising CoO phase particles to activate the Fischer-Tropsch synthesis catalyst; And c) performing a Fischer-Tropsch synthesis reaction by the activated Fischer-Tropsch synthesis catalyst.
본 발명에 따른 액체 탄화수소 제조방법은 적어도 c) 단계 이전에, 천연가스를 개질하여 합성가스(CO/H2)를 준비할 수 있다.In the liquid hydrocarbon production method according to the present invention, at least before step c), natural gas may be reformed to prepare syngas (CO / H 2 ).
한편, 피셔-트롭시 합성반응기는 고정층, 유동층 또는 슬러리 반응기일 수 있다.On the other hand, the Fischer-Tropsch synthesis reactor may be a fixed bed, fluidized bed, or slurry reactor.
본 발명에 따라 CoO 상(phase) 입자들을 일부 또는 전부 포함하는 피셔-트롭시 합성용 촉매를 사용하면 b) 단계는 별도의 소성과정 없이 수소 분위기 하에서 피셔-트롭시 합성용 촉매를 환원시켜 활성화시킬 수 있다.According to the present invention, if the Fischer-Tropsch synthesis catalyst including some or all of the CoO phase particles is used, step b) may be performed by reducing the Fischer-Tropsch synthesis catalyst under a hydrogen atmosphere without a separate firing process. Can be.
b) 단계는 100℃ 내지 500℃의 수소분위기에서 수행되는 것이 바람직하다.Step b) is preferably carried out in a hydrogen atmosphere of 100 ℃ to 500 ℃.
한편, 피셔 트롭시 합성 반응에 해당하는 c) 단계는 200℃ 내지 350℃, 반응 압력 5 내지 30 kg/cm3, 공간속도 1000 - 10000 h-1에서 수행될 수 있으나, 이에 한정되는 것은 아니다.Meanwhile, step c) corresponding to the Fischer Tropsch synthesis reaction may be performed at 200 ° C. to 350 ° C., a reaction pressure of 5 to 30 kg / cm 3 , and a space velocity of 1000 to 10000 h −1 , but is not limited thereto.
피셔 트롭시 합성 반응은 수소/일산화탄소 반응비는 1 내지 25 몰비를 유지하면서 수행하는 것이 바람직하다.Fischer Tropsch synthesis reaction is preferably carried out while maintaining the hydrogen / carbon monoxide reaction ratio of 1 to 25 molar ratio.
또한, 본 발명에 따른 액체 탄화수소 제조방법은 c) 단계 이후 피셔 트롭시 합성 반응 생성물의 개질 반응 단계를 추가로 포함할 수 있다.In addition, the method for producing a liquid hydrocarbon according to the present invention may further include a step of reforming the Fischer Tropsch synthesis reaction product after step c).
본 발명에 따라 제조되는 피셔-트롭시 합성용 촉매는 낮은 환원 온도에서도 높은 활성을 나타내고, 일산화탄소의 높은 전환율과 액체탄화수소로의 안정적인 선택성 및 촉매의 비활성화를 억제할 수 있다.The Fischer-Tropsch synthesis catalyst prepared according to the present invention exhibits high activity even at low reduction temperatures, and can suppress high conversion of carbon monoxide, stable selectivity to liquid hydrocarbons, and deactivation of the catalyst.
본 발명에 따른 촉매를 환원시킨 후 피셔-트롭시 합성반응을 통해 액체 탄화수소를 제조한 결과, 피셔 트롭시 합성 반응의 코발트 산화물 환원도 및 CO 선택도가 개선되며, C5+ 카본 선택도가 증가하였다.As a result of the reduction of the catalyst according to the present invention, liquid hydrocarbons were prepared through Fischer-Tropsch synthesis, resulting in improved cobalt oxide reduction and CO selectivity in Fischer-Tropsch synthesis, and increased C5 + carbon selectivity.
본 발명에 따라 제조된 CoO 상(phase) 입자를 포함하는 분리된 피셔-트롭시 합성용 촉매는, 높은 분산도를 가지며 쉽게 환원이 되기 때문에 낮은 환원온도에서도 높은 활성을 나타낸다. 상기 촉매를 피셔 트롭시 합성 반응에 적용하는 경우, 일산화탄소의 높은 전환율 및 액체탄화수소의 안정적인 선택성을 보이며, 촉매의 비활성화를 억제할 수 있어서 경쟁력 있는 GTL 공정의 개발이 가능하다. The separated Fischer-Tropsch synthesis catalyst comprising CoO phase particles prepared according to the present invention exhibits high activity even at low reduction temperatures because of its high dispersion and easy reduction. When the catalyst is applied to the Fischer Tropsch synthesis reaction, it exhibits high conversion of carbon monoxide and stable selectivity of liquid hydrocarbon, and can inhibit the deactivation of the catalyst, thereby enabling the development of a competitive GTL process.
도 1은 각 실시예 및 비교예에서 제조된 산화코발트 나노입자의 투과전자현미경(TEM) 사진이다(a: 실시예 1, b: 실시예 2, c: 실시예 3, d: 비교예 1).1 is a transmission electron microscope (TEM) photograph of cobalt oxide nanoparticles prepared in each of Examples and Comparative Examples (a: Example 1, b: Example 2, c: Example 3, d: Comparative Example 1) .
도 2는 각 실시예 및 비교예에서 제조된 나노입자의 X선 회절패턴(XRD)을 나타낸 것이다(a: 실시예 1, b: 실시예 2, c: 실시예 3, d: 비교예 1).Figure 2 shows the X-ray diffraction pattern (XRD) of the nanoparticles prepared in each Example and Comparative Example (a: Example 1, b: Example 2, c: Example 3, d: Comparative Example 1) .
도 3은 각 실시예 및 비교예에서 제조된 산화코발트 나노입자가 감마-알루미나 지지체에 담지된 촉매의 투과전자현미경 사진이다(a: 실시예 1, b: 실시예 2, c: 실시예 3, d: 비교예 1).3 is a transmission electron micrograph of a catalyst in which cobalt oxide nanoparticles prepared in Examples and Comparative Examples are supported on a gamma-alumina support (a: Example 1, b: Example 2, c: Example 3, d: comparative example 1).
도 4는 각 실시예 및 비교예에서 제조된 산화코발트 나노입자가 감마-알루미나 지지체에 담지된 촉매의 X선 회절패턴(XRD)을 나타낸 것이다(a: 실시예 1, b: 실시예 2, c: 실시예 3, d: 비교예 1). FIG. 4 shows X-ray diffraction patterns (XRD) of a catalyst in which cobalt oxide nanoparticles prepared in each example and a comparative example are supported on a gamma-alumina support (a: Example 1, b: Example 2, c Example 3, d: Comparative Example 1).
이하, 실시예를 통하여 본 발명을 더욱 상세히 설명하고자 한다. 이들 실시예는 본 발명을 보다 구체적으로 설명하기 위한 것으로, 본 발명의 범위가 이들 실시예에 의해 제한되는 것은 아니다.Hereinafter, the present invention will be described in more detail with reference to Examples. These examples are intended to illustrate the present invention more specifically, but the scope of the present invention is not limited by these examples.
실시예 1: CoO상 100%로 이루어진 코발트 촉매의 제조 (5% Co/Al2O3 - CoO 100%)Example 1: Preparation of CoO the cobalt catalyst consisting of 100% (5% Co / Al 2 O 3 - CoO 100%)
1-1. 산화코발트 나노입자의 제조1-1. Preparation of Cobalt Oxide Nanoparticles
100 mL의 증류수에 28%의 수산화암모늄(NH4OH) 15.3 g이 녹아있는 용액에, 200 mL의 증류수에 30 g의 질화코발트(Co(NO3)2·H2O)가 녹아있는 용액을 교반하면서 침전반응을 통해 슬러리 침전물을 수득하였다. 생성된 침전물을 필터로 거르고, 1500 mL의 증류수로 3차례 나누어 세척하였다. 세척한 침전물을 다시 증류수에 분산하여 수산화코발트 슬러리(수산화 코발트 함량 10%) 용액을 제조하였다. In a solution containing 15.3 g of 28% ammonium hydroxide (NH 4 OH) in 100 mL of distilled water and 30 g of cobalt nitride (Co (NO 3 ) 2 H 2 O) dissolved in 200 mL of distilled water. Slurry precipitate was obtained through precipitation with stirring. The resulting precipitate was filtered off and washed three times with 1500 mL of distilled water. The washed precipitate was further dispersed in distilled water to prepare a cobalt hydroxide slurry (cobalt hydroxide content 10%) solution.
상기 제조된 수산화코발트 슬러리 수용액에 1-헥사데칸(1-hexadecane) 19.0 g과 올레인산 7.1 g을 혼합하고 100 ℃에서 30분 동안 교반하였다. 상기 교반 중 수산화코발트는 올레산과 반응하여 표면이 올레산으로 캡핑되고, 이는 비극성 용매인 1-헥사데칸에 녹아들어 수용층과 오일층으로 분리되었다. 상층의 수용액층을 단순히 분리하여 제거하고, 캡핑된 코발트가 함유된 오일층을 회수하였다. 상기 회수된 용액을 300 ℃에서 3 시간 가열하여 CoO상의 산화코발트 나노결정을 제조하였다. 19.0 g of 1-hexadecane and 7.1 g of oleic acid were mixed in the cobalt hydroxide slurry solution prepared above, and stirred at 100 ° C. for 30 minutes. During the stirring, the cobalt hydroxide reacts with oleic acid and the surface is capped with oleic acid, which is dissolved in 1-hexadecane, a nonpolar solvent, and separated into an aqueous layer and an oil layer. The aqueous layer of the upper layer was simply separated and removed, and the oil layer containing the capped cobalt was recovered. The recovered solution was heated at 300 ° C. for 3 hours to prepare cobalt oxide nanocrystals on CoO.
상기 제조된 산화코발트의 나노입자의 투과전자현미경(TEM)사진을 도 1(a)에 나타내었다. 도 1(a)의 TEM 사진을 통해, 제조된 산화코발트 입자의 평균 크기가 13.7 nm임을 확인할 수 있었다. 또한, 디바이-셰러(Debye-Scherrer)식을 사용하여 산화코발트의 평균크기를 계산하였고 이는 15.4 ㎚로, TEM 결과와 유사함을 확인할 수 있었다. The transmission electron microscope (TEM) photograph of the prepared cobalt oxide nanoparticles is shown in Figure 1 (a). Through the TEM photograph of FIG. 1 (a), it could be confirmed that the average size of the prepared cobalt oxide particles was 13.7 nm. In addition, the average size of cobalt oxide was calculated using the Debye-Scherrer equation, which was found to be 15.4 nm, similar to the TEM result.
또한, 상기 제조된 산화코발트 나노입자의 X선 회절분석(XRD)을 도 2(a)에 나타내었다. 그 결과 CoO상에 해당하는 피크만 관찰됨으로써 본 실시예 1의 코발트 나노입자가 모두 CoO 상으로만 이루어졌음을 확인할 수 있었다. In addition, X-ray diffraction analysis (XRD) of the prepared cobalt oxide nanoparticles is shown in Figure 2 (a). As a result, only the peak corresponding to the CoO phase was observed, and it was confirmed that all of the cobalt nanoparticles of Example 1 consisted of only the CoO phase.
1-2. 제조된 산화코발트 나노입자의 지지체 담지1-2. Support of Cobalt Oxide Nanoparticles Prepared
상기 제조된 산화코발트 나노입자 용액에 메탄올 100 mL를 혼합하여 산화코발트 나노입자를 응집-침전시킨 후, 이를 1-헥사데칸 용매로부터 분리하였다. 분리된 나노입자에 헥산을 혼합하여, 코발트 나노입자의 농도가 5 중량%인 콜로이드 용액을 제조하였다.100 mL of methanol was mixed with the cobalt oxide nanoparticle solution prepared above to coagulate-precipitate the cobalt oxide nanoparticles, and this was separated from the 1-hexadecane solvent. Hexane was mixed with the separated nanoparticles to prepare a colloidal solution having a concentration of 5% by weight of cobalt nanoparticles.
상기 제조된 5 중량% 산화코발트 나노입자 용액 10 g을 취하여 촉매지지체인 감마-알루미나(Al2O3, 비표면적: 320m2/g) 10 g에 함침시켰다. 50℃에서 헥산 용매를 증발시키고, 100℃ 오븐에서 건조하여 촉매를 제조하였다. 이때 제조된 촉매의 조성은 5%Co/Al2O3이다.10 g of the 5 wt% cobalt oxide nanoparticle solution prepared above was taken and impregnated into 10 g of a catalyst support, gamma-alumina (Al 2 O 3 , specific surface area: 320 m 2 / g). The hexane solvent was evaporated at 50 ° C. and dried in an 100 ° C. oven to prepare a catalyst. At this time, the composition of the prepared catalyst is 5% Co / Al 2 O 3 .
상기 지지체에 담지된 촉매의 TEM 이미지를 도 3(a)에, XRD 패턴을 도 4(a)에 나타내었다. 도 3(a)를 통해 상기 산화코발트 나노입자가 지지체에 고르게 담지되어 있음을 확인할 수 있었다. A TEM image of the catalyst supported on the support is shown in FIG. 3 (a), and an XRD pattern is shown in FIG. 4 (a). 3 (a) it was confirmed that the cobalt oxide nanoparticles are evenly supported on the support.
실시예 2: CoO상 70%와 Co3O4상 30%로 이루어진 코발트 촉매의 제조 (5% Co/Al2O3 - CoO 70%)Example 2: a 70% CoO and Co 3 O 4 phase producing a cobalt catalyst consisting of 30% (5% Co / Al 2 O 3 - CoO 70%)
상기 실시예 1의 캡핑된 코발트가 함유된 오일층을 270℃로 3시간 가열하는 것을 제외하고는, 실시예 1과 동일하게 코발트 나노입자를 제조하였다. Cobalt nanoparticles were prepared in the same manner as in Example 1, except that the capped cobalt-containing oil layer of Example 1 was heated to 270 ° C. for 3 hours.
상기 제조된 산화코발트의 나노입자의 투과전자현미경(TEM)사진을 도 1(b)에 나타내었다. 도 1(b)의 TEM 사진을 통해, 제조된 산화코발트 입자의 평균 크기가 14.2 nm임을 확인할 수 있었다. 또한, 디바이-셰러(Debye-Scherrer)식을 사용하여 산화코발트의 평균크기를 계산하였고 이는 15.2 ㎚로, TEM 결과와 유사함을 확인할 수 있었다.A transmission electron microscope (TEM) photograph of the prepared cobalt oxide nanoparticles is shown in FIG. 1 (b). From the TEM photograph of FIG. 1 (b), it could be confirmed that the average size of the prepared cobalt oxide particles was 14.2 nm. In addition, the average size of cobalt oxide was calculated using the Debye-Scherrer equation, which was found to be 15.2 nm, similar to the TEM result.
또한, 상기 제조된 산화코발트 나노입자의 X선 회절분석(XRD)을 도 2(b)에 나타내었다. 그 결과 CoO상에 해당하는 피크와 Co3O4상에 해당하는 피크가 모두 나타났고,상기 피크의 분포를 통해 CoO상의 함량이 70%임을 확인할 수 있었다.In addition, X-ray diffraction analysis (XRD) of the prepared cobalt oxide nanoparticles is shown in Figure 2 (b). As a result, both a peak corresponding to a CoO phase and a peak corresponding to a Co 3 O 4 phase appeared, and it was confirmed that the content of the CoO phase was 70% through the distribution of the peaks.
상기 제조된 코발트 나노입자의 지지체의 담지 역시, 실시예 1과 동일하게 수행하였다. 담지된 코발트 나노입자의 TEM 사진과 X선 회절분석 이미지를 각각 도 3(b)와 도 4(b)에 나타내었다. Support of the prepared cobalt nanoparticles was also carried out in the same manner as in Example 1. TEM images and X-ray diffraction images of the supported cobalt nanoparticles are shown in FIGS. 3 (b) and 4 (b), respectively.
실시예 3: CoO상 30%와 Co3O4상 70%로 이루어진 코발트 촉매의 제조 (5% Co/Al2O3 - CoO 30%)Example 3: a 30% CoO and Co 3 O 4 phase producing a cobalt catalyst consisting of 70% (5% Co / Al 2 O 3 - CoO 30%)
상기 실시예 1의 캡핑된 코발트가 함유된 오일층을 230℃로 3시간 가열하는 것을 제외하고는, 실시예 1과 동일하게 코발트 나노입자를 제조하였다.Cobalt nanoparticles were prepared in the same manner as in Example 1, except that the capped cobalt-containing oil layer of Example 1 was heated to 230 ° C. for 3 hours.
상기 제조된 산화코발트의 나노입자의 투과전자현미경(TEM)사진을 도 1(c)에 나타내었다. 도 1(c)의 TEM 사진을 통해, 제조된 산화코발트 입자의 평균 크기가 14.5 nm임을 확인할 수 있었다. 또한, 디바이-셰러(Debye-Scherrer)식을 사용하여 산화코발트의 평균크기를 계산하였고 이는 15.2 ㎚로, TEM 결과와 유사함을 확인할 수 있었다.A transmission electron microscope (TEM) photograph of the prepared cobalt oxide nanoparticles is shown in FIG. 1 (c). From the TEM photograph of FIG. 1 (c), it could be confirmed that the average size of the prepared cobalt oxide particles was 14.5 nm. In addition, the average size of cobalt oxide was calculated using the Debye-Scherrer equation, which was found to be 15.2 nm, similar to the TEM result.
또한, 상기 제조된 산화코발트 나노입자의 X선 회절분석(XRD)을 도 2(c)에 나타내었다. 그 결과 CoO상에 해당하는 피크와 Co3O4상에 해당하는 피크가 모두 나타났고, 상기 피크의 분포를 통해 CoO상의 함량이 30%임을 확인할 수 있었다.In addition, X-ray diffraction analysis (XRD) of the prepared cobalt oxide nanoparticles is shown in Figure 2 (c). As a result, both the peak corresponding to the CoO phase and the peak corresponding to the Co 3 O 4 phase appeared, and it was confirmed that the content of the CoO phase was 30% through the distribution of the peaks.
상기 제조된 코발트 나노입자의 지지체의 담지 역시, 실시예 1과 동일하게 수행하였다. 담지된 코발트 나노입자의 TEM 사진과 X선 회절분석 이미지를 각각 도 3(c)와 도 4(c)에 나타내었다.Support of the prepared cobalt nanoparticles was also carried out in the same manner as in Example 1. TEM images and X-ray diffraction images of the supported cobalt nanoparticles are shown in FIGS. 3 (c) and 4 (c), respectively.
비교예 1: Co3O4 (100%) 상만으로 이루어진 코발트계 촉매 제조Comparative Example 1: Co 3 O 4 (100%) Preparation of cobalt based catalyst consisting of only phase
상기 실시예 1의 캡핑된 코발트가 함유된 오일층을 200℃로 3시간 가열하는 것을 제외하고는, 실시예 1과 동일하게 코발트 나노입자를 제조하였다.Cobalt nanoparticles were prepared in the same manner as in Example 1, except that the capped cobalt-containing oil layer of Example 1 was heated to 200 ° C. for 3 hours.
상기 제조된 산화코발트의 나노입자의 투과전자현미경(TEM)사진을 도 1(d)에 나타내었다. 도 1(d)의 TEM 사진을 통해, 제조된 산화코발트 입자의 평균 크기가 14.8 nm임을 확인할 수 있었다. 또한, 디바이-셰러(Debye-Scherrer)식을 사용하여 산화코발트의 평균크기를 계산하였고 이는 15.7 ㎚로, TEM 결과와 유사함을 확인할 수 있었다.A transmission electron microscope (TEM) photograph of the prepared cobalt oxide nanoparticles is shown in FIG. 1 (d). Through the TEM photograph of FIG. 1 (d), it could be confirmed that the average size of the prepared cobalt oxide particles was 14.8 nm. In addition, the average size of cobalt oxide was calculated using the Debye-Scherrer equation, which was found to be 15.7 nm, similar to the TEM result.
또한, 상기 제조된 산화코발트 나노입자의 X선 회절분석(XRD)을 도 2(d)에 나타내었다. 그 결과 Co3O4상에 해당하는 피크만 관찰됨으로써 본 실시예 1의 코발트 나노입자가 모두 Co3O4 상으로만 이루어졌음을 확인할 수 있었다.In addition, X-ray diffraction analysis (XRD) of the prepared cobalt oxide nanoparticles is shown in Figure 2 (d). As a result, only the peak corresponding to the Co 3 O 4 phase was observed, it could be confirmed that all of the cobalt nanoparticles of Example 1 consisted of only the Co 3 O 4 phase.
비교예 2: 종래의 함침법에 의한 피셔-트롭시 합성용 촉매의 제조Comparative Example 2: Preparation of Fischer-Tropsch Synthesis Catalyst by Conventional Impregnation
20 mL의 3차 증류수와 질산코발트(Co(NO3)2·6H2O) 14g이 섞인 용액에 감마-알루미나 26.9g을 첨가하였다. 상기 슬러리를 100℃에서 12시간 이상 건조한 후, 500℃의 공기 분위기에서 5시간 동안 소성 처리하여 10% 코발트/알루미나 촉매를 제조하였다.26.9 g of gamma-alumina was added to a solution containing 20 mL of tertiary distilled water and 14 g of cobalt nitrate (Co (NO 3 ) 2 .6H 2 O). The slurry was dried at 100 ° C. for at least 12 hours, and then calcined at 500 ° C. for 5 hours to prepare a 10% cobalt / alumina catalyst.
비교예 3: 종래의 공침법에 의한 피셔-트롭시 합성용 촉매의 제조Comparative Example 3: Preparation of Fischer-Tropsch Synthesis Catalyst by Conventional Coprecipitation Method
20 mL의 3차 증류수와 28%의 수산화암모늄(NH4OH) 2.9 g이 섞인 용액을 준비하였다. 50 mL의 3차 증류수에 질산코발트(Co(NO3)2·6H2O) 7g 및 감마-알루미나 26.9g 이 섞인 슬러리에, 상기 용액을 격렬한 교반하에서 첨가하였다. 상기 첨가로 인해 침전된 수산화코발트-알루미나 슬러리를 회수한 후, 이를 필터하고 증류수 500 mL로 여러 번 나누어 세척하였다. 상기 슬러리를 100 ℃에서 12 시간 이상 건조한 후, 500 ℃의 공기 분위기에서 5 시간 동안 소성 처리하여 5% 코발트/알루미나 촉매를 제조하였다.A solution containing 20 mL of tertiary distilled water and 2.9 g of 28% ammonium hydroxide (NH 4 OH) was prepared. To a slurry of 7 g of cobalt nitrate (Co (NO 3 ) 2 .6H 2 O) and 26.9 g of gamma-alumina in 50 mL of tertiary distilled water, the solution was added under vigorous stirring. After recovering the cobalt hydroxide-alumina slurry precipitated by the addition, it was filtered and washed several times with distilled water 500 mL. The slurry was dried at 100 ° C. for at least 12 hours, and then calcined at 500 ° C. for 5 hours to prepare a 5% cobalt / alumina catalyst.
실험예 1: CoO 함량에 따른 촉매의 활성 조사Experimental Example 1 Investigation of Catalyst Activity According to CoO Content
상기 실시예 1 내지 3, 비교예 1 내지 3에서 제조된 촉매를 이용하여 피셔-트롭시 반응을 수행하고, 각 촉매의 활성을 비교분석 하였다.Fischer-Tropsch reaction was performed using the catalysts prepared in Examples 1 to 3 and Comparative Examples 1 to 3, and the activity of each catalyst was compared and analyzed.
실험을 위해, 1/2인치 스테인리스 고정층 반응기에 0.5g의 각 촉매를 장입하고, 350 ℃의 수소(5부피% H2/He) 분위기 하에서 5시간 환원 처리하였다. 반응온도 240 ℃, 반응압력 10 kg/cm2, 공간속도 3600 L/kgcat/hr의 조건에서 반응물인 일산화탄소 : 수소 : 아르곤(내부 표준물질)의 몰비를 31.5: 63.0: 5.5의 비율로 고정하여 반응기로 주입하였다. 피셔 트롭시 반응을 수행하고, 반응시간 40시간 후 촉매의 활성을 측정한 결과를 하기 표 1에 나타내었다.For the experiment, 0.5 g of each catalyst was charged to a 1/2 inch stainless steel fixed bed reactor and reduced for 5 hours under hydrogen (5% by volume H 2 / He) atmosphere at 350 ° C. Reaction temperature 240 ℃, reaction pressure 10 kg / cm 2 , The molar ratio of reactant carbon monoxide: hydrogen: argon (internal standard) at a rate of 3600 L / kg cat / hr was fixed at a ratio of 31.5: 63.0: 5.5 and injected into the reactor. Fischer Tropsi reaction was carried out, and the results of measuring the activity of the catalyst after the reaction time 40 hours are shown in Table 1 below.
표 1
Table 1
| 구분 | 촉매 | 코발트 산화물의 상(phase) | Co dispersion(%) | 수소흡착량(μmol/g)* | 코발트 산화물 환원도** | CoOX 나노입자 크기(nm)*** | CO 전환율(carbon mol%) | 카본 선택도(carbon mol%) | ||
| C1 | C2-C4 | C5+ | ||||||||
| 실시예 1 | 5%Co/γ-Al2O3 | CoO 100% | 4.0 | 15.9 | 73.1 | 14.8 | 64.4 | 18.4 | 11.8 | 69.8 |
| 실시예 2 | 5%Co/γ-Al2O3 | CoO 70%Co3O4 30% | 3.8 | 15.3 | 62.1 | 14.5 | 53.6 | 17.6 | 10.7 | 71.7 |
| 실시예 3 | 5%Co/γ-Al2O3 | CoO 30%Co3O4 70% | 3.5 | 14.1 | 48.7 | 14.2 | 36.6 | 16.8 | 8.9 | 74.3 |
| 비교예 1 | 5%Co/γ-Al2O3 | Co3O4 100% | 3.3 | 13.2 | 43.2 | 13.7 | 29.4 | 16.0 | 8.7 | 75.3 |
| 비교예 2 | 5%Co/γ-Al2O3 | Co3O4 100% | - | 8.5 | 32.5 | 7.5 | 8.5 | 23.1 | 17.8 | 59.1 |
| 비교예 3 | 10%Co/γ-Al2O3 | Co3O4 100% | - | 7.1 | 45.6 | <5 | 9.2 | 19.7 | 15.8 | 64.5 |
| division | catalyst | Phase of cobalt oxide | Co dispersion (%) | Hydrogen adsorption amount (μmol / g) * | Cobalt Oxide Reduction ** | CoO X nanoparticle size (nm) *** | CO conversion (carbon mol%) | Carbon selectivity (carbon mol%) | ||
| C 1 | C 2 -C 4 | C 5+ | ||||||||
| Example 1 | 5% Co / γ-Al 2 O 3 | CoO 100% | 4.0 | 15.9 | 73.1 | 14.8 | 64.4 | 18.4 | 11.8 | 69.8 |
| Example 2 | 5% Co / γ-Al 2 O 3 | CoO 70% Co 3 O 4 30% | 3.8 | 15.3 | 62.1 | 14.5 | 53.6 | 17.6 | 10.7 | 71.7 |
| Example 3 | 5% Co / γ-Al 2 O 3 | CoO 30% Co 3 O 4 70% | 3.5 | 14.1 | 48.7 | 14.2 | 36.6 | 16.8 | 8.9 | 74.3 |
| Comparative Example 1 | 5% Co / γ-Al 2 O 3 | Co 3 O 4 100% | 3.3 | 13.2 | 43.2 | 13.7 | 29.4 | 16.0 | 8.7 | 75.3 |
| Comparative Example 2 | 5% Co / γ-Al 2 O 3 | Co 3 O 4 100% | - | 8.5 | 32.5 | 7.5 | 8.5 | 23.1 | 17.8 | 59.1 |
| Comparative Example 3 | 10% Co / γ-Al 2 O 3 | Co 3 O 4 100% | - | 7.1 | 45.6 | <5 | 9.2 | 19.7 | 15.8 | 64.5 |
* 350℃에서 환원된 촉매의 100℃에서 화학흡착된 수소량* The amount of chemisorbed hydrogen at 100 ° C. of the catalyst reduced at 350 ° C.
** 350℃에서 환원된 촉매를 350℃에서 화학흡착된 산소량으로부터 계산된 코발트 산화물의 환원도** Reduction of cobalt oxide calculated from the amount of oxygen chemisorbed at 350 ° C. for a catalyst reduced at 350 ° C.
*** 제조한 촉매의 TEM에 의해 측정된 산화코발트의 크기 *** Size of cobalt oxide as measured by TEM of prepared catalyst
실시예 1 내지 3에서 제조한 촉매는, 담지된 촉매의 양이 5%로 작음에도 불구하고 촉매의 활성이 우수하였고, CoO상이 많을수록 촉매활성이 높게 나타났다.(실시예 1 > 실시예 2 > 실시예 3). The catalysts prepared in Examples 1 to 3 had excellent catalyst activity despite the small amount of supported catalyst (5%), and the higher the CoO phase, the higher the catalytic activity. (Example 1> Example 2> Example Example 3).
상기 표를 통해 알 수 있듯이, CoO상을 함유하는 실시예 1 내지 3은 Co3O4 상만으로 이루어진 비교예 1 내지 3에 비하여 C5+ 카본 선택도가 유사하면서도, 수소흡착량 및 CO 전환율이 훨씬 뛰어난 결과를 보여주었다. As can be seen from the table, Examples 1 to 3 containing the CoO phase is similar to the C5 + carbon selectivity compared to Comparative Examples 1 to 3 consisting of only the Co 3 O 4 phase, but the hydrogen adsorption amount and CO conversion rate is much better Showed results.
또한, 실시예 1 내지 3의 Co 분산(3.5~4.0)이 비교예 1의 분산(3.3)보다 우수함을 확인할 수 있었다. In addition, it was confirmed that the Co dispersion (3.5 to 4.0) of Examples 1 to 3 is superior to the dispersion (3.3) of Comparative Example 1.
따라서, 본 발명의 제조방법에 따라 제조된, CoO 상을 함유하는 피셔-트롭시 촉매가 기존 촉매에 비하여 수소흡착량 및 CO 전환율이 현저함을 확인할 수 있었다. Therefore, Fischer-Tropsch catalyst prepared according to the production method of the present invention, CoO phase was confirmed that the hydrogen adsorption amount and CO conversion rate is remarkable compared to the existing catalyst.
실시예 4: CoO상 100%의 코발트 나노입자가 감마-알루미자 지지체에 10% 담지된 촉매의 제조 (10% Co/Al2O3 - CoO 100%)Example 4: CoO phase of 100% cobalt nanoparticles gamma-manufacture of the supported catalyst in 10% aluminum chair support (10% Co / Al 2 O 3 - CoO 100%)
실시예 1과 동일하게 코발트 나노입자를 제조하였다. 제조된 촉매 지지체로의 담지는 나노 산화코발트 용액 20g을 취하여 감마-알루미나 10g에 함침하는 것을 제외하고는 실시예 1과 동일하게 제조하였다.Cobalt nanoparticles were prepared in the same manner as in Example 1. The supported catalyst was prepared in the same manner as in Example 1 except that 20 g of nanocobalt oxide solution was taken and impregnated in 10 g of gamma-alumina.
실시예 5: CoO상 100%의 코발트 나노입자가 감마-알루미자 지지체에 20% 담지된 촉매의 제조 (20% Co/Al2O3 - CoO 100%)Example 5: CoO phase of 100% cobalt nanoparticles gamma-manufacture of the supported catalyst in 20% aluminum chair support (20% Co / Al 2 O 3 - CoO 100%)
실시예 1과 동일하게 코발트 나노입자를 제조하였다. 제조된 촉매 지지체로의 담지는 나노 산화코발트 용액 40g을 취하여 감마-알루미나 10g에 함침하는 것을 제외하고는 실시예 1과 동일하게 제조하였다.Cobalt nanoparticles were prepared in the same manner as in Example 1. The supported catalyst was prepared in the same manner as in Example 1 except that 40 g of nanocobalt oxide solution was taken and impregnated into 10 g of gamma-alumina.
실시예 6: CoO상 100%의 코발트 나노입자가 감마-알루미자 지지체에 30% 담지된 촉매의 제조 (30% Co/Al2O3 - CoO 100%)Example 6: 100% CoO phase of the cobalt nanoparticles gamma-manufacture of the supported catalyst in 30% aluminum chair support (30% Co / Al 2 O 3 - CoO 100%)
실시예 1과 동일하게 코발트 나노입자를 제조하였다. 제조된 촉매 지지체로의 담지는 나노 산화코발트 용액 60g을 취하여 감마-알루미나 10g에 함침하는 것을 제외하고는 실시예 1과 동일하게 제조하였다.Cobalt nanoparticles were prepared in the same manner as in Example 1. The supported catalyst was prepared in the same manner as in Example 1 except that 60 g of nanocobalt oxide solution was taken and impregnated in 10 g of gamma-alumina.
비교예 4: CoO상 100%의 코발트 나노입자가 감마-알루미자 지지체에 2% 담지된 촉매의 제조 (2% Co/Al2O3 - CoO 100%)Comparative Example 4: 100% of CoO phase cobalt nanoparticles are gamma-manufacture of the supported 2% aluminum chair support catalyst (2% Co / Al 2 O 3 - CoO 100%)
실시예 1과 동일하게 코발트 나노입자를 제조하였다. 제조된 촉매 지지체로의 담지는 나노 산화코발트 용액 4g과 헥산 10g을 혼합한 용액을 취하여 감마-알루미나 10g에 함침하는 것을 제외하고는 실시예 1과 동일하게 제조하였다.Cobalt nanoparticles were prepared in the same manner as in Example 1. The supported catalyst was prepared in the same manner as in Example 1 except that 4 g of the nanocobalt oxide solution and 10 g of hexane were mixed and impregnated in 10 g of gamma-alumina.
비교예 5: CoO상 100%의 코발트 나노입자가 감마-알루미자 지지체에 50% 담지된 촉매의 제조 (50% Co/Al2O3 - CoO 100%)Comparative Example 5: 100% of CoO phase cobalt nanoparticles are gamma-manufacture of the supported catalyst in 50% aluminum chair support (50% Co / Al 2 O 3 - CoO 100%)
실시예 1과 동일하게 코발트 나노입자를 제조하였다. 제조된 촉매 지지체로의 담지는 나노 산화코발트 용액 100g을 취하여 감마-알루미나 10g에 함침하는 것을 제외하고는 실시예 1과 동일하게 제조하였다.Cobalt nanoparticles were prepared in the same manner as in Example 1. The supported catalyst was prepared in the same manner as in Example 1 except that 100 g of nanocobalt oxide solution was taken and impregnated in 10 g of gamma-alumina.
실험예 2: 코발트 나노입자 담지량에 따른 촉매의 활성 조사Experimental Example 2: Investigation of the Activity of the Catalyst According to the Cobalt Nanoparticle Supported Amount
상기 실시예 4 내지 6, 비교예 4 내지 5에서 제조된 촉매를 사용하는 것을 제외하고는, 실험예 1과 동일하게 피셔-트롭시 반응을 수행하였다. 상기 결과를 표 2에 나타내었다.Fischer-Tropsch reaction was performed in the same manner as in Experimental Example 1, except that the catalysts prepared in Examples 4 to 6 and Comparative Examples 4 to 5 were used. The results are shown in Table 2.
표 2
TABLE 2
| 구분 | 촉매 | 코발트 산화물의 상(phase) | 수소흡착량(μmol/g)* | 코발트 산화물 환원도** | CoOX 나노입자 크기(nm)*** | CO 전환율(carbon mol%) | 카본 선택도(carbon mol%) | ||
| C1 | C2-C4 | C5+ | |||||||
| 실시예 4 | 10%Co/γ-Al2O3 | CoO 100% | 30.2 | 76.2 | 14.9 | 72.7 | 13.3 | 9.3 | 77.4 |
| 실시예 5 | 20%Co/γ-Al2O3 | CoO 100% | 57.4 | 78.6 | 15.0 | 83.7 | 12.1 | 8.8 | 79.1 |
| 실시예 6 | 30%Co/γ-Al2O3 | CoO 100% | 81.6 | 79.4 | 15.3 | 89.6 | 10.9 | 8.4 | 80.7 |
| 비교예 4 | 2%Co/γ-Al2O3 | CoO 100% | 5.1 | 69.2 | 14.7 | 25.1 | 21.2 | 15.7 | 63.1 |
| 비교예 5 | 50%Co/γ-Al2O3 | CoO 100% | 69.30 | 80.5 | 15.5 | 69.3 | 8.9 | 6.6 | 84.5 |
| division | catalyst | Phase of cobalt oxide | Hydrogen adsorption amount (μmol / g) * | Cobalt Oxide Reduction ** | CoO X nanoparticle size (nm) *** | CO conversion (carbon mol%) | Carbon selectivity (carbon mol%) | ||
| C 1 | C 2 -C 4 | C 5+ | |||||||
| Example 4 | 10% Co / γ-Al 2 O 3 | CoO 100% | 30.2 | 76.2 | 14.9 | 72.7 | 13.3 | 9.3 | 77.4 |
| Example 5 | 20% Co / γ-Al 2 O 3 | CoO 100% | 57.4 | 78.6 | 15.0 | 83.7 | 12.1 | 8.8 | 79.1 |
| Example 6 | 30% Co / γ-Al 2 O 3 | CoO 100% | 81.6 | 79.4 | 15.3 | 89.6 | 10.9 | 8.4 | 80.7 |
| Comparative Example 4 | 2% Co / γ-Al 2 O 3 | CoO 100% | 5.1 | 69.2 | 14.7 | 25.1 | 21.2 | 15.7 | 63.1 |
| Comparative Example 5 | 50% Co / γ-Al 2 O 3 | CoO 100% | 69.30 | 80.5 | 15.5 | 69.3 | 8.9 | 6.6 | 84.5 |
* 350℃에서 환원된 촉매의 100℃에서 화학흡착된 수소량* The amount of chemisorbed hydrogen at 100 ° C. of the catalyst reduced at 350 ° C.
** 350℃에서 환원된 촉매를 350℃에서 화학흡착된 산소량으로부터 계산된 코발트 산화물의 환원도** Reduction of cobalt oxide calculated from the amount of oxygen chemisorbed at 350 ° C. for a catalyst reduced at 350 ° C.
*** 제조한 촉매의 TEM에 의해 측정된 산화코발트의 크기*** Size of cobalt oxide as measured by TEM of prepared catalyst
즉, 상기 표를 통해 알 수 있듯이 코발트 나노입자의 담지량이 10% 내지 30% 사이일 때 코발트 산화물 환원도 및 CO 전환율이 우수하였다. 실시예 4 내지 6에서, CoO의 담지량이 증가할수록 촉매 활성과 C5+ 선택성이 증가하였다. 반면, 코발트 나노입자의 담지량이 너무 작은 경우(2%, 비교예 4)에는 촉매활성과 선택도가 감소하였으며, 코발트 나노입자의 담지량이 큰 경우(50%, 비교예 5)에도 실시예 4 내지 6에 비하여 CO 전환율이 낮음을 확인할 수 있었다. 즉, 바람직한 코발트 나노입자의 담지량이 10% 내지 30%임을 확인할 수 있었다. That is, as can be seen through the above table, the cobalt oxide reduction and CO conversion were excellent when the supported amount of cobalt nanoparticles was between 10% and 30%. In Examples 4 to 6, as the amount of CoO supported, the catalytic activity and C5 + selectivity increased. On the other hand, when the supported amount of cobalt nanoparticles was too small (2%, Comparative Example 4), the catalytic activity and selectivity decreased, and even when the supported amount of cobalt nanoparticles was large (50%, Comparative Example 5) Compared to 6 it was confirmed that the CO conversion rate is low. That is, it was confirmed that the supported amount of the cobalt nanoparticles is 10% to 30%.
실시예 7: CoO상 100%의 코발트 나노입자가 실리카 지지체에 10% 담지된 촉매의 제조 (10%Co/SiO2 - CoO 100%)Example 7 Preparation of a Catalyst in which 10% of Cobalt Nanoparticles on CoO Supported on a Silica Support 10% (10% Co / SiO 2 -CoO 100%)
촉매 지지체로 실리카(SiO2, 비표면적 260m2/g, 평균 세공 직경 10 nm)를 이용한 것을 제외하고는 실시예 4와 동일한 방법으로 촉매를 제조하였다.A catalyst was prepared in the same manner as in Example 4, except that silica (SiO 2, specific surface area of 260 m 2 / g, average pore diameter of 10 nm) was used as the catalyst support.
실시예 8: CoO상 100%의 코발트 나노입자가 티타니아 지지체에 10% 담지된 촉매의 제조 (10%Co/SiO2 - CoO 100%)Example 8 Preparation of Catalyst with 10% Cobalt Nanoparticles on CoO Supported on Titania Support (10% Co / SiO 2- CoO 100%)
촉매 지지체로 티타니아(TiO2, 비표면적 120m2/g, 평균 세공 직경 12 nm)를 이용한 것을 제외하고는 실시예 4와 동일한 방법으로 촉매를 제조하였다.A catalyst was prepared in the same manner as in Example 4, except that titania (TiO 2, specific surface area of 120 m 2 / g, average pore diameter of 12 nm) was used as the catalyst support.
실시예 9: CoO상 100%의 코발트 나노입자가 SiO2로 개질된 감마-알루미나 지지체에 10% 담지된 촉매의 제조 (10%Co/3%SiO2/Al2O3 - CoO 100%)Example 9 Preparation of a Catalyst in which 100% of Cobalt Nanoparticles on CoO Are 10% Supported on a Gamma-Alumina Support Modified with SiO 2 (10% Co / 3% SiO 2 / Al 2 O 3 -CoO 100%)
에탄올 4g, 증류수 0.36g과 테트라에틸 오소실리케이트(tetraethyl orthosilicate, TEOS) 1.06g을 혼합하였다. 이를 감마-알루미나 10g에 담지시킨 후 80도로 가열하였다. 상기 가열로 TEOS가 가수분해되고, 표면이 SiO2로 개질된 감마-알루미나 촉매 지지체인 3%SiO2/Al2O3를 제조하였다. 4 g of ethanol, 0.36 g of distilled water, and 1.06 g of tetraethyl orthosilicate (TEOS) were mixed. It was loaded on 10 g of gamma-alumina and heated to 80 degrees. The TEOS is hydrolyzed by the heat, the surface is modified by SiO 2 gamma-alumina catalyst was prepared in the support chain 3% SiO 2 / Al 2 O 3.
촉매 지지체로 상기 3%SiO2/Al2O3를 이용한 것을 제외하고는 실시예 4와 동일한 방법으로 촉매를 제조하였다. A catalyst was prepared in the same manner as in Example 4, except that 3% SiO 2 / Al 2 O 3 was used as the catalyst support.
실험예 3: 촉매 지지체의 종류에 따른 촉매의 활성조사Experimental Example 3: Investigation of the Activity of the Catalyst According to the Type of Catalyst Support
상기 실시예 7 내지 실시예 9에서 제조된 촉매를 사용하는 것을 제외하고는, 실험예 1과 동일하게 피셔-트롭시 반응을 수행하였다. 상기 결과를 하기 표 3에 나타내었다.The Fischer-Tropsch reaction was performed in the same manner as in Experiment 1, except that the catalysts prepared in Examples 7 to 9 were used. The results are shown in Table 3 below.
표 3
TABLE 3
| 구분 | 촉매 | 코발트 산화물의 상(phase) | 수소흡착량(μmol/g)* | 코발트 산화물 환원도** | CoOX 나노입자 크기(nm)*** | CO 전환율(carbon mol%) | 카본 선택도(carbon mol%) | ||
| C1 | C2-C4 | C5+ | |||||||
| 실시예 7 | 10%Co/SiO2 | CoO 100% | 31.7 | 78.7 | 15.2 | 68.2 | 10.2 | 7.3 | 82.5 |
| 실시예 8 | 10%Co/TiO2 | CoO 100% | 27.2 | 73.1 | 14.6 | 61.2 | 12.7 | 9.5 | 77.8 |
| 실시예 9 | 10%Co/3%SiO2/γ-Al2O3 | CoO 100% | 30.8 | 78.6 | 14.9 | 75.3 | 14.5 | 10.4 | 75.1 |
| division | catalyst | Phase of cobalt oxide | Hydrogen adsorption amount (μmol / g) * | Cobalt Oxide Reduction ** | CoO X nanoparticle size (nm) *** | CO conversion (carbon mol%) | Carbon selectivity (carbon mol%) | ||
| C 1 | C 2 -C 4 | C 5+ | |||||||
| Example 7 | 10% Co / SiO 2 | CoO 100% | 31.7 | 78.7 | 15.2 | 68.2 | 10.2 | 7.3 | 82.5 |
| Example 8 | 10% Co / TiO 2 | CoO 100% | 27.2 | 73.1 | 14.6 | 61.2 | 12.7 | 9.5 | 77.8 |
| Example 9 | 10% Co / 3% SiO 2 / γ-Al 2 O 3 | CoO 100% | 30.8 | 78.6 | 14.9 | 75.3 | 14.5 | 10.4 | 75.1 |
* 350℃에서 환원된 촉매의 100℃에서 화학흡착된 수소량* The amount of chemisorbed hydrogen at 100 ° C. of the catalyst reduced at 350 ° C.
** 350℃에서 환원된 촉매를 350℃에서 화학흡착된 산소량으로부터 계산된 코발트 산화물의 환원도** Reduction of cobalt oxide calculated from the amount of oxygen chemisorbed at 350 ° C. for a catalyst reduced at 350 ° C.
*** 제조한 촉매의 TEM에 의해 측정된 산화코발트의 크기*** Size of cobalt oxide as measured by TEM of prepared catalyst
그 결과, 촉매 지지체로 다양한 물질(실리카, 티타니아, 표면이 개질된 지지체)을 사용하여도 본 발명 촉매의 수소흡착량 및 CO 전환율, 카본 선택도등의 성질이 우수하게 유지됨을 확인할 수 있었다. As a result, even when various materials (silica, titania, surface-modified support) were used as the catalyst support, it was confirmed that the properties of the hydrogen adsorption amount, CO conversion rate, and carbon selectivity of the catalyst of the present invention were excellently maintained.
실시예 10: 백금 조촉매 첨가Example 10 Platinum Promoter Addition
실시예 4에서 제조된 촉매에 증류수 6g에 백금 전구체인 테트라아민플래티늄 나이트레이트(tetraamineplatinum(II) nitrate) 0.02g을 용해시켜 추가로 담지하여 촉매를 제조하였다(실시예 10). The catalyst was prepared by further dissolving 0.02 g of tetraamineplatinum (II) nitrate, a platinum precursor, in 6 g of distilled water in the catalyst prepared in Example 4 (Example 10).
상기 실시예 10에서 제조된 백금 조촉매가 포함된 촉매를 사용하는 것을 제외하고는, 실험예 1과 동일하게 피셔-트롭시 반응을 수행하였다. 상기 결과를 하기 표 4에 나타내었다.Fischer-Tropsch reaction was performed in the same manner as in Experiment 1, except that the catalyst containing the platinum promoter prepared in Example 10 was used. The results are shown in Table 4 below.
표 4
Table 4
| 구분 | 촉매 | 코발트 산화물의 상(phase) | 수소흡착량(μmol/g)* | 코발트 산화물 환원도** | CoOX 나노입자 크기(nm)*** | CO 전환율(carbon mol%) | 카본 선택도(carbon mol%) | ||
| C1 | C2-C4 | C5+ | |||||||
| 실시예 10 | 0.1%Pt- 10%Co/γ-Al2O | CoO 100% | 33.9 | 82.5 | 14.6 | 90.3 | 15.2 | 11.2 | 73.6 |
| division | catalyst | Phase of cobalt oxide | Hydrogen adsorption amount (μmol / g) * | Cobalt Oxide Reduction ** | CoO X nanoparticle size (nm) *** | CO conversion (carbon mol%) | Carbon selectivity (carbon mol%) | ||
| C 1 | C 2 -C 4 | C 5+ | |||||||
| Example 10 | 0.1% Pt-10% Co / γ-Al 2 O | CoO 100% | 33.9 | 82.5 | 14.6 | 90.3 | 15.2 | 11.2 | 73.6 |
* 350℃에서 환원된 촉매의 100℃에서 화학흡착된 수소량* The amount of chemisorbed hydrogen at 100 ° C. of the catalyst reduced at 350 ° C.
** 350℃에서 환원된 촉매를 350℃에서 화학흡착된 산소량으로부터 계산된 코발트 산화물의 환원도** Reduction of cobalt oxide calculated from the amount of oxygen chemisorbed at 350 ° C. for a catalyst reduced at 350 ° C.
*** 제조한 촉매의 TEM에 의해 측정된 산화코발트의 크기*** Size of cobalt oxide as measured by TEM of prepared catalyst
그 결과 백금 조촉매를 첨가하는 경우, 백금 조촉매가 첨가되지 않은 촉매에 비하여 코발트 산화물 환원도 및 CO 전환율에 있어서 우수한 활성을 보임을 확인할 수 있었다.As a result, it was confirmed that the addition of the platinum promoter showed excellent activity in the reduction of cobalt oxide and the CO conversion compared to the catalyst without the platinum promoter.
실험예 4: 소성하여 환원시킨 경우 촉매의 활성 비교Experimental Example 4: Comparison of Catalyst Activity in the Case of Firing by Reduction
실시예 1 내지 4의 촉매를, 온도 400℃에서 5시간 동안 소성시켜 각각 비교예 6 내지 9의 촉매를 제조하였다.(비교예 6: 실시예 1의 촉매 소성, 비교예 7: 실시예 2의 촉매 소성, 비교예 8: 실시예 3의 촉매 소성, 비교예 9: 실시예 4의 촉매 소성)The catalysts of Examples 1 to 4 were calcined at a temperature of 400 ° C. for 5 hours to prepare catalysts of Comparative Examples 6 to 9, respectively. (Comparative Example 6: Catalyst Calcining of Example 1, Comparative Example 7: Catalytic Firing, Comparative Example 8: Catalytic Firing of Example 3, Comparative Example 9: Catalytic Firing of Example 4)
상기 비교예 6 내지 9에서 제조된 촉매를 사용하는 것을 제외하고는, 실험예 1과 동일하게 피셔-트롭시 반응을 수행하였다. 상기 결과를 표 5에 나타내었다.Fischer-Tropsch reaction was performed in the same manner as in Experiment 1, except that the catalysts prepared in Comparative Examples 6 to 9 were used. The results are shown in Table 5.
표 5
Table 5
| 구분 | 촉매 | 코발트 산화물의 상(phase) | Co dispersion(%) | 수소흡착량(μmol/g)* | 코발트 산화물 환원도** | CoOX 나노입자 크기(nm)*** | CO 전환율(carbon mol%) | 카본 선택도(carbon mol%) | ||
| C1 | C2-C4 | C5+ | ||||||||
| 비교예 6 | 5%Co/γ-Al2O3 | Co3O4 100% | 0.9 | 3.5 | 78.2 | 23.7 | 10.3 | 13.0 | 14.9 | 72.1 |
| 비교예 7 | 5%Co/γ-Al2O3 | Co3O4 100% | 1.5 | 6.1 | 63.1 | 21.7 | 18.5 | 13.2 | 15.8 | 71.0 |
| 비교예 8 | 5%Co/γ-Al2O3 | Co3O4 100% | 2.5 | 9.8 | 50.4 | 19.3 | 27.0 | 14.8 | 15.8 | 69.4 |
| 비교예 9 | 10%Co/γ-Al2O3 | Co3O4 100% | - | 12.2 | 44.8 | 35.4 | 35.4 | 15.2 | 16.0 | 68.8 |
| division | catalyst | Phase of cobalt oxide | Co dispersion (%) | Hydrogen adsorption amount (μmol / g) * | Cobalt Oxide Reduction ** | CoO X nanoparticle size (nm) *** | CO conversion (carbon mol%) | Carbon selectivity (carbon mol%) | ||
| C 1 | C 2 -C 4 | C 5+ | ||||||||
| Comparative Example 6 | 5% Co / γ-Al 2 O 3 | Co 3 O 4 100% | 0.9 | 3.5 | 78.2 | 23.7 | 10.3 | 13.0 | 14.9 | 72.1 |
| Comparative Example 7 | 5% Co / γ-Al 2 O 3 | Co 3 O 4 100% | 1.5 | 6.1 | 63.1 | 21.7 | 18.5 | 13.2 | 15.8 | 71.0 |
| Comparative Example 8 | 5% Co / γ-Al 2 O 3 | Co 3 O 4 100% | 2.5 | 9.8 | 50.4 | 19.3 | 27.0 | 14.8 | 15.8 | 69.4 |
| Comparative Example 9 | 10% Co / γ-Al 2 O 3 | Co 3 O 4 100% | - | 12.2 | 44.8 | 35.4 | 35.4 | 15.2 | 16.0 | 68.8 |
상기 표를 통해 알 수 있듯이, 실시예 1 내지 4에서 제조된 촉매를 소성하자 모두 Co3O4상이 100% 인 촉매로 되었다. 상기 Co3O4 상으로만 이루어진 촉매는 입자의 크기가 소성 전에 비하여 커졌으며, CO 전환율이 소성 전에 비하여 절반 이하로 감소하는 것을 확인할 수 있었다. 즉, 소성을 한 촉매는 소성을 하지 않은 촉매보다 촉매활성이 낮음을 확인할 수 있었다. As can be seen from the table, when the catalysts prepared in Examples 1 to 4 were calcined, all of them were catalysts having a Co 3 O 4 phase of 100%. The catalyst consisting of only the Co 3 O 4 phase was larger than the size of the particles before firing, it was confirmed that the CO conversion is reduced to less than half compared to before firing. In other words, the calcined catalyst was found to have lower catalytic activity than the uncalcined catalyst.
또한, 소성을 한 경우 Co 분산도가 2.5 미만으로 현저하게 감소함을 확인할 수 있었다. 소성을 하지 않은 실시예 1 내지 3의 분산도가 3.5 이상이었던 것에 비해 이는 현저하게 작은 수치로서, 소성을 통해 입자들의 응집이 일어났기 때문으로 판단된다. 즉, 기존 Co3O4 촉매는 고온 소성을 거쳐야 하므로 분산도가 떨어지게 되지만, 본원발명의 CoO 상을 포함하는 촉매는 소성과정 없이 환원되어 사용되므로 높은 분산도를 유지할 수 있음을 확인하였다.In addition, it was confirmed that Co dispersion significantly decreased to less than 2.5 when calcined. The dispersity of Examples 1 to 3, which did not fire, was 3.5 or more, which is a remarkably small value, which is considered to be due to the aggregation of particles through firing. That is, the existing Co 3 O 4 catalyst has a high degree of sintering, so that the dispersibility is reduced, but it was confirmed that the catalyst including the CoO phase of the present invention can be used without reduction because it can maintain a high degree of dispersion.
Claims (19)
- CoO 상(phase) 입자를 포함하는 피셔-트롭시 합성용 촉매의 제조방법에 있어서,In the manufacturing method of the catalyst for Fischer-Tropsch synthesis comprising CoO phase particles,코발트 공급 전구체 수용액과 염기성 화합물 수용액을 반응시켜 침전물을 형성하는 제1 단계;A first step of reacting a cobalt feed precursor aqueous solution with an aqueous basic compound solution to form a precipitate;상기 침전물을 캡핑(capping) 분자 및 비극성 유기 용매와 혼합하여 가열하는 제2 단계; 및A second step of heating the precipitate by mixing with a capping molecule and a nonpolar organic solvent; And상기 혼합물 중 유기 용매층을 회수하고 CoO 상 입자들을 형성하도록 230℃ 내지 350℃에서 가열하는 제3 단계;A third step of recovering the organic solvent layer in the mixture and heating at 230 ° C. to 350 ° C. to form CoO phase particles;를 포함하는 것이 특징인 제조방법. Manufacturing method characterized in that it comprises a.
- 제1항에 있어서, 이전 단계에서 제조된 CoO 상(phase) 입자들을 일부 또는 전부 포함하는 코발트 산화물 입자들을 지지체에 담지하는 제4단계를 추가로 더 포함하는 것이 특징인 제조방법. The method of claim 1, further comprising a fourth step of supporting the cobalt oxide particles including some or all of the CoO phase particles prepared in the previous step on the support.
- 제1항에 있어서, 제3단계에서 형성된 CoO 상 입자들의 함량이 촉매 성분인 코발트 산화물 100중량부를 기준으로 10중량부 내지 100중량부인 것이 특징인 제조방법.The method according to claim 1, wherein the content of the CoO phase particles formed in the third step is 10 parts by weight to 100 parts by weight based on 100 parts by weight of cobalt oxide as a catalyst component.
- 제1항에 있어서, 제3단계에서 형성된 CoO 상 입자들의 평균 직경은 5 내지 50 nm인 것이 특징인 제조방법. The method of claim 1, wherein the average diameter of the CoO phase particles formed in the third step is 5 to 50 nm.
- 제1항에 있어서, 제1 단계에서 코발트 공급 전구체는 질산코발트(Co(NO3)2·H2O), 염화코발트(CoCl2·H2O), 황산코발트(CoSO4), 초산코발트(Co(AC)2) 및 이의 혼합물로 이루어진 군에서 선택된 것이 특징인 제조방법. The cobalt feed precursor in the first step is cobalt nitrate (Co (NO 3 ) 2 H 2 O), cobalt chloride (CoCl 2 H 2 O), cobalt sulfate (CoSO 4 ), cobalt acetate ( Co (AC) 2 ) and a mixture thereof.
- 제1항에 있어서, 제1 단계에서 염기성 화합물은 암모니아, 수산화나트륨, 수산화칼륨, 수산화마그네슘, 수산화칼슘, 수산화암모늄, 탄산암모늄, 탄산수소암모늄, 탄산나트륨, 탄산수소나트륨, 탄산칼륨, 탄산수소칼륨 및 이의 혼합물로 이루어진 군에서 선택된 것이 특징인 제조방법. The method of claim 1, wherein in the first step, the basic compound is ammonia, sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide, ammonium hydroxide, ammonium carbonate, ammonium bicarbonate, sodium carbonate, sodium bicarbonate, potassium carbonate, potassium hydrogen carbonate and its Method for producing a mixture characterized in that selected from the group consisting of.
- 제1항에 있어서, 제2 단계에서 캡핑 분자는 포화 또는 불포화 C6 -C30 유기산 또는 지방산인 것이 특징인 제조방법.The method of claim 1 wherein the capping molecule in the second step is a saturated or unsaturated C 6 -C 30 organic acid or fatty acid.
- 제1항에 있어서, 제2 단계에서 캡핑 분자는 코발트 공급 전구체 1몰에 대하여 0.1 내지 2.5의 몰비로 사용되는 것이 특징인 제조방법.The method of claim 1 wherein the capping molecule is used in a second step in a molar ratio of 0.1 to 2.5 per mole of cobalt feed precursor.
- 제2항에 있어서, 상기 지지체는 감마-알루미나, 실리카, 티타니아, 개질된 감마-알루미나, 개질된 실리카, 개질된 티타니아 및 이의 혼합물로 이루어진 군에서 선택된 것이 특징인 제조방법.The method of claim 2, wherein the support is selected from the group consisting of gamma-alumina, silica, titania, modified gamma-alumina, modified silica, modified titania, and mixtures thereof.
- 제1항 내지 제9항 중 어느 한 항에 기재된 방법에 의해 제조된 것으로, CoO 상(phase) 입자를 포함하는 분리된 피셔-트롭시 합성용 촉매.A catalyst for separated Fischer-Tropsch synthesis, prepared by the method of any one of claims 1 to 9, comprising CoO phase particles.
- 제10항에 있어서, CoO 상(phase) 입자들이 지지체에 담지된 것이 특징인 피셔-트롭시 합성용 촉매.The catalyst for Fischer-Tropsch synthesis according to claim 10, wherein the CoO phase particles are supported on a support.
- 제11항에 있어서, 상기 지지체 100중량부를 기준으로 CoO 상 입자를 포함하는 촉매 성분 함량이 3중량부 내지 40중량부인 것이 특징인 피셔-트롭시 합성용 촉매.According to claim 11, Fischer-Tropsch synthesis catalyst, characterized in that the content of the catalyst component containing 3 to 40 parts by weight of CoO phase particles based on 100 parts by weight of the support.
- 제10항에 있어서, 상기 촉매는 백금, 루테늄, 레늄 또는 이의 혼합물로 이루어진 군에서 선택되는 귀금속을 추가로 더 포함하는 것이 특징인 피셔-트롭시 합성용 촉매. The catalyst for Fischer-Tropsch synthesis according to claim 10, wherein the catalyst further comprises a noble metal selected from the group consisting of platinum, ruthenium, rhenium or mixtures thereof.
- 제13항에 있어서, 촉매 100중량부를 기준으로 상기 귀금속의 함량이 0.01중량부 내지 1중량부인 것이 특징인 피셔-트롭시 합성용 촉매.The catalyst for Fischer-Tropsch synthesis according to claim 13, wherein the content of the noble metal is 0.01 part by weight to 1 part by weight based on 100 parts by weight of the catalyst.
- 피셔-트롭시 합성반응을 이용하여 천연가스로부터 액체 탄화수소를 제조하는 방법에 있어서, In the method for producing a liquid hydrocarbon from natural gas using a Fischer-Tropsch synthesis reaction,제1항 내지 제9항 중 어느 한 항에 기재된 방법에 의해 제조된 피셔-트롭시 합성용 촉매를 피셔-트롭시 합성반응기에 적용하는 a) 단계;A) applying the Fischer-Tropsch synthesis catalyst prepared by the method of any one of claims 1 to 9 to a Fischer-Tropsch synthesis reactor;CoO 상(phase) 입자를 포함하는 분리된 피셔-트롭시 합성용 촉매를 환원시켜 피셔-트롭시 합성용 촉매로 활성화시키는 b) 단계; 및B) reducing the separated Fischer-Tropsch synthesis catalyst comprising CoO phase particles to activate the Fischer-Tropsch synthesis catalyst; And상기 활성화된 피셔-트롭시 합성용 촉매에 의해 피셔-트롭시 합성반응을 수행하는 c) 단계를 포함하는 것이 특징인 제조방법.And c) performing a Fischer-Tropsch synthesis reaction by the activated Fischer-Tropsch synthesis catalyst.
- 제15항에 있어서, b) 단계는 별도의 소성과정 없이 수소 분위기 하에서 피셔-트롭시 합성용 촉매를 환원시키는 것이 특징인 제조방법.16. The method according to claim 15, wherein step b) reduces the Fischer-Tropsch synthesis catalyst under a hydrogen atmosphere without a separate firing process.
- 제16항에 있어서, b) 단계는 100℃ 내지 500℃의 수소분위기에서 수행되는 것이 특징인 제조방법. The method of claim 16, wherein step b) is carried out in a hydrogen atmosphere of 100 ℃ to 500 ℃.
- 제15항에 있어서, c) 단계는 200℃ 내지 350℃, 반응 압력 5 내지 30 kg/cm3, 공간속도 1000 - 10000 h-1에서 수행되는 것이 특징인 제조방법.The method according to claim 15, wherein the step c) is performed at 200 ° C to 350 ° C, a reaction pressure of 5 to 30 kg / cm 3 , and a space velocity of 1000 to 10000 h −1 .
- 제15항에 있어서, a) 단계에서 사용되는 촉매는 백금, 루테늄, 레늄 또는 이의 혼합물로 이루어진 군에서 선택되는 귀금속을 추가로 더 포함하는 것이 특징인 제조방법.The method of claim 15, wherein the catalyst used in step a) further comprises a precious metal selected from the group consisting of platinum, ruthenium, rhenium or mixtures thereof.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104289231A (en) * | 2014-10-09 | 2015-01-21 | 武汉凯迪工程技术研究总院有限公司 | High-dispersity cobalt-based Fischer-Tropsch synthesis catalyst as well as preparation method and application thereof |
| EP3345677A4 (en) * | 2016-06-07 | 2018-08-15 | LG Chem, Ltd. | Oxidative dehydrogenation reaction catalyst and preparation method therefor |
| CN109364881A (en) * | 2018-12-13 | 2019-02-22 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of feeble-acid-ammonium salt modified activated carbon and products thereof and application |
| CN114804221A (en) * | 2022-04-28 | 2022-07-29 | 荆门市格林美新材料有限公司 | Cobaltous oxide and preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20030030728A (en) * | 2001-10-12 | 2003-04-18 | 주식회사 한국나노기술 | Synthesis of Monodisperse and Highly-Crystalline Nanoparticles of Metals, Alloys, Metal Oxides, and Multi-metallic Oxides without a Size-selection Process |
| US20030211940A1 (en) * | 2000-06-12 | 2003-11-13 | Sasol Technology (Proprietary) Limited | Cobalt catalysts |
| US20080051474A1 (en) * | 2004-11-29 | 2008-02-28 | Dogterom Ronald J | Catalytic Process For The Conversion Of Co (II)Hydroxide In Co (III)Hydroxide |
| KR20090116054A (en) * | 2008-05-06 | 2009-11-11 | 한국화학연구원 | Cobalt-based catalyst for fischer-tropsch synthesis and method for preparing the same |
| KR20100007541A (en) * | 2008-07-14 | 2010-01-22 | 한국화학연구원 | Catalyst for synthesizing filamentous carbons at low temperature and preparation methods thereof |
-
2013
- 2013-01-30 KR KR1020130010728A patent/KR101578192B1/en active IP Right Grant
-
2014
- 2014-01-23 WO PCT/KR2014/000647 patent/WO2014119870A1/en active Application Filing
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030211940A1 (en) * | 2000-06-12 | 2003-11-13 | Sasol Technology (Proprietary) Limited | Cobalt catalysts |
| KR20030030728A (en) * | 2001-10-12 | 2003-04-18 | 주식회사 한국나노기술 | Synthesis of Monodisperse and Highly-Crystalline Nanoparticles of Metals, Alloys, Metal Oxides, and Multi-metallic Oxides without a Size-selection Process |
| US20080051474A1 (en) * | 2004-11-29 | 2008-02-28 | Dogterom Ronald J | Catalytic Process For The Conversion Of Co (II)Hydroxide In Co (III)Hydroxide |
| KR20090116054A (en) * | 2008-05-06 | 2009-11-11 | 한국화학연구원 | Cobalt-based catalyst for fischer-tropsch synthesis and method for preparing the same |
| KR20100007541A (en) * | 2008-07-14 | 2010-01-22 | 한국화학연구원 | Catalyst for synthesizing filamentous carbons at low temperature and preparation methods thereof |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104289231A (en) * | 2014-10-09 | 2015-01-21 | 武汉凯迪工程技术研究总院有限公司 | High-dispersity cobalt-based Fischer-Tropsch synthesis catalyst as well as preparation method and application thereof |
| EP3345677A4 (en) * | 2016-06-07 | 2018-08-15 | LG Chem, Ltd. | Oxidative dehydrogenation reaction catalyst and preparation method therefor |
| US10994262B2 (en) | 2016-06-07 | 2021-05-04 | Lg Chem, Ltd. | Catalyst for oxidative dehydrogenation and method of preparing the same |
| CN109364881A (en) * | 2018-12-13 | 2019-02-22 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of feeble-acid-ammonium salt modified activated carbon and products thereof and application |
| CN114804221A (en) * | 2022-04-28 | 2022-07-29 | 荆门市格林美新材料有限公司 | Cobaltous oxide and preparation method and application thereof |
| CN114804221B (en) * | 2022-04-28 | 2023-11-03 | 荆门市格林美新材料有限公司 | Cobalt oxide and preparation method and application thereof |
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