WO2018151568A1 - Catalyst for producing high-calorie synthetic natural gas and use thereof - Google Patents

Catalyst for producing high-calorie synthetic natural gas and use thereof Download PDF

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WO2018151568A1
WO2018151568A1 PCT/KR2018/002026 KR2018002026W WO2018151568A1 WO 2018151568 A1 WO2018151568 A1 WO 2018151568A1 KR 2018002026 W KR2018002026 W KR 2018002026W WO 2018151568 A1 WO2018151568 A1 WO 2018151568A1
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catalyst
iron
nickel
natural gas
weight
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French (fr)
Korean (ko)
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전기원
강석창
곽근재
김용태
김형식
박진모
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한국가스공사
한국화학연구원
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/005—Spinels
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/745—Iron
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/755—Nickel
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—
    • B01J35/40—
    • B01J35/60—
    • B01J35/613—
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/009—Preparation by separation, e.g. by filtration, decantation, screening
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
    • C10K3/00—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide
    • C10K3/02—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide by catalytic treatment

Definitions

  • the present invention relates to a catalyst for producing high-calorie synthetic natural gas, and a method and use thereof.
  • the catalyst according to the present invention is capable of producing a high calorific value synthetic natural gas having a high content of methane and C2-C4 paraffins from hydrogen and carbon monoxide, and simplifies the process due to high C1-C4 productivity.
  • Natural gas is a major component of CH 4 and is a clean fuel that generates little SO 2 during combustion and generates much less NOx, dust, and CO 2 than coal or oil.
  • carbon-containing materials such as coal, biomass, and waste are gasified to produce syngas which is a mixture of H 2 and CO, and the synthesis gas is used by using a catalyst.
  • Catalytic methanation technology that produces synthetic natural gas (SNG) by methanation has received new attention around the world.
  • Coal has the advantage of being longer than 200 years, the longest among the current fossil fuels, the relatively low price per calories, and distributed in various parts of the world in terms of supply and demand and energy security.
  • Coal gasification technology converts most of the energy of coal into chemical energy, which reduces the efficiency of the entire process due to temperature change in the post-refining process.
  • the main products of the coal gasification reaction are carbon monoxide and hydrogen, which produce a large amount of heat during combustion. That is, a large part of the energy in the sample is converted into gas containing chemical energy such as carbon monoxide or hydrogen by gasification reaction, and even though the gas is rapidly cooled, its own chemical energy is kept as it is, and if it is combusted, it is gas turbine or steam turbine. It has the advantage of recovering energy through.
  • Coal gasification technology injects coal into the gasifier to incomplete combustion to produce syngas containing CO and H 2 as main components, and then, through gas purification process, sulfur compounds such as COS and H 2 S Technology to produce synthetic natural gas (SNG), synthetic petroleum (Coal to Liquid, CTL), chemicals (methanol, DME, etc.) and power using the synthesis / power generation process.
  • SNG synthetic natural gas
  • CTL synthetic petroleum
  • chemicals methanol, DME, etc.
  • Coal gasification system is composed of gasifier, air separation equipment (oxygen supply equipment) and gas purification equipment, and other equipments are linked according to the final application purpose.
  • IGCC Gasification Combined Cycle
  • Synthetic natural gas may be natural gas obtained from coal.
  • the method for obtaining SNG from coal includes a method of obtaining synthesis gas obtained through coal gasification through a methane synthesis reaction (Gasification), a method of obtaining SNG by directly reacting coal with hydrogen (Hydrogasification), and a catalyst. Coal is reacted with steam at low temperature to obtain SNG.
  • Synthetic natural gas production process from the gasification of coal developed to date consists of coal gasification process and methanation process of syngas produced by coal gasification.
  • the gasification process of coal itself is complicated, the synthesis gas methanation process up to now is composed of two or three methanation reactors, or the process configuration is complicated by linking the methanation process with the C2-C4 paraffin production process. Difficulties in process operation and facility acquisition.
  • Catalyst technology the core technology of the synthetic natural gas production process, was developed mainly by nickel-based catalysts by Haldor-Topsoe, BASF, Johson & Metthey and Sud-Chemie.
  • Ni-based catalysts produce 1 mole of methane and 1 mole of water from 2 moles of carbon monoxide and the composition of the product is mostly methane. Therefore, the calorific value of the synthetic natural gas produced from the Ni-based catalyst is about 8500 Kcal / Nm 3, which is very low compared to LNG (about 10,500 Kcal / Nm 3 ) and LPG (about 12,000 Kcal / Nm 3 ), as described above. Processes are becoming more complex, such as linking C2-C4 paraffin production. Therefore, efforts have been made to develop a catalyst capable of simultaneously producing methane and C2-C4 paraffin and simplifying the process.
  • An object of the present invention is to provide a high calorific value of natural gas (SNG) production of methane and C2-C4 paraffins from hydrogen and carbon monoxide, and to provide a catalyst and a method for preparing the same, which can be simplified due to high C1-C4 productivity. I would like to.
  • SNG natural gas
  • a synthetic natural gas containing methane and C2-C4 paraffin from carbon monoxide in the presence of a Ni and Fe containing catalyst containing 80 to 95 parts by weight and 5 to 20 parts by weight of iron and nickel, respectively, and containing a spinel-structured magnetite It provides a method characterized by including the step.
  • CH 4 selectivity increased more than 2 times by addition of Ni active metal, and showed about 90% CH 4 selectivity when Ni ratio was over 20% of all active metals.
  • C 2 -C 4 selectivity and C 5+ selectivity were greatly reduced by the addition of Ni active metal, and in C 2 -C 4 hydrocarbons paraffin selectivity reached 100% by Ni addition.
  • the present invention is based on this finding, and the present invention controls the predominance of methanation reaction by Ni by controlling the ratio of Ni in the active metal to less than 20wt% in Ni and Fe-containing catalysts in which Fischer-Tropsh synthesis reaction and methanation reaction occur simultaneously. It is characterized by the production of high calorific value synthetic natural gas having a high C 2 -C 4 selectivity.
  • Ni and Fe-containing catalyst according to the present invention is based on iron and nickel 100 parts by weight of the active metal, iron and nickel are respectively 80 to 95 parts by weight and 5 to 20 Since parts by weight, nickel is not the main catalyst but iron is the main catalyst, and it is possible to produce a synthetic natural gas having a composition exhibiting a high calorific value of 9,000 Kcal / Nm 3 to 13,000 Kcal / Nm 3 .
  • the active metal in the catalyst may be iron oxide, nickel oxide, iron, nickel, iron-nickel alloy or a mixture thereof.
  • the catalyst may include a spinel structure of magnetite in an oxidized state, and may be mainly composed of a spinel structure of magnetite in a reduced state.
  • Ni and Fe-containing catalyst according to the present invention is a catalyst using two or more active metals so that the FT synthesis reaction and the methanation reaction simultaneously occur, composed of methane from hydrogen and carbon monoxide, and has a high C2-C4 paraffin content. It is possible to produce synthetic natural gas of calories, and because of high C1-C4 productivity, it is a catalyst that can simplify the process compared to the existing natural gas synthesis process.
  • the Ni and Fe-containing catalyst according to the present invention may have a specific surface area of 75 to 150 m 2 / g and an average particle diameter of pores of 4 to 8 nm.
  • Fe- and Ni-containing catalysts in which Fischer-Tropsh synthesis reaction and methanation reaction occur simultaneously, can increase the C2 ⁇ C4 composition ratio in SNG through Fischer-Tropsh synthesis reaction during SNG synthesis, and the Fischer-Tropsh synthesis reaction through methanation Unreacted CO and CO 2 can be methanated to increase the SNG yield. Due to these effects, it is possible to synthesize high calorific value SNG with high yield by the above method in which Fischer-Tropsh synthesis reaction and methanation reaction occur simultaneously.
  • Synthetic natural gas produced by the catalyst according to the invention is 9,000 Kcal / Nm 3 It may have a composition exhibiting a high calorific value of ⁇ 13,000 Kcal / Nm 3 .
  • a method for preparing a Ni- and Fe-containing catalyst for synthesizing natural gas with a composition exhibiting a high calorific value of methane: C 2 -C 4 paraffin (molar ratio) 1: 0.05 to 0.5,
  • a fourth step of precipitating and filtering the mixed solution obtained in the third step is a fourth step of precipitating and filtering the mixed solution obtained in the third step.
  • the filtrate obtained in the fourth step was dried and calcined at 450 to 650 ° C. to prepare a catalyst containing a spinel-structured magnetite with a specific surface area of 75 to 150 m 2 / g and an average particle diameter of 4 to 8 nm.
  • a fifth step is included.
  • Non-limiting examples of Fe-based precursors include iron nitrate, iron chloride, iron sulfate, iron acetate, and mixtures thereof.
  • Non-limiting examples of Ni-based precursors include nickel nitrate, nickel chloride, nickel sulfate, nickel acetate, and mixtures thereof. There is this.
  • the catalyst according to the present invention may further contain a promoter capable of easily controlling the catalytic performance, and non-limiting examples of promoter components include Mn, Cu, Co, Zn, K, Ce, Mg and combinations thereof. .
  • promoter components include Mn, Cu, Co, Zn, K, Ce, Mg and combinations thereof.
  • Mn a promoter capable of easily controlling the catalytic performance
  • Co promoters, methane and paraffin selectivity can be increased, and in the case of Mn, the catalyst selectivity and the hydrocarbon selectivity for high-calorie SNG synthesis are enhanced. Is effective.
  • the promoter component is preferably maintained at 0.5 to 5 parts by weight based on 100 parts by weight of Fe and Ni metals used. If the weight part of the cocatalyst is less than the lower limit, the enhancement effect by the cocatalyst is inadequate and undesirable. If the weight part of the cocatalyst is exceeded, undesirable side reactions occur by the cocatalyst, which is not preferable.
  • the catalyst according to the present invention may further comprise an inert structural enhancer component, and may include, but are not limited to, a metal oxide such as alumina or silica.
  • Structural enhancers can be used to disperse active metals in Fe oxide structures. Therefore, without using an alumina support with other nickel / iron precursors, a structural enhancer can be added to the catalyst by coprecipitation using an aluminum precursor (eg, aluminum nitrate (Al (NO 3 ) 3 .9H 2 O)). have.
  • Al precursor aluminum nitrate (Al (NO 3 ) 3 .9H 2 O
  • the precursor of the promoter and / or the precursor of the structural enhancer may be further included in the precursor solution of the first step.
  • Non-limiting examples of precursors of cocatalysts and / or precursors of structure enhancers include nitrates, chlorides, sulfur oxides, superoxides and mixtures thereof.
  • the second step is to prepare a mixed solution of the precipitant and distilled water, it is preferable that the precipitant mixed solution is an aqueous basic compound solution to co-precipitate the active metal and / or the promoter precursor and / or the structure enhancer precursor.
  • Non-limiting examples of precipitants include ammonia water, sodium hydroxide, potassium hydroxide, magnesium hydroxide, ammonium carbonate, sodium carbonate, potassium carbonate and mixtures thereof.
  • the precipitant is preferably used in the range of 0.9 to 1.1 equivalents relative to 1 equivalent of the active metal and the promoter and the structural enhancer component. If the amount of the basic compound is less than 0.9 equivalent ratio, the precipitation of the catalyst component is not complete, and if it exceeds 1.1 equivalent ratio, the precipitated catalyst component is dissolved again or the pH of the solution is too high. In addition, the pH of the aqueous basic compound solution is preferably maintained in the range of 6-9.
  • the third step is to mix the catalyst precursor solution and the precipitant solution.
  • the mixed solution obtained in the third step may be in a slurry state.
  • the third step can be stirred by heating during mixing.
  • the prepared slurry is subjected to a heating and stirring process for a predetermined time, the heating temperature and the heating time is preferably 60 to 100 °C and 1 to 5 hours.
  • the heating temperature and the heating time is less than the lower limit, it is not preferable because uniform dispersion of the active ingredient and the cocatalyst is difficult, and if the upper limit is exceeded, the catalyst particle size increases and the active point decreases and it takes a lot of time to be efficient. Therefore, it is not preferable.
  • the fourth step is the precipitation filtration process.
  • the slurry is washed with deionized water, and the amount of deionized water used is preferably washed three to five times using 30 to 50 ml per 1 g of slurry mass.
  • the amount of deionized water and the number of times of washing are less than the lower limit, the removal of impurities due to the precursor and the precipitant is not preferable, and if the upper limit is exceeded, there is no significant difference from the upper limit, which is not preferable because it is inefficient.
  • the water content of the filtrate obtained through the fourth step is preferably 50 to 80%.
  • the slurry filtration takes a considerable time and is inefficient, and if the water content exceeds the upper limit, pores are formed by rapid evaporation of water in the slurry during drying, resulting in deeper carbon deposition and reduced catalyst life. can do.
  • the fifth step is the drying and firing process of the filtrate.
  • the filtrate is preferably dried for 3 to 5 hours per g of slurry at a temperature of 90 to 110 °C, the product obtained after drying is preferably baked for 4 to 6 hours at 450 to 650 °C.
  • drying temperature When the drying temperature is less than the lower limit, it takes a considerable time to dry the slurry, which is not efficient. When the drying temperature is exceeded, pores may be formed by rapid evaporation of moisture in the slurry, resulting in deeper carbon deposition and reduced catalyst life. .
  • drying time is a lower limit, it is not preferable because the dried state of the slurry is insufficient, and if it exceeds the upper limit, it is not so different from the upper limit, which is not preferable because it is inefficient.
  • the calcination temperature is lower than the lower limit, it is not preferable because the solvent and organic impurities used in the manufacturing process are difficult to be completely removed by calcination, the uniform dispersion of the active ingredient and the enhancer is lowered, and the catalyst strength is weak, and the upper limit is exceeded. In this case, it is preferable to maintain the above range because a problem of lowering the specific surface area and the active point of the catalyst component due to the sintering phenomenon of the catalyst active component decreases the catalytic activity.
  • the calorific value of synthetic natural gas decreased with increasing catalyst firing temperature from 10,600 Kcal / Nm 3 to 10,350 Kcal / Nm 3 up to 550 °C, and again over 11,500 Kcal / Nm 3 above 600 °C. It showed a tendency to increase.
  • the yield of SNG showed the opposite trend of calorific value and was the highest with more than 70% at 550 ° C calcination catalyst.
  • the specific surface area of the final product obtained through the above processes is preferably 75 to 150 m 2 / g, and the average particle diameter of the pores is preferably 4 to 8 nm.
  • the specific surface area is less than the lower limit, the dispersion of the active metal and the enhancer is insufficient and not preferable. If the specific surface area is exceeded, the dispersibility of the active metal and the enhancer is increased, but the catalyst strength is lowered, which is not preferable.
  • the methanation reaction is insufficient to increase the liquid hydrocarbon production rate, thereby reducing the SNG yield.
  • the final product may be formed of iron oxide, nickel oxide, iron or nickel aluminate, or the like, and may include a magnetite having a spinel structure.
  • the activated (reduced) catalyst may be made of iron oxide, nickel oxide, iron, nickel, iron-nickel alloy.
  • the iron oxide as the active metal is Fe 2 O 3 , Fe 3 O 4 , or both
  • the nickel oxide may be NiO, Ni 2 O 3 , or both, and may mainly consist of magnetite having a spinel structure.
  • the final product is preferably 80 to 95 parts by weight and 5 to 20 parts by weight of iron and nickel, based on 100 parts by weight of iron and nickel, which are active metals.
  • the methanation reaction is insufficient to lower the SNG yield, which is not preferable. If the nickel content is exceeded, the FT synthesis reaction is insufficient and the C2-C4 hydrocarbon selectivity of the product is not preferable.
  • step a it may further comprise the step of reducing the catalyst in a hydrogen atmosphere in the temperature range of 300 ⁇ 600 °C.
  • the Fe- and Ni-containing catalysts according to the present invention allow the synthesis gas to be simultaneously FT synthesized and methanated to produce C1-C4 high calorific value synthetic natural gas.
  • step a The selectivity of methane is 33 ⁇ 82 carbon mol%, the selectivity of C2-C4 hydrocarbons may range from 3 to 17 carbon mol%, the ratio of paraffins in the C2-C4 hydrocarbons may range from 90 to 100 carbon mol%.
  • the carbon monoxide-containing feed gas of step a may be syngas produced by gasifying coal, biomass, or carbon-containing waste, or purified gas therefrom.
  • the H 2 / CO ratio of the feed gas (feed gas) is preferably 1.5 to 3.5.
  • the SNG yield decreases due to the water gas shift reaction and carbon deposition is intensified, and when the upper limit is exceeded, the selectivity of C2-C4 hydrocarbons is low, and the calorific value of SNG is reduced. It is not preferable because it is.
  • the synthetic natural gas synthesis reaction conditions are generally used and are not particularly limited.
  • the catalyst of the present invention can be utilized in the reaction after reduction in a hydrogen atmosphere in the temperature range of 300 to 600 °C in a fixed bed, fluidized bed and slurry reactor.
  • the reaction temperature is 300 to 400 °C
  • the reaction pressure is 20 to 40 bar
  • the space velocity is preferably 1000 ml / g cat h ⁇ 10000 ml / g cat ⁇ h.
  • the conversion is in the range of 90 to 100 carbon mole% at reaction conditions of 350 ° C., 30 atm and 6000 ml / g cat.h space velocity on the catalyst prepared by the process of the invention.
  • the composition of the synthetic natural gas produced is 33 to 82 carbon mol% of methane, C2-C4 hydrocarbons range from 3 to 17 carbon mol%.
  • the proportion of paraffins in the C2-C4 hydrocarbons ranges from 90 to 100 carbon mole%, and the gasoline fraction of by-product C5 or more hydrocarbons, specifically C5-C12, ranges from 6 to 13 carbon mole%.
  • the present invention is a catalyst produced by using two or more metals, using FT synthesis reaction and methanation simultaneously, producing and processing high calorific value natural natural gas composed mainly of methane and having high C2-C4 paraffin content.
  • a catalyst that can be simplified can be prepared.
  • Figure 1 shows the conversion and hydrocarbon selectivity by the catalyst prepared in Example 1 and Comparative Examples 1 to 3.
  • Figure 2 shows the calorific value and yield of SNG by the catalyst prepared in Example 1 and Comparative Examples 1 to 3.
  • Figure 6 shows the conversion and hydrocarbon selectivity by the catalyst prepared in Examples 2-5 and Comparative Example 4.
  • FIG. 7 shows the SNG calorific value and yield by the catalysts prepared in Examples 2 to 5 and Comparative Example 4.
  • Figure 8 shows the conversion and hydrocarbon selectivity in Examples 6 and 7 and Comparative Example 5.
  • 9 is a conceptual diagram of a method for obtaining SNG from coal.
  • the catalyst composition is 50Fe-50Ni-20Al, 80Fe-20Ni-20Al, 95Fe-5Ni-20Al, 98Fe-2Ni-20Al, respectively, so that the iron nitrate as shown in Table 1 (the amount of metal precursor used in the Fe-Ni catalyst according to the composition) (Fe (NO 3 ) 3 ⁇ 9H 2 O), nickel nitrate (Ni (NO 3 ) 2 ⁇ 6H 2 O), and aluminum nitrate (Al (NO 3 ) 3 ⁇ 9H 2 O) were dissolved in 200 ml of distilled water to prepare the precursor solution. Prepared.
  • the precipitant solution was prepared by dissolving 99.5% potassium carbonate (K 2 CO 3 ) in 300 ml of distilled water, as shown in Table 2 (the amount of precipitant used in the Fe-Ni catalyst according to the composition).
  • the precursor solution was added to the precipitant solution under vigorous stirring to prepare a precipitate slurry, and after stirring at 80 ° C. for 3 hours, the resulting precipitate was filtered and washed several times with distilled water 1,000 ml.
  • Iron hydroxide cake produced by the above process was filtered and dried until the water content is 55%.
  • the dried iron hydroxide cake was dried at 110 ° C. for 12 hours in a drying oven, and then fired at 450 ° C. for 4 hours under an air atmosphere in a kiln.
  • the prepared catalyst was consistent with the XRF analysis result and the designed catalyst composition as shown in Table 3, and from this, the catalyst preparation method confirmed that the catalyst composition could be produced in accordance with the catalyst composition designed according to the catalyst active metal ratio. It was.
  • the prepared catalyst was charged with 1 g of the catalyst prepared in Examples and Comparative Examples in a 1/2 inch stainless fixed bed reactor, and after 6 hours of reduction treatment under an H 2 atmosphere of 400 ° C., a reaction temperature of 350 ° C., The reactant synthesis gas was reacted at a reaction pressure of 30 bar and a space velocity of 6,000 ml / g cat.h , injected into the reactor at a fixed H 2 / CO ratio of 3 to carry out SNG synthesis.
  • the conversion of CO was close to 100% at all composition ratios and the CO to CO 2 conversion was decreased by the addition of Ni activated metal. In the case of Fe monocatalyst, the CO to CO 2 conversion was very high.
  • CH 4 selectivity increased more than 2 times by the addition of Ni active metal, and showed about 90% CH 4 selectivity when the Ni ratio was more than 20% of the total active metal.
  • C 2 -C 4 selectivity and C 5+ selectivity were greatly reduced by the addition of Ni active metal, and in C 2 -C 4 hydrocarbons paraffin selectivity reached 100% by Ni addition.
  • Fe monometallic catalyst is not suitable as a catalyst for SNG synthesis because of high CO to CO 2 conversion and low SNG yield, and high CH 4 selectivity and low C when Ni in the active metal is more than 20%. Due to the 2 -C 4 selectivity, since the calorific value is lowered, it is not suitable for the synthesis of high calorific value SNG.
  • the catalyst composition was 95Fe-5Ni-20Al, and iron nitrate (Fe (NO 3 ) 3 ⁇ 9H 2 O), nickel nitrate (Ni (NO 3 ) 2 ⁇ 6H 2 O) and aluminum nitrate (Al) as shown in the following table, respectively.
  • the precursor solution was added to a solution containing 38 g of 99.5% potassium carbonate (K 2 CO 3 ) and 300 ml of distilled water under vigorous stirring to stir the precipitate slurry at 80 ° C. for 3 hours, and then the resulting precipitate was filtered
  • the solution was washed several times with 1,000 ml of distilled water.
  • Iron hydroxide cake produced by the above process was filtered and dried until the water content is 55%.
  • the dried iron hydroxide cake was dried at 110 ° C. for 12 hours in a drying oven, and then calcined at 450 ° C., 500 ° C., 550 ° C., 600 ° C., and 700 ° C. for 4 hours in an air atmosphere in a kiln.
  • X-ray fluorescence (XRF), X-ray diffraction (XRD), temperature-reduction characterization (TPR) and BET pore characteristics of the iron-nickel dissimilar metal catalyst prepared above are shown in Table 4 (composition).
  • XRF analysis results of Fe-Ni catalyst according to the present invention is shown in FIGS. 3, 4, and 5.
  • the prepared catalyst was consistent with the XRF analysis result and the designed catalyst composition as shown in Table 4, and no change was observed with the calcination temperature. From this it was confirmed that by the catalyst preparation method, it can be produced in accordance with the designed catalyst composition, without a change according to the catalyst firing temperature.
  • Fe 2 O 3 and Fe 3 O 4 which are oxides of Fe, account for most of the active metal ratio.
  • peak The NiO peak and aluminate peaks of Fe and Ni were observed. Peak intensity markedly increased with increasing crystal size at firing temperature above 550 °C.
  • the Fe 2 O 3 peak was not observed or the intensity was greatly decreased among the XRD peaks of the catalyst, and the peak indicating the Fe 3 O 4 was the main peak.
  • iron metal peak and Fe-Ni alloy peak were observed by catalytic reduction, and intensity increased with increasing catalyst firing temperature.
  • TPR temperature-reduction characterization
  • the adsorption amount of catalyst N 2 decreased due to the decrease in porosity due to the sintering of the active ingredient with increasing catalyst firing temperature, and the distribution of hysteresis shifted to a higher relative pressure.
  • the specific surface area and pore volume of Table 5 showed a tendency to decrease with the catalyst firing temperature, and in particular, the specific surface area was greatly decreased above 550 ° C.
  • the pore size increased with the catalyst firing temperature, and the pore distribution of the catalyst according to each example in the pore distribution diagram of FIG. 5 was shifted to 6-12 nm in the distribution of 2-6 nm mainly with increasing the firing temperature.
  • the prepared catalyst was charged with 1 g of the catalyst prepared in Examples and Comparative Examples in a 1/2 inch stainless fixed bed reactor and reduced for 6 hours under an H 2 atmosphere of 400 ° C., followed by reaction temperature, 350 ° C., and reaction.
  • the reactant syngas was reacted at a pressure of 30 bar and a space velocity of 6,000 ml / g cat.h , and injected into the reactor with the H 2 / CO ratio set at 3 to perform the SNG synthesis reaction.
  • the CO conversion of 95Fe-5Ni-20Al catalyst was close to 100% regardless of the firing temperature except the 700 ° C firing catalyst, but the 700 ° C firing catalyst greatly reduced the CO conversion compared to other catalysts due to metal-aluminate formation. WGS activity was very high. In the case of the firing catalyst at 550 °C, the CO to CO 2 conversion and C 5+ selectivity were the lowest.
  • the amount of calorific value decreased from 10,600 Kcal / Nm 3 to 10,350 Kcal / Nm 3 up to 550 ° C, and increased to 11,500 Kcal / Nm 3 above 600 ° C.
  • the yield of SNG showed the opposite trend of calorific value and was the highest with more than 70% at 550 ° C calcination catalyst.
  • the calcination temperature of the catalyst is less than 450 degrees, it is difficult to completely remove the solvent and organic impurities used in the manufacturing process by calcination, the uniform dispersion of the active ingredient and the enhancer is lowered, and the catalyst strength is weak, so that high calorific value SNG synthesis is performed. It is not suitable as a catalyst for high calorific value SNG synthesis by reducing the reduction degree and deactivation due to excessive formation of Fe-aluminate and Ni-Aluminate and insufficient pore structure formation by sintering. not.

Abstract

In the present invention, a methane- and C2-C4 paraffin-containing synthetic natural gas is prepared from carbon monoxide in the presence of a Ni- and Fe-containing catalyst, which contains, on the basis of 100 parts by weight of iron and nickel as active metals, 80-95 parts by weight and 5-20 parts by weight of iron and nickel, respectively, and contains a spinel structure of magnetite. The catalyst according to the present invention, which is a catalyst using two or more kinds of active metals to induce simultaneous occurrence of an FT synthesis reaction and a methanation reaction, can produce a synthetic natural gas, which is mainly configured of methane from hydrogen and carbon monoxide and has a high content of C2-C4 paraffin and a high calorific value of 9,000-13,000 Kcal/Nm3, and can simplify the process compared with an existing natural gas synthesis process due to high productivity of C1-C4.

Description

고열량 합성천연가스 생산용 촉매 및 이의 용도Catalyst for producing high calorific synthetic natural gas and uses thereof
본 발명은 고열량 합성천연가스 생산용 촉매 및 이의 제조방법 및 용도에 관한 것이다. 본 발명에 따른 촉매는 수소 및 일산화탄소로부터 메탄 및 C2-C4 파라핀 함량이 높은 고발열량의 합성천연가스 생산이 가능하고, 높은 C1-C4 생산성으로 인하여 공정 간소화를 가능하게 한다. The present invention relates to a catalyst for producing high-calorie synthetic natural gas, and a method and use thereof. The catalyst according to the present invention is capable of producing a high calorific value synthetic natural gas having a high content of methane and C2-C4 paraffins from hydrogen and carbon monoxide, and simplifies the process due to high C1-C4 productivity.
천연가스는 CH4가 주성분이며 연소시 SO2는 거의 발생시키지 않고 NOx, 먼지, CO2 등을 석탄 또는 오일 보다 훨씬 적게 발생시키는 청정연료이므로 그 수요가 전세계적으로 계속 증가하고 있다. 그러나, 향후 천연가스의 공급이 수요 증가를 따르지 못할 것이 예상됨에 따라 석탄, 바이오매스, 폐기물 등의 탄소 함유 물질을 가스화하여 H2와 CO의 혼합물인 합성가스를 생산하고, 촉매를 사용하여 합성가스를 메탄화시켜 합성천연가스(SNG : synthetic natural gas)를 생산하는 촉매 메탄화 기술이 전세계적으로 새로운 관심을 받고 있다.Natural gas is a major component of CH 4 and is a clean fuel that generates little SO 2 during combustion and generates much less NOx, dust, and CO 2 than coal or oil. However, as the supply of natural gas is not expected to follow the increase in demand in the future, carbon-containing materials such as coal, biomass, and waste are gasified to produce syngas which is a mixture of H 2 and CO, and the synthesis gas is used by using a catalyst. Catalytic methanation technology that produces synthetic natural gas (SNG) by methanation has received new attention around the world.
석탄은 가채연한이 200년 이상으로 현재의 화석연료 중에 가장 길고, 열량당 가격이 상대적으로 저렴하며, 전세계 다양한 지역에 분포되어 수급 및 에너지 안보 측면에서 유리하다는 장점이 있다. Coal has the advantage of being longer than 200 years, the longest among the current fossil fuels, the relatively low price per calories, and distributed in various parts of the world in terms of supply and demand and energy security.
석탄가스화 기술은 석탄이 갖고 있는 에너지의 대부분을 화학에너지(chemical energy)로 전환함으로써 후단 정제공정에서의 온도변화로 인한 전체공정의 효율감소가 적다. 석탄가스화 반응의 주요 생산물은 일산화탄소와 수소이며 이들 가스는 연소 시 큰 발열량을 내게 된다. 즉, 가스화반응에 의해 시료 내의 상당부분 에너지가 일산화탄소나 수소 같이 화학에너지를 포함한 가스로 변환되고 이들 가스는 급속 냉각을 시키더라도 자체의 화학에너지가 그대로 유지되어 필요시 연소를 시키면 가스터빈이나 증기터빈을 통해 에너지를 재회수할 수 있다는 장점을 갖고 있다.Coal gasification technology converts most of the energy of coal into chemical energy, which reduces the efficiency of the entire process due to temperature change in the post-refining process. The main products of the coal gasification reaction are carbon monoxide and hydrogen, which produce a large amount of heat during combustion. That is, a large part of the energy in the sample is converted into gas containing chemical energy such as carbon monoxide or hydrogen by gasification reaction, and even though the gas is rapidly cooled, its own chemical energy is kept as it is, and if it is combusted, it is gas turbine or steam turbine. It has the advantage of recovering energy through.
석유자원의 무분별한 소비로 인하여 유가 상승세 및 최근 셰일가스 개발로 인한 석탄의 수요 감소로 석탄 가격의 하향세가 지속되고 있다. 또한, 중국의 석탄화학산업 발전계획에 의하여, 비교적 가채연한이 길고 가격이 저렴한 석탄을 이용한 에너지 및 화학제품 생산기술이 주목을 받고 있다. 그 중 석탄으로부터의 합성천연가스 생산기술은 1960년대 미국 내 천연가스 수요의 급증으로 인하여 석탄의 메탄화 공정을 개발하면서 시작되어, 1970년대 석유파동을 거쳐 현재까지 활발하게 연구되고 있다. The downward trend in coal prices is continuing due to rising oil prices due to reckless consumption of petroleum resources and the decrease in coal demand due to recent shale gas development. In addition, according to China's coal chemical industry development plan, the technology of producing energy and chemical products using coal, which is relatively long and inexpensive, has attracted attention. Among them, synthetic natural gas production technology from coal began with the development of coal methanation process due to the rapid increase of natural gas demand in the United States in the 1960s, and has been actively studied through the petroleum wave in the 1970s.
석탄가스화(Coal Gasification) 기술은 석탄을 가스화기에 주입하여 불완전 연소시켜 CO와 H2를 주성분으로 하는 합성가스(Syngas)를 제조한 후, 가스정제 공정을 거쳐서 COS, H2S등의 황화합물을 제거하고, 합성/발전 공정을 이용하여 합성천연가스(Synthetic Natural Gas, SNG), 합성석유(Coal to Liquid, CTL), 화학제품(메탄올, DME 등) 및 전력을 생산하는 기술이다.Coal gasification technology injects coal into the gasifier to incomplete combustion to produce syngas containing CO and H 2 as main components, and then, through gas purification process, sulfur compounds such as COS and H 2 S Technology to produce synthetic natural gas (SNG), synthetic petroleum (Coal to Liquid, CTL), chemicals (methanol, DME, etc.) and power using the synthesis / power generation process.
석탄가스화 시스템은 가스화기, 산소공급 장치인 공기분리설비, 가스정제설비로 구성되며, 최종 활용목적에 따라 다른 설비가 연계된다.Coal gasification system is composed of gasifier, air separation equipment (oxygen supply equipment) and gas purification equipment, and other equipments are linked according to the final application purpose.
석탄가스화 기술 중 가장 널리 알려진, 가스화 복합발전(IGCC)은 저급연료를 고온·고압 조건에서 불완전연소 및 가스화반응을 시켜 합성가스를 만들어 정제공정을 거친 후 가스터빈 및 증기터빈을 구동하는 친환경 차세대 발전기술이다.Gasification Combined Cycle (IGCC), one of the most popular coal gasification technologies, is an eco-friendly next-generation power generation that operates gas turbines and steam turbines by producing synthetic gas by incomplete combustion and gasification of low-grade fuel at high temperature and high pressure conditions. Technology.
합성천연가스(SNG)는 석탄으로부터 얻어진 천연가스일 수 있다. 도 9에 나타낸 바와 같이, 석탄으로부터 SNG를 얻는 방법에는 석탄 가스화를 통해 얻어진 합성가스를 메탄합성 반응을 통해 얻는 방법(Gasification), 석탄을 직접 수소와 반응시켜 SNG를 얻는 방법(Hydrogasification), 촉매를 이용하여 석탄을 저온에서 증기와 반응시켜 SNG를 얻는 방법(Catalytic Gasification)이 있다.Synthetic natural gas (SNG) may be natural gas obtained from coal. As shown in FIG. 9, the method for obtaining SNG from coal includes a method of obtaining synthesis gas obtained through coal gasification through a methane synthesis reaction (Gasification), a method of obtaining SNG by directly reacting coal with hydrogen (Hydrogasification), and a catalyst. Coal is reacted with steam at low temperature to obtain SNG.
현재까지 개발된 석탄의 가스화로부터 합성천연가스 생산공정은 석탄의 가스화 공정 및 석탄가스화로 생산된 합성가스의 메탄화 공정으로 이루어져 있다. 석탄의 가스화 공정 자체도 복잡하지만, 현재까지의 합성가스 메탄화 공정은 2 ~ 3기의 메탄화 반응기로 이루어지거나, 메탄화 공정과 C2-C4 파라핀 생산공정이 연계되는 방식으로 공정구성이 복잡하여 공정운영 및 설비확보에 어려움이 있다. Synthetic natural gas production process from the gasification of coal developed to date consists of coal gasification process and methanation process of syngas produced by coal gasification. Although the gasification process of coal itself is complicated, the synthesis gas methanation process up to now is composed of two or three methanation reactors, or the process configuration is complicated by linking the methanation process with the C2-C4 paraffin production process. Difficulties in process operation and facility acquisition.
합성천연가스 생산 공정의 핵심기술인 촉매기술은 Haldor-Topsoe, BASF, Johson & Metthey 및 Sud-Chemie사 등에 의하여 주로 니켈계 촉매를 중심으로 개발되었다. Catalyst technology, the core technology of the synthetic natural gas production process, was developed mainly by nickel-based catalysts by Haldor-Topsoe, BASF, Johson & Metthey and Sud-Chemie.
Ni 계 촉매는 2몰의 일산화탄소로부터 1몰의 메탄과 1몰의 물을 생성하여 생성물의 조성은 대부분 메탄으로 이루어진다. 그로 인하여, Ni계 촉매로부터 생산된 합성천연가스의 발열량은 약 8500 Kcal/Nm3으로, LNG(약 10,500 Kcal/Nm3) 및 LPG(약 12,000 Kcal/Nm3) 비하여 매우 낮기 때문에, 상기와 같이 C2-C4 파라핀 생산공정을 연계하는 등 공정이 복잡해지고 있다. 따라서, 메탄 및 C2-C4 파라핀 동시 생산이 가능한 촉매의 개발 및 이를 통한 공정 간소화 노력이 계속되고 있다. Ni-based catalysts produce 1 mole of methane and 1 mole of water from 2 moles of carbon monoxide and the composition of the product is mostly methane. Therefore, the calorific value of the synthetic natural gas produced from the Ni-based catalyst is about 8500 Kcal / Nm 3, which is very low compared to LNG (about 10,500 Kcal / Nm 3 ) and LPG (about 12,000 Kcal / Nm 3 ), as described above. Processes are becoming more complex, such as linking C2-C4 paraffin production. Therefore, efforts have been made to develop a catalyst capable of simultaneously producing methane and C2-C4 paraffin and simplifying the process.
본 발명의 목적은 수소 및 일산화탄소로부터 메탄 및 C2-C4 파라핀 함량이 높은 고발열량의 합성천연가스(SNG) 생산이 가능하고, 높은 C1-C4 생산성으로 인하여 공정 간소화가 가능한 촉매 및 이의 제조방법을 제공하고자 한다. An object of the present invention is to provide a high calorific value of natural gas (SNG) production of methane and C2-C4 paraffins from hydrogen and carbon monoxide, and to provide a catalyst and a method for preparing the same, which can be simplified due to high C1-C4 productivity. I would like to.
본 발명의 제1양태는 메탄 : C2-C4 파라핀 (몰비) = 1 : 0.05 ~ 0.5 로 고발열량을 발휘하는 조성의 합성천연가스를 제조하는 방법에 있어서, 활성금속인 철과 니켈 100 중량부를 기준으로, 철 및 니켈이 각각 80 내지 95 중량부 및 5 내지 20 중량부이고 스피넬 구조의 magnetite를 함유하는 Ni 및 Fe 함유 촉매 존재 하에, 일산화탄소로부터 메탄 및 C2-C4 파라핀 함유 합성천연가스를 제조하는 a단계를 포함하는 것이 특징인 방법을 제공한다.The first aspect of the present invention is a method for producing a synthetic natural gas having a composition exhibiting a high calorific value of methane: C 2 -C 4 paraffin (molar ratio) = 1: 0.05 to 0.5, based on 100 parts by weight of iron and nickel as active metals In order to prepare a synthetic natural gas containing methane and C2-C4 paraffin from carbon monoxide in the presence of a Ni and Fe containing catalyst containing 80 to 95 parts by weight and 5 to 20 parts by weight of iron and nickel, respectively, and containing a spinel-structured magnetite It provides a method characterized by including the step.
본 발명의 제2양태는 메탄 : C2-C4 파라핀 (몰비) = 1 : 0.05 ~ 0.5 로 고발열량을 발휘하는 조성의 합성천연가스 생산용 촉매로서, 활성금속인 철과 니켈 100 중량부를 기준으로, 철 및 니켈이 각각 80 내지 95 중량부 및 5 내지 20 중량부이고 스피넬 구조의 magnetite를 함유하는 것이 특징인 Ni 및 Fe 함유, FT 합성 및 메탄화 동시 반응용 촉매를 제공한다.The second aspect of the present invention is a catalyst for the production of synthetic natural gas having a high calorific value of methane: C2-C4 paraffin (molar ratio) = 1: 0.05 to 0.5, based on 100 parts by weight of iron and nickel as active metals, Ni and Fe characterized in that iron and nickel are 80 to 95 parts by weight and 5 to 20 parts by weight, respectively, and contain a spinel-structured magnetite Containing, for FT synthesis and methanation simultaneous reaction.
본 발명의 제3양태는 메탄 : C2-C4 파라핀 (몰비) = 1 : 0.05 ~ 0.5 로 고발열량을 발휘하는 조성의 합성천연가스 생산용 Ni 및 Fe 함유 촉매를 제조하는 방법에 있어서, 철과 니켈 100 중량부를 기준으로, 철 및 니켈이 각각 80 내지 95 중량부 및 5 내지 20 중량부가 되도록 Fe계 전구체 및 Ni계 전구체를 혼합하여 전구체 용액을 제조하는 제1단계; 침전제와 증류수의 혼합용액을 제조하는 제2단계; 상기 제1단계에서 얻어진 용액을 상기 제2단계에서 얻어진 용액과 혼합하는 제3단계; 상기 제3단계에서 얻어진 혼합용액을 침전여과하는 제4단계; 및 제4단계에서 얻어진 여과물을 건조 및 450 내지 650 ℃에서 소성하여, 스피넬 구조의 magnetite를 함유하면서 비표면적이 75 내지 150 m2/g이고 기공의 평균입경이 4 내지 8 nm인 촉매를 제조하는 제5단계를 포함하는 것이 특징인 촉매 제조방법을 제공한다.A third aspect of the present invention is a method for producing a Ni and Fe-containing catalyst for synthesizing natural gas production of a composition exhibiting a high calorific value of methane: C 2 -C 4 paraffin (molar ratio) = 1: 0.05 to 0.5. A first step of preparing a precursor solution by mixing Fe-based precursors and Ni-based precursors such that iron and nickel are 80 to 95 parts by weight and 5 to 20 parts by weight, respectively, based on 100 parts by weight; A second step of preparing a mixed solution of a precipitant and distilled water; A third step of mixing the solution obtained in the first step with the solution obtained in the second step; A fourth step of precipitating and filtering the mixed solution obtained in the third step; And drying the filtrate obtained in the fourth step and firing at 450 to 650 ° C. to prepare a catalyst containing a spinel structure of magnetite, having a specific surface area of 75 to 150 m 2 / g, and an average particle diameter of 4 to 8 nm. It provides a catalyst manufacturing method characterized in that it comprises a fifth step.
이하, 본 발명을 자세히 설명한다.Hereinafter, the present invention will be described in detail.
본 발명자들은 실험을 통해, 촉매 조성에 따라 다음과 같은 결과들을 처음으로 확인하였다: Through experiments, the inventors first confirmed the following results depending on the catalyst composition:
(i) Fe 단일금속 촉매의 경우, 발열량은 매우 높지만, CO to CO2 전환율이 높아, SNG 수율이 낮기 때문에 SNG 합성용 촉매로서 적합하지 않다. (i) In the case of Fe monometallic catalyst, the calorific value is very high, but it is not suitable as a catalyst for SNG synthesis because of high CO to CO 2 conversion and low SNG yield.
(ii) Ni 활성메탈의 첨가에 의하여 CO 전환율은 모든 조성비에서 100%에 근접하였으며, CO to CO2 전환율이 감소하였다.(ii) The conversion of CO was close to 100% at all composition ratios by the addition of Ni activated metal, and the CO to CO 2 conversion was decreased.
(iii) Ni 활성메탈의 첨가에 의하여 CH4 선택도는 2배 이상 증가되었으며, Ni 비율이 전체 활성메탈 중 20% 이상일 경우 약 90%의 CH4 선택도를 보였다. C2-C4 선택도 및 C5+ 선택도는 Ni 활성메탈 첨가에 의하여 크게 감소하였으며, C2-C4 탄화수소 내 paraffin 선택도는 Ni 첨가에 의하여 100%에 도달하였다. (iii) CH 4 selectivity increased more than 2 times by addition of Ni active metal, and showed about 90% CH 4 selectivity when Ni ratio was over 20% of all active metals. C 2 -C 4 selectivity and C 5+ selectivity were greatly reduced by the addition of Ni active metal, and in C 2 -C 4 hydrocarbons paraffin selectivity reached 100% by Ni addition.
(iv) SNG 수율은 Ni 첨가 및 첨가량에 따라 탄화수소 선택도 중 C5+ 선택도가 감소하여 증가하였으나, Fe:Ni이 50:50, 80:20 촉매의 경우 높은 SNG 수율에 비하여 발열량이 매우 낮은 문제점을 발견하였다. 예컨대, Ni 첨가시 Fe 단일 금속 촉매에 비하여, 발열량은 12,800 Kcal/Nm3에서 9,700 Kcal/Nm3로 크게 저하되었으며, Fe:Ni이 50:50 및 80:20에서 큰 차이는 없었다. 즉, 활성메탈 중 Ni의 비율이 20% 이상일 경우, 높은 CH4 선택도 및 낮은 C2-C4 선택도로 인하여, 발열량이 낮아지기 때문에, 고열량 SNG의 합성에는 적합하지 않다.(iv) The SNG yield increased with the addition of Ni and the amount of C 5+ selectivity in the hydrocarbon selectivity, but the Fe: Ni 50:50 and 80:20 catalysts had very low calorific value compared to the high SNG yield. I found a problem. For example, when Ni was added, the calorific value dropped significantly from 12,800 Kcal / Nm 3 to 9,700 Kcal / Nm 3 , and Fe: Ni was not significantly different at 50:50 and 80:20. That is, when the ratio of Ni in the active metal is 20% or more, the calorific value is low due to the high CH 4 selectivity and the low C 2 -C 4 selectivity, which is not suitable for the synthesis of high calorific value SNG.
(v) Fe:Ni이 95:5에서 SNG 발열량은 10,500 Kcal/Nm3 으로, 50:50 및 80:20에 비하여 높다는 것을 발견하였다. 활성메탈 중 철의 비율이 80% 미만일 경우, Ni에 의한 메탄화반응이 우세하여 생성물의 C2-C4 탄화수소 선택성이 저하되어 발열량이 낮아지는 것을 발견하였다.(v) Fe: Ni was found to have a SNG calorific value of 10,500 Kcal / Nm 3 at 95: 5, which is higher than that of 50:50 and 80:20. When the proportion of iron in the active metal is less than 80%, it was found that methanation reaction with Ni prevails, thereby lowering the C2-C4 hydrocarbon selectivity of the product and lowering the calorific value.
본 발명은 이러한 발견에 기초한 것으로, 본 발명은 Fischer-Tropsh 합성반응 및 메탄화 반응이 동시에 일어나는 Ni 및 Fe 함유 촉매에서 활성 메탈 중 Ni 비율을 20wt% 미만으로 조절하여 Ni에 의한 메탄화반응 우세를 저해하여 C2-C4 선택도가 높은 조성비의 고발열량 합성천연가스를 제조하는 것이 특징이다. The present invention is based on this finding, and the present invention controls the predominance of methanation reaction by Ni by controlling the ratio of Ni in the active metal to less than 20wt% in Ni and Fe-containing catalysts in which Fischer-Tropsh synthesis reaction and methanation reaction occur simultaneously. It is characterized by the production of high calorific value synthetic natural gas having a high C 2 -C 4 selectivity.
본 발명에 따른 Ni 및 Fe 함유 촉매는 활성금속인 철과 니켈 100 중량부를 기준으로, 철 및 니켈이 각각 80 내지 95 중량부 및 5 내지 20 중량부이므로, 니켈이 주된 촉매가 아니라 철이 주된 촉매이며, 9,000 Kcal/Nm3 ~ 13,000 Kcal/Nm3의 고발열량을 발휘하는 조성의 합성천연가스를 생산할 수 있다.Ni and Fe-containing catalyst according to the present invention is based on iron and nickel 100 parts by weight of the active metal, iron and nickel are respectively 80 to 95 parts by weight and 5 to 20 Since parts by weight, nickel is not the main catalyst but iron is the main catalyst, and it is possible to produce a synthetic natural gas having a composition exhibiting a high calorific value of 9,000 Kcal / Nm 3 to 13,000 Kcal / Nm 3 .
상기 촉매 중 활성금속은 철산화물, 니켈산화물, 철, 니켈, 철-니켈 합금 또는 이의 혼합물일 수 있다. 또한, 상기 촉매는 산화상태에서 magnetite의 스피넬 구조를 포함할 수 있으며, 환원 상태에서 주로 magnetite의 스피넬 구조로 이루어질 수 있다.The active metal in the catalyst may be iron oxide, nickel oxide, iron, nickel, iron-nickel alloy or a mixture thereof. In addition, the catalyst may include a spinel structure of magnetite in an oxidized state, and may be mainly composed of a spinel structure of magnetite in a reduced state.
본 발명에 따른 Ni 및 Fe 함유 촉매는, FT 합성반응 및 메탄화 반응이 동시에 일어나도록 2종 이상의 활성금속을 사용하는 촉매로서, 수소 및 일산화탄소로부터 주로 메탄으로 구성되고 C2-C4 파라핀 함량이 높은 고발열량의 합성천연가스의 생산이 가능하며, 높은 C1-C4 생산성으로 인하여 기존 천연가스합성공정에 비하여 공정의 간소화가 가능한 촉매이다. Ni and Fe-containing catalyst according to the present invention is a catalyst using two or more active metals so that the FT synthesis reaction and the methanation reaction simultaneously occur, composed of methane from hydrogen and carbon monoxide, and has a high C2-C4 paraffin content. It is possible to produce synthetic natural gas of calories, and because of high C1-C4 productivity, it is a catalyst that can simplify the process compared to the existing natural gas synthesis process.
<Fischer-Tropsch 합성 반응><Fischer-Tropsch Synthesis Reaction>
nCO + 2nH2 → -(CH2)n- + nH2OnCO + 2nH 2 →-(CH 2 ) n- + nH 2 O
<메탄화 반응><Methanation reaction>
nCO + 3nH2 ↔ nCH4 + nH2OnCO + 3nH 2 ↔ nCH 4 + nH 2 O
본 발명에 따른 Ni 및 Fe 함유 촉매는, 비표면적이 75 내지 150 m2/g이고 기공의 평균입경이 4 내지 8 nm일 수 있다.The Ni and Fe-containing catalyst according to the present invention may have a specific surface area of 75 to 150 m 2 / g and an average particle diameter of pores of 4 to 8 nm.
Fischer-Tropsh 합성반응 및 메탄화 반응이 동시에 일어나는 Fe 및 Ni 함유 촉매는 SNG 합성시 Fischer-Tropsh 합성반응을 통하여 SNG 내 C2~C4 조성비를 높일 수 있으며, 메탄화 반응을 통한 Fischer-Tropsh 합성반응의 미반응 CO 및 CO2를 메탄화하여, SNG 수율을 높일 수 있다. 이러한 효과들로 인하여, Fischer-Tropsh 합성반응 및 메탄화반응이 동시에 일어나는 상기 방법으로 높은 수율로 고발열량의 SNG 합성이 가능하다.Fe- and Ni-containing catalysts, in which Fischer-Tropsh synthesis reaction and methanation reaction occur simultaneously, can increase the C2 ~ C4 composition ratio in SNG through Fischer-Tropsh synthesis reaction during SNG synthesis, and the Fischer-Tropsh synthesis reaction through methanation Unreacted CO and CO 2 can be methanated to increase the SNG yield. Due to these effects, it is possible to synthesize high calorific value SNG with high yield by the above method in which Fischer-Tropsh synthesis reaction and methanation reaction occur simultaneously.
본 발명에 따른 촉매에 의해 제조되는 합성천연가스는 9,000 Kcal/Nm3 ~ 13,000 Kcal/Nm3의 높은 발열량을 발휘하는 조성을 가질 수 있다. 일구체예로, 합성천연가스는 메탄 : C2-C4 파라핀 (몰비) = 1 : 0.05 ~ 0.5 일 수 있다.Synthetic natural gas produced by the catalyst according to the invention is 9,000 Kcal / Nm 3 It may have a composition exhibiting a high calorific value of ~ 13,000 Kcal / Nm 3 . In one embodiment, the synthetic natural gas may be methane: C2-C4 paraffin (molar ratio) = 1: 0.05 to 0.5.
본 발명에 따라 메탄 : C2-C4 파라핀 (몰비) = 1 : 0.05 ~ 0.5 로 고발열량을 발휘하는 조성의 합성천연가스 생산용 Ni 및 Fe 함유 촉매를 제조하는 방법은,According to the present invention, a method for preparing a Ni- and Fe-containing catalyst for synthesizing natural gas with a composition exhibiting a high calorific value of methane: C 2 -C 4 paraffin (molar ratio) = 1: 0.05 to 0.5,
철과 니켈 100 중량부를 기준으로, 철 및 니켈이 각각 80 내지 95 중량부 및 5 내지 20 중량부가 되도록 Fe계 전구체 및 Ni계 전구체를 혼합하여 전구체 용액을 제조하는 제1단계; A first step of preparing a precursor solution by mixing Fe-based precursors and Ni-based precursors such that iron and nickel are 80 to 95 parts by weight and 5 to 20 parts by weight, respectively, based on 100 parts by weight of iron and nickel;
침전제와 증류수의 혼합용액을 제조하는 제2단계; A second step of preparing a mixed solution of a precipitant and distilled water;
상기 제1단계에서 얻어진 용액을 상기 제2단계에서 얻어진 용액과 혼합하는 제3단계; A third step of mixing the solution obtained in the first step with the solution obtained in the second step;
상기 제3단계에서 얻어진 혼합용액을 침전여과하는 제4단계; 및A fourth step of precipitating and filtering the mixed solution obtained in the third step; And
제4단계에서 얻어진 여과물을 건조 및 450 내지 650 ℃에서 소성하여, 스피넬 구조의 magnetite를 함유하면서 비표면적이 75 내지 150 m2/g이고 기공의 평균입경이 4 내지 8 nm인 촉매를 제조하는 제5단계를 포함한다. The filtrate obtained in the fourth step was dried and calcined at 450 to 650 ° C. to prepare a catalyst containing a spinel-structured magnetite with a specific surface area of 75 to 150 m 2 / g and an average particle diameter of 4 to 8 nm. A fifth step is included.
여기서, 활성금속의 조성비 및 소성온도에 따라 기공구조 및 phase의 특이성이 나타나는 것으로 유추된다.Here, it is inferred that the specificity of the pore structure and the phase appears depending on the composition ratio and firing temperature of the active metal.
Fe계 전구체의 비제한적인 예는 질산철, 염화철, 황산철, 초산철 및 이들의 혼합물이 있고, Ni계 전구체의 비제한적인 예는 질산니켈, 염화니켈, 황산니켈, 초산니켈 및 이들의 혼합물이 있다.Non-limiting examples of Fe-based precursors include iron nitrate, iron chloride, iron sulfate, iron acetate, and mixtures thereof. Non-limiting examples of Ni-based precursors include nickel nitrate, nickel chloride, nickel sulfate, nickel acetate, and mixtures thereof. There is this.
본 발명에 따른 촉매는 촉매성능을 용이하게 조절할 수 있는 조촉매를 더 함유할 수 있으며, 조촉매 성분의 비제한적인 예로는 Mn, Cu,Co, Zn, K, Ce, Mg 및 이의 조합이 있다. Cu,Co 조촉매의 경우 메탄 및 파라핀 선택도를 높일 수 있으며, Mn의 경우 Fe 활성금속의 안정성 증진, Ce의 경우 Ni 활성금속의 안정성 증진 등, 촉매 안정성 및 고열량 SNG 합성을 위한 탄화수소 선택도 증진에 효과가 있다.The catalyst according to the present invention may further contain a promoter capable of easily controlling the catalytic performance, and non-limiting examples of promoter components include Mn, Cu, Co, Zn, K, Ce, Mg and combinations thereof. . In the case of Cu, Co promoters, methane and paraffin selectivity can be increased, and in the case of Mn, the catalyst selectivity and the hydrocarbon selectivity for high-calorie SNG synthesis are enhanced. Is effective.
상기 조촉매 성분은 사용되는 Fe 및 Ni 금속 100 중량부를 기준으로 0.5 내지 5 중량부를 유지하는 것이 바람직하다. 상기 조촉매의 중량부가 하한 미만일 경우, 조촉매에 의한 증진효과가 미흡하여 바람직하지 않고, 상한을 초과할 경우 조촉매에 의하여 원하지 않는 부반응이 발생하여 바람직하지 않다.The promoter component is preferably maintained at 0.5 to 5 parts by weight based on 100 parts by weight of Fe and Ni metals used. If the weight part of the cocatalyst is less than the lower limit, the enhancement effect by the cocatalyst is inadequate and undesirable. If the weight part of the cocatalyst is exceeded, undesirable side reactions occur by the cocatalyst, which is not preferable.
본 발명에 따른 촉매는 활성이 없는 구조증진제 성분을 더 포함할 수 있으며, 비제한적인 예로 알루미나 또는 실리카와 같은 금속산화물일 수 있다. 구조증진제는 Fe 산화물 구조에 활성금속 분산을 위하여 사용될 수 있다. 따라서, 알루미나 지지체를 다른 니켈/철 전구체와 사용하지 아니하고, 알루미늄 전구체(예, 질산알루미늄(Al(NO3)3·9H2O))를 사용하여 공침법에 의해 구조증진제를 촉매에 추가할 수 있다. 또한, 알루미늄 전구체를 사용하는 경우, 촉매의 전체 조성 중 활성금속의 비율을 극대화 할 수 있기 때문에, 반응활성이 높은 촉매의 제조가 가능하다.The catalyst according to the present invention may further comprise an inert structural enhancer component, and may include, but are not limited to, a metal oxide such as alumina or silica. Structural enhancers can be used to disperse active metals in Fe oxide structures. Therefore, without using an alumina support with other nickel / iron precursors, a structural enhancer can be added to the catalyst by coprecipitation using an aluminum precursor (eg, aluminum nitrate (Al (NO 3 ) 3 .9H 2 O)). have. In addition, in the case of using the aluminum precursor, since the ratio of the active metal in the total composition of the catalyst can be maximized, it is possible to manufacture a catalyst with high reaction activity.
조촉매의 전구체 및/또는 구조증진제의 전구체는 제1단계의 전구체 용액에 추가로 더 포함될 수 있다.The precursor of the promoter and / or the precursor of the structural enhancer may be further included in the precursor solution of the first step.
조촉매의 전구체 및/또는 구조증진제의 전구체의 비제한적인 예로는, 질산화물, 염화물, 황산화물, 초산화물 및 이들의 혼합물이 있다.Non-limiting examples of precursors of cocatalysts and / or precursors of structure enhancers include nitrates, chlorides, sulfur oxides, superoxides and mixtures thereof.
제2단계는 침전제와 증류수의 혼합용액을 제조하는 단계로서, 활성금속 및/또는 조촉매 전구체 및/또는 구조증진제 전구체를 공침하기 위해 침전제 혼합용액은 염기성 화합물 수용액인 것이 좋다.The second step is to prepare a mixed solution of the precipitant and distilled water, it is preferable that the precipitant mixed solution is an aqueous basic compound solution to co-precipitate the active metal and / or the promoter precursor and / or the structure enhancer precursor.
침전제의 비제한적인 예로는 암모니아수, 수산화나트륨, 수산화칼륨, 수산화마그네슘, 탄산암모늄, 탄산나트륨, 탄산칼륨 및 이들의 혼합물 등이 있다.Non-limiting examples of precipitants include ammonia water, sodium hydroxide, potassium hydroxide, magnesium hydroxide, ammonium carbonate, sodium carbonate, potassium carbonate and mixtures thereof.
침전제는 활성금속 및 조촉매 및 구조증진제 성분의 1당량에 대하여 0.9 내지 1.1 당량비 범위로 사용하는 것이 바람직하다. 상기 염기성 화합물의 사용량이 0.9 당량비 미만이면 촉매성분의 침전이 완전하지 않으며, 1.1 당량비를 초과하는 경우에는 침전된 촉매성분이 다시 녹거나 용액의 pH가 너무 올라가는 문제가 발생한다. 또한, 상기 염기성 화합물 수용액의 pH는 6 ~ 9 범위를 유지하는 것이 바람직하다.The precipitant is preferably used in the range of 0.9 to 1.1 equivalents relative to 1 equivalent of the active metal and the promoter and the structural enhancer component. If the amount of the basic compound is less than 0.9 equivalent ratio, the precipitation of the catalyst component is not complete, and if it exceeds 1.1 equivalent ratio, the precipitated catalyst component is dissolved again or the pH of the solution is too high. In addition, the pH of the aqueous basic compound solution is preferably maintained in the range of 6-9.
제3단계는 촉매 전구체 용액과 침전제 용액을 혼합하는 단계이다. 제3단계에서 얻어진 혼합용액은 슬러리 상태일 수 있다. The third step is to mix the catalyst precursor solution and the precipitant solution. The mixed solution obtained in the third step may be in a slurry state.
제3단계는 혼합시 가열교반할 수 있다. 상기 제조된 슬러리는 일정시간 가열교반 과정을 거치며, 가열 온도 및 가열 시간은 60 내지 100 ℃ 및 1 시간 내지 5 시간이 바람직하다.The third step can be stirred by heating during mixing. The prepared slurry is subjected to a heating and stirring process for a predetermined time, the heating temperature and the heating time is preferably 60 to 100 ℃ and 1 to 5 hours.
가열온도 및 가열시간이 상기 하한 미만일 경우 활성성분 및 조촉매의 균일한 분산이 어렵기 때문에 바람직하지 않고, 상기 상한을 초과할 경우 촉매 입자 사이즈가 증가하여 활성점이 감소하고 많은 시간이 소요되어 효율적이지 않으므로 바람직하지 않다.If the heating temperature and the heating time is less than the lower limit, it is not preferable because uniform dispersion of the active ingredient and the cocatalyst is difficult, and if the upper limit is exceeded, the catalyst particle size increases and the active point decreases and it takes a lot of time to be efficient. Therefore, it is not preferable.
제4단계는 침전여과 과정이다. 침전여과 과정에서 슬러리는 탈 이온수를 사용하여 세척되며, 이때 사용되는 탈 이온수의 양은 슬러리 질량 1g 당 30 내지 50 ml를 사용하여 3 내지 5 회 세척하는 것이 바람직하다.The fourth step is the precipitation filtration process. In the precipitation filtration process, the slurry is washed with deionized water, and the amount of deionized water used is preferably washed three to five times using 30 to 50 ml per 1 g of slurry mass.
상기 탈 이온수의 양 및 세척횟수가 하한 미만일 경우, 전구체 및 침전제로 인한 불순물의 제거가 미흡하기 때문에 바람직하지 않고, 상한을 초과할 경우 상한과 큰 차이가 없어, 비효율적이기 때문에 바람직하지 않다.If the amount of deionized water and the number of times of washing are less than the lower limit, the removal of impurities due to the precursor and the precipitant is not preferable, and if the upper limit is exceeded, there is no significant difference from the upper limit, which is not preferable because it is inefficient.
상기 제4단계를 통하여 얻어진 여과물의 함수율은 50 내지 80 % 가 바람직하다.The water content of the filtrate obtained through the fourth step is preferably 50 to 80%.
상기 함수율이 하한 미만일 경우 슬러리 여과에 상당한 시간이 소요되어 비효율적이기 때문에 바람직하지 않고, 상한을 초과할 경우, 건조시 슬러리내 수분의 급격한 증발로 공극이 형성되어 탄소침적이 심화되고, 촉매수명이 감소할 수 있다.If the water content is less than the lower limit, it is not preferable because the slurry filtration takes a considerable time and is inefficient, and if the water content exceeds the upper limit, pores are formed by rapid evaporation of water in the slurry during drying, resulting in deeper carbon deposition and reduced catalyst life. can do.
제5단계는 여과물의 건조 및 소성과정이다. 여과물은 90 내지 110℃의 온도에서 슬러리 1g 당 3 내지 5 시간 동안 건조하는 것이 바람직하며, 건조 후 얻어진 생성물은 450 내지 650 ℃에서 4 내지 6 시간 동안 소성하는 것이 바람직하다. The fifth step is the drying and firing process of the filtrate. The filtrate is preferably dried for 3 to 5 hours per g of slurry at a temperature of 90 to 110 ℃, the product obtained after drying is preferably baked for 4 to 6 hours at 450 to 650 ℃.
상기 건조 온도가 하한 미만일 경우, 슬러리 건조에 상당한 시간이 소요되어 효율적이지 않고, 상한을 초과할 경우, 슬러리내 수분의 급격한 증발로 공극이 형성되어 탄소침적이 심화되고, 촉매수명이 감소할 수 있다.When the drying temperature is less than the lower limit, it takes a considerable time to dry the slurry, which is not efficient. When the drying temperature is exceeded, pores may be formed by rapid evaporation of moisture in the slurry, resulting in deeper carbon deposition and reduced catalyst life. .
상기 건조 시간이 하한일 경우, 슬러리의 건조상태가 미흡하기 때문에 바람직하지 않고, 상한을 초과할 경우, 상한과 크게 다르지 않아, 비효율적이기 때문에 바람직하지 않다. If the drying time is a lower limit, it is not preferable because the dried state of the slurry is insufficient, and if it exceeds the upper limit, it is not so different from the upper limit, which is not preferable because it is inefficient.
상기 소성온도가 하한 미만이면 제조 과정에 사용된 용매 및 유기 불순물이 소성에 의해 완전히 제거하기가 어렵고, 활성성분과 증진제의 균일한 분산이 저하되며, 촉매 강도가 약하기 때문에 바람직하지 않고, 상한을 초과할 경우 촉매 활성성분의 소결(sintering) 현상에 의한 촉매성분의 비표면적 및 활성점을 감소시켜 촉매활성을 저하시키는 문제가 발생하므로 상기 범위를 유지하는 것이 바람직하다. If the calcination temperature is lower than the lower limit, it is not preferable because the solvent and organic impurities used in the manufacturing process are difficult to be completely removed by calcination, the uniform dispersion of the active ingredient and the enhancer is lowered, and the catalyst strength is weak, and the upper limit is exceeded. In this case, it is preferable to maintain the above range because a problem of lowering the specific surface area and the active point of the catalyst component due to the sintering phenomenon of the catalyst active component decreases the catalytic activity.
합성천연가스의 발열량은 촉매 소성 온도의 증가에 따라 550 ℃ 까지 10,600 Kcal/Nm3에서 10,350 Kcal/Nm3까지 감소하는 경향을 보였으며, 600 ℃ 이상에서는 다시 11,500 Kcal/Nm3 까지 증가하는 경향을 보였다. SNG 수율은 발열량과 반대 경향을 보였으며, 550 ℃ 소성 촉매에서 70% 이상으로 가장 높았다.The calorific value of synthetic natural gas decreased with increasing catalyst firing temperature from 10,600 Kcal / Nm 3 to 10,350 Kcal / Nm 3 up to 550 ℃, and again over 11,500 Kcal / Nm 3 above 600 ℃. It showed a tendency to increase. The yield of SNG showed the opposite trend of calorific value and was the highest with more than 70% at 550 ° C calcination catalyst.
상기 과정들을 통하여 얻어진 최종생성물의 비표면적은 75 내지 150 m2/g이 바람직하며, 기공의 평균입경은 4 내지 8 nm가 바람직하다.The specific surface area of the final product obtained through the above processes is preferably 75 to 150 m 2 / g, and the average particle diameter of the pores is preferably 4 to 8 nm.
상기 비표면적이 하한 미만일 경우, 활성금속 및 증진제의 분산이 미흡하여 바람직하지 않고, 상한을 초과할 경우 활성금속 및 증진제의 분산성이 높아지지만, 촉매 강도가 저하되어 바람직하지 않다.If the specific surface area is less than the lower limit, the dispersion of the active metal and the enhancer is insufficient and not preferable. If the specific surface area is exceeded, the dispersibility of the active metal and the enhancer is increased, but the catalyst strength is lowered, which is not preferable.
상기 기공크기가 하한 미만일 경우, 또는 상한을 초과할 경우 메탄화 반응이 미흡하여 액상탄화수소 생성률이 증가하며, 그로 인하여, SNG 수율이 저하된다.If the pore size is less than the lower limit, or exceeds the upper limit, the methanation reaction is insufficient to increase the liquid hydrocarbon production rate, thereby reducing the SNG yield.
상기 최종생성물의 형태는 철산화물, 니켈산화물, 철 또는 니켈알루미네이트 등으로 이루어질 수 있으며, 스피넬 구조의 magnetite를 포함할 수 있다. 또한, 활성화(환원)된 촉매는 철산화물, 니켈산화물, 철, 니켈, 철-니켈 합금으로 이루어질 수 있다. 이때, 활성금속인 철산화물은 Fe2O3, Fe3O4, 또는 둘다이고, 니켈산화물은 NiO, Ni2O3, 또는 둘다일 수 있으며, 주로 스피넬 구조의 magnetite로 이루어질 수 있다. The final product may be formed of iron oxide, nickel oxide, iron or nickel aluminate, or the like, and may include a magnetite having a spinel structure. In addition, the activated (reduced) catalyst may be made of iron oxide, nickel oxide, iron, nickel, iron-nickel alloy. In this case, the iron oxide as the active metal is Fe 2 O 3 , Fe 3 O 4 , or both, The nickel oxide may be NiO, Ni 2 O 3 , or both, and may mainly consist of magnetite having a spinel structure.
상기 최종생성물의 조성은 활성금속인 철과 니켈 100 중량부를 기준으로, 철 및 니켈이 각각 80 내지 95 중량부 및 5 내지 20 중량부인 것이 바람직하다.The final product is preferably 80 to 95 parts by weight and 5 to 20 parts by weight of iron and nickel, based on 100 parts by weight of iron and nickel, which are active metals.
상기 철의 조성이 하한 미만일 경우, Ni에 의한 메탄화반응이 우세하여 생성물의 C2-C4 탄화수소 선택성이 저하되어 발열량이 낮기 때문에 바람직하지 않고, 상한을 초과할 경우 Fe의 특성이 우세하여 수성가스 전환반응으로 인한 SNG 수율이 저하되고 올레핀 선택도가 높기 때문에 바람직하지 않다.When the iron composition is less than the lower limit, methanation reaction with Ni is predominant, and the C2-C4 hydrocarbon selectivity of the product is lowered, which is not preferable because the calorific value is low. It is not preferable because the SNG yield due to the reaction is lowered and the olefin selectivity is high.
상기 니켈의 조성이 하한 미만일 경우, 메탄화반응이 미흡하여 SNG 수율이 저하되어 바람직하지 않고, 상한을 초과할 경우 FT 합성반응이 미흡하여 생성물의 C2-C4 탄화수소 선택도가 낮기 때문에 바람직하지 않다.If the composition of the nickel is less than the lower limit, the methanation reaction is insufficient to lower the SNG yield, which is not preferable. If the nickel content is exceeded, the FT synthesis reaction is insufficient and the C2-C4 hydrocarbon selectivity of the product is not preferable.
또한, 본 발명은 메탄 : C2-C4 파라핀 (몰비) = 1 : 0.05 ~ 0.5 로 고발열량을 발휘하는 조성의 합성천연가스를 제조하는 방법으로서,In addition, the present invention is a method for producing a synthetic natural gas of a composition exhibiting a high calorific value of methane: C2-C4 paraffin (molar ratio) = 1: 0.05 to 0.5,
활성금속인 철과 니켈 100 중량부를 기준으로, 철 및 니켈이 각각 80 내지 95 중량부 및 5 내지 20 중량부이고 스피넬 구조의 magnetite를 함유하는 Ni 및 Fe 함유 촉매 존재 하에, 일산화탄소로부터 메탄 및 C2-C4 파라핀 함유 합성천연가스를 제조하는 a단계를 포함하는 것이 특징인 방법을 제공한다.Based on 100 parts by weight of the active metals iron and nickel, methane and C2- from carbon monoxide in the presence of a Ni and Fe-containing catalyst containing 80 to 95 parts by weight and 5 to 20 parts by weight respectively and containing a spinite-structured magnetite It provides a method characterized by comprising a step of preparing a C4 paraffin-containing synthetic natural gas.
이때, a단계 이전 또는 이후에, 300 ∼ 600 ℃의 온도 범위의 수소 분위기에서 촉매를 환원하는 단계를 더 포함할 수 있다.At this time, before or after step a, it may further comprise the step of reducing the catalyst in a hydrogen atmosphere in the temperature range of 300 ~ 600 ℃.
본 발명에 따른 Fe 및 Ni 함유 촉매에 의해 합성가스를 동시에 FT 합성반응 및 메탄화반응하게 함으로써, C1-C4의 고발열량 합성천연가스를 제조할 수 있다. The Fe- and Ni-containing catalysts according to the present invention allow the synthesis gas to be simultaneously FT synthesized and methanated to produce C1-C4 high calorific value synthetic natural gas.
따라서, a단계에서 메탄의 선택도는 33~82 카본 몰 % 이고, C2-C4 탄화수소의 선택도는 3~17 카본 몰 % 범위이며, C2-C4 탄화수소 중 파라핀의 비율이 90 ~ 100 카본몰 % 범위일 수 있다. Therefore, in step a The selectivity of methane is 33 ~ 82 carbon mol%, the selectivity of C2-C4 hydrocarbons may range from 3 to 17 carbon mol%, the ratio of paraffins in the C2-C4 hydrocarbons may range from 90 to 100 carbon mol%.
a단계의 일산화탄소 함유 공급가스는 석탄, 바이오매스, 또는 탄소 함유 폐기물을 가스화하여 생산된 합성가스 또는 이로부터 정제된 가스일 수 있다.The carbon monoxide-containing feed gas of step a may be syngas produced by gasifying coal, biomass, or carbon-containing waste, or purified gas therefrom.
a단계에서 공급가스(feed gas)의 H2/CO 비는 1.5 내지 3.5 인 것이 바람직하다. In step a, the H 2 / CO ratio of the feed gas (feed gas) is preferably 1.5 to 3.5.
상기 H2/CO 비가 하한 미만일 경우 수성가스전환반응에 의한 SNG 수율 저하 및 탄소침적 발생이 심화되기 때문에 바람직하지 않고, 상한을 초과할 경우 C2-C4 탄화수소의 선택도가 낮아, SNG의 발열량이 감소하기 때문에 바람직하지 않다.When the H 2 / CO ratio is less than the lower limit, the SNG yield decreases due to the water gas shift reaction and carbon deposition is intensified, and when the upper limit is exceeded, the selectivity of C2-C4 hydrocarbons is low, and the calorific value of SNG is reduced. It is not preferable because it is.
상기 합성천연가스 합성 반응 조건은 일반적으로 사용되는 것으로 특별히 한정하지는 않는다.The synthetic natural gas synthesis reaction conditions are generally used and are not particularly limited.
본 발명의 촉매는 고정층, 유동층 및 슬러리 반응기에서 300 ∼ 600 ℃의 온도 범위의 수소 분위기에서 환원한 후에 반응에 활용할 수 있다. The catalyst of the present invention can be utilized in the reaction after reduction in a hydrogen atmosphere in the temperature range of 300 to 600 ℃ in a fixed bed, fluidized bed and slurry reactor.
상기 a단계에서, 반응 온도는 300 ∼ 400 ℃, 반응 압력은 20 ∼ 40 bar, 공간속도는 1000 ml/gcat·h ∼ 10000 ml/gcat·h 인 것이 바람직하다. In the step a, the reaction temperature is 300 to 400 ℃, the reaction pressure is 20 to 40 bar, the space velocity is preferably 1000 ml / g cat h ~ 10000 ml / g cat · h.
본 발명의 방법으로 제조된 촉매 상에서 350 ℃, 30 기압 및 6000 ml/gcat·h 공간속도의 반응 조건에서 전환율은 90 ∼ 100 카본 몰% 범위를 나타낸다. The conversion is in the range of 90 to 100 carbon mole% at reaction conditions of 350 ° C., 30 atm and 6000 ml / g cat.h space velocity on the catalyst prepared by the process of the invention.
제조되는 합성천연가스의 조성은 메탄이 33~82 카본 몰 % 이며, C2-C4 탄화수소가 3~17 카본 몰 % 범위를 나타낸다. C2-C4 탄화수소 중 파라핀의 비율은 90 ~ 100 카본몰 % 범위를 나타내며, 부산물인 C5이상 탄화수소, 구체적으로 C5-C12의 가솔린 유분은 6 ∼ 13 카본 몰% 범위를 나타낸다.The composition of the synthetic natural gas produced is 33 to 82 carbon mol% of methane, C2-C4 hydrocarbons range from 3 to 17 carbon mol%. The proportion of paraffins in the C2-C4 hydrocarbons ranges from 90 to 100 carbon mole%, and the gasoline fraction of by-product C5 or more hydrocarbons, specifically C5-C12, ranges from 6 to 13 carbon mole%.
본 발명은, 2종 이상의 금속을 이용하여 제조된 촉매로서, FT 합성반응 및 메탄화 반응을 동시에 이용하여, 메탄으로 주로 구성되고 C2-C4 파라핀 함량이 높은 고발열량의 합성천연가스의 생산과 공정 간소화가 가능한 촉매를 제조할 수 있다. The present invention is a catalyst produced by using two or more metals, using FT synthesis reaction and methanation simultaneously, producing and processing high calorific value natural natural gas composed mainly of methane and having high C2-C4 paraffin content. A catalyst that can be simplified can be prepared.
도 1은 실시예 1 및 비교예 1~3에서 제조된 촉매에 의한 전환율 및 탄화수소 선택도를 나타낸 것이다.Figure 1 shows the conversion and hydrocarbon selectivity by the catalyst prepared in Example 1 and Comparative Examples 1 to 3.
도 2는 실시예 1 및 비교예 1~3에서 제조된 촉매에 의한 SNG의 발열량 및 수율을 나타낸 것이다.Figure 2 shows the calorific value and yield of SNG by the catalyst prepared in Example 1 and Comparative Examples 1 to 3.
도 3, 도 4, 및 도 5는 각각 실시예 2~5 및 비교예 4에서 제조된 촉매의 X-선 회절분석(XRD), 승온-환원 특성분석(TPR) 및 BET 기공특성분석 결과이다. 3, 4, and 5 are the results of X-ray diffraction (XRD), temperature-reduction characterization (TPR) and BET pore characteristics of the catalyst prepared in Examples 2 to 5 and Comparative Example 4, respectively.
도 6은 실시예 2~5 및 비교예 4에서 제조된 촉매에 의한 전환율 및 탄화수소 선택도를 나타낸 것이다.Figure 6 shows the conversion and hydrocarbon selectivity by the catalyst prepared in Examples 2-5 and Comparative Example 4.
도 7은 실시예 2~5 및 비교예 4에서 제조된 촉매에 의한 SNG 발열량 및 수율을 나타낸 것이다.7 shows the SNG calorific value and yield by the catalysts prepared in Examples 2 to 5 and Comparative Example 4. FIG.
도 8에 실시예 6 및 7 및 비교예 5에서의 전환율 및 탄화수소 선택도를 나타낸 것이다.Figure 8 shows the conversion and hydrocarbon selectivity in Examples 6 and 7 and Comparative Example 5.
도 9는 석탄으로부터 SNG를 얻는 방법에 대한 개념도이다.9 is a conceptual diagram of a method for obtaining SNG from coal.
이하, 본 발명을 실시예를 통하여 보다 구체적으로 설명한다. 다만, 하기 실시예는 본 발명의 기술적 특징을 명확하게 예시하기 위한 것일 뿐 본 발명의 보호범위를 한정하는 것은 아니다.Hereinafter, the present invention will be described in more detail with reference to Examples. However, the following examples are only intended to clearly illustrate the technical features of the present invention and do not limit the protection scope of the present invention.
<< 실시예Example 1,  One, 비교예Comparative example 1 내지  1 to 3> Fe:Ni3> Fe: Ni 비율에 따른 고열량  High calorie value according to ratio 합성천연가스Synthetic natural gas 합성용 Fe- Synthetic Fe- NiNi 이종금속 촉매 제조 Dissimilar Metal Catalyst Manufacturing
촉매조성은 각각 50Fe-50Ni-20Al, 80Fe-20Ni-20Al, 95Fe-5Ni-20Al, 98Fe-2Ni-20Al이 되도록, 하기 표 1(조성에 따른 Fe-Ni 촉매의 금속 전구체 사용량)과 같이 질산철 (Fe(NO3)3·9H2O), 질산니켈 (Ni(NO3)2·6H2O) 및 질산알루미늄(Al(NO3)3·9H2O)을 200ml 증류수에 녹여 전구체 용액을 제조하였다.The catalyst composition is 50Fe-50Ni-20Al, 80Fe-20Ni-20Al, 95Fe-5Ni-20Al, 98Fe-2Ni-20Al, respectively, so that the iron nitrate as shown in Table 1 (the amount of metal precursor used in the Fe-Ni catalyst according to the composition) (Fe (NO 3 ) 3 · 9H 2 O), nickel nitrate (Ni (NO 3 ) 2 · 6H 2 O), and aluminum nitrate (Al (NO 3 ) 3 · 9H 2 O) were dissolved in 200 ml of distilled water to prepare the precursor solution. Prepared.
구분division 촉매조성Catalyst composition 전구체 사용량 (g)Precursor Usage (g)
Fe(NO3)3·9H2OFe (NO 3 ) 3 .9H 2 O Ni(NO3)2·6H2ONi (NO 3 ) 2 · 6H 2 O Al(NO3)3·9H2OAl (NO 3 ) 3 · 9H 2 O
비교예1Comparative Example 1 100Fe-20Al100Fe-20Al 5050 00 19.3219.32
비교예2Comparative Example 2 50Fe-50Ni-20Al50Fe-50Ni-20Al 5050 34.4234.42 38.6438.64
비교예3Comparative Example 3 80Fe-20Ni-20Al80Fe-20Ni-20Al 5050 8.618.61 24.1524.15
실시예1Example 1 95Fe-5Ni-20Al95Fe-5Ni-20Al 5050 1.811.81 20.3420.34
침전제 용액은 하기 표 2(조성에 따른 Fe-Ni 촉매의 침전제 사용량)와 같이 99.5 %의 탄산칼륨(K2CO3)을 각각 300 ml의 증류수에 녹여 제조하였다. The precipitant solution was prepared by dissolving 99.5% potassium carbonate (K 2 CO 3 ) in 300 ml of distilled water, as shown in Table 2 (the amount of precipitant used in the Fe-Ni catalyst according to the composition).
구분division 촉매조성Catalyst composition K2CO3 사용량 (g)K 2 CO 3 Usage (g)
비교예1Comparative Example 1 100Fe-20Al100Fe-20Al 36.5236.52
비교예2Comparative Example 2 50Fe-50Ni-20Al50Fe-50Ni-20Al 63.763.7
비교예3Comparative Example 3 80Fe-20Ni-20Al80Fe-20Ni-20Al 43.343.3
실시예1Example 1 95Fe-5Ni-20Al95Fe-5Ni-20Al 38.038.0
상기 전구체 용액은 격렬한 교반하의 침전제 용액에 첨가하여 침전 슬러리를 제조하고, 80 ℃에서 3 시간 동안 교반한 후, 생성된 침전물을 여과하고 증류수 1,000 ml로 여러 차례 나누어 세척하였다. 상기 과정으로 생성된 수산화철 cake는 함수율이 55%가 될 때까지 여과 및 건조하였다. 건조된 수산화철 cake는 건조오븐에서 110 ℃에서 12 시간 동안 건조 후, 소성로에서 air 분위기 하에, 450 ℃에서 4 시간 동안 소성하였다. The precursor solution was added to the precipitant solution under vigorous stirring to prepare a precipitate slurry, and after stirring at 80 ° C. for 3 hours, the resulting precipitate was filtered and washed several times with distilled water 1,000 ml. Iron hydroxide cake produced by the above process was filtered and dried until the water content is 55%. The dried iron hydroxide cake was dried at 110 ° C. for 12 hours in a drying oven, and then fired at 450 ° C. for 4 hours under an air atmosphere in a kiln.
하기 표 3(조성에 따른 Fe-Ni 촉매의 XRF 분석 결과)에 제조된 촉매의 X-선 형광 분석(XRF) 결과를 나타내었다. The X-ray fluorescence analysis (XRF) results of the catalysts prepared in Table 3 (the XRF analysis results of the Fe—Ni catalyst according to the composition) are shown.
전체 금속 비율 (wt%)Total metal ratio (wt%) 활성금속 비율 (wt%)Active metal ratio (wt%)
Fe Fe Ni Ni AlAl Fe Fe NiNi
비교예1Comparative Example 1 93.193.1 00 6.96.9 100.0100.0 0.00.0
비교예2Comparative Example 2 50.650.6 41.941.9 7.57.5 50.050.0 50.050.0
비교예3Comparative Example 3 72.772.7 20.820.8 6.56.5 80.080.0 20.020.0
실시예1Example 1 90.090.0 3.43.4 6.56.5 95.095.0 5.05.0
제조된 촉매는 상기 표 3과 같이 XRF 분석 결과와 상기 디자인 한 촉매조성이 일치하였으며, 이로부터 상기 촉매 제조방법에 의하여, 촉매 활성금속 비율에 따라 디자인 된 촉매조성과 일치하게 제조할 수 있음을 확인하였다.The prepared catalyst was consistent with the XRF analysis result and the designed catalyst composition as shown in Table 3, and from this, the catalyst preparation method confirmed that the catalyst composition could be produced in accordance with the catalyst composition designed according to the catalyst active metal ratio. It was.
상기 제조된 촉매는 1/2인치 스테인레스 고정층 반응기에 1 g의 실시예 및 비교예에서 제조된 촉매를 장입하고, 400 ℃의 H2 분위기 하에서 6시간 동안 환원 처리한 후에, 반응온도, 350 ℃, 반응압력 30 bar, 공간속도 6,000 ml/gcat·h의 조건에서 반응물인 합성가스는 H2/CO 비를 3으로 고정하여 반응기로 주입하여 SNG 합성반응을 수행하였다.The prepared catalyst was charged with 1 g of the catalyst prepared in Examples and Comparative Examples in a 1/2 inch stainless fixed bed reactor, and after 6 hours of reduction treatment under an H 2 atmosphere of 400 ° C., a reaction temperature of 350 ° C., The reactant synthesis gas was reacted at a reaction pressure of 30 bar and a space velocity of 6,000 ml / g cat.h , injected into the reactor at a fixed H 2 / CO ratio of 3 to carry out SNG synthesis.
하기 도 1에 실시예 및 비교예에 의한 전환율 및 탄화수소 선택도를 나타내었다.1 shows the conversion and hydrocarbon selectivity according to Examples and Comparative Examples.
Ni 활성메탈의 첨가에 의하여 CO 전환율은 모든 조성비에서 100%에 근접하였으며, CO to CO2 전환율이 감소하였다. Fe 단일촉매의 경우, CO to CO2 전환율이 매우 높았다.The conversion of CO was close to 100% at all composition ratios and the CO to CO 2 conversion was decreased by the addition of Ni activated metal. In the case of Fe monocatalyst, the CO to CO 2 conversion was very high.
Ni 활성메탈의 첨가에 의하여 CH4 선택도는 2배 이상 증가되었으며, Ni 비율이 전체 활성메탈 중 20% 이상일 경우 약 90%의 CH4 선택도를 보였다. C2-C4 선택도 및 C5+ 선택도는 Ni 활성메탈 첨가에 의하여 크게 감소하였으며, C2-C4 탄화수소 내 paraffin 선택도는 Ni 첨가에 의하여 100%에 도달하였다. CH 4 selectivity increased more than 2 times by the addition of Ni active metal, and showed about 90% CH 4 selectivity when the Ni ratio was more than 20% of the total active metal. C 2 -C 4 selectivity and C 5+ selectivity were greatly reduced by the addition of Ni active metal, and in C 2 -C 4 hydrocarbons paraffin selectivity reached 100% by Ni addition.
탄화수소 선택도 중 C5+ 선택도의 감소는 SNG 수율의 향상을 유도할 수 있으나, CH4 선택도의 증가 및 C2-C4 선택도의 감소는 SNG의 발열량의 감소로 이어지기 때문에, 비교적 C2-C4 선택도가 높은 조성비(활성 메탈 중 Ni 비율이 20% 미만)가 최적으로 판단된다. Reduction of C 5+ selectivity in hydrocarbon selectivity can lead to an improvement in SNG yield, but an increase in CH 4 selectivity and a decrease in C 2 -C 4 selectivity leads to a decrease in calorific value of SNG. A composition ratio with a high C 2 -C 4 selectivity (less than 20% of Ni in the active metal) is judged to be optimal.
하기 도 2에 실시예 및 비교예에 의한 SNG의 발열량 및 수율을 나타내었다. 2 shows the calorific value and yield of SNG according to Examples and Comparative Examples.
Ni 첨가시 Fe 단일 금속 촉매에 비하여, 발열량은 12,800 Kcal/Nm3에서 9,800 Kcal/Nm3로 크게 저하되었으며, Fe:Ni이 50:50 및 80:20에서 큰 차이는 없었다. Fe:Ni이 95:5에서 SNG 발열량은 10,500 Kcal/Nm3 으로, 50:50 및 80:20에 비하여 높았다. SNG 수율은 Ni 첨가 및 첨가량에 따라 증가하였으나, Fe:Ni이 50:50, 80:20 촉매의 경우 높은 SNG 수율에 비하여 발열량이 매우 낮았으며, Ni이 첨가되지 않은 촉매의 경우 발열량은 매우 높지만, 수율이 매우 낮았다.When Ni was added, the calorific value decreased significantly from 12,800 Kcal / Nm 3 to 9,800 Kcal / Nm 3 , and Fe: Ni was not significantly different at 50:50 and 80:20. At 95: 5 Fe: Ni, the SNG calorific value was 10,500 Kcal / Nm 3, which was higher than that of 50:50 and 80:20. SNG yield increased with addition and addition of Ni, but the Fe: Ni 50:50 and 80:20 catalysts had a very low calorific value compared to the high SNG yield. Yield was very low.
따라서 Fe 단일금속 촉매의 경우, CO to CO2 전환율이 높아, SNG 수율이 낮기 때문에 SNG 합성용 촉매로서 적합하지 않으며, 활성메탈 중 Ni의 비율이 20% 이상일 경우, 높은 CH4 선택도 및 낮은 C2-C4 선택도로 인하여, 발열량이 낮아지기 때문에, 고열량 SNG의 합성에는 적합하지 않다.Therefore, Fe monometallic catalyst is not suitable as a catalyst for SNG synthesis because of high CO to CO 2 conversion and low SNG yield, and high CH 4 selectivity and low C when Ni in the active metal is more than 20%. Due to the 2 -C 4 selectivity, since the calorific value is lowered, it is not suitable for the synthesis of high calorific value SNG.
<실시예 2~5> 소성온도에 따른 고열량 합성천연가스 합성용 Fe-Ni 이종금속 촉매 제조<Examples 2 to 5> Preparation of Fe-Ni dissimilar metal catalyst for synthesizing high-calorie synthetic natural gas according to firing temperature
촉매조성은 95Fe-5Ni-20Al이 되도록, 각각 하기 표와 같이 질산철 (Fe(NO3)3·9H2O), 질산니켈 (Ni(NO3)2·6H2O) 및 질산알루미늄(Al(NO3)3·9H2O) 각각 50 g, 1.81 g 및 20.34 g을 200ml 증류수에 녹여 전구체 용액을 제조하였다.The catalyst composition was 95Fe-5Ni-20Al, and iron nitrate (Fe (NO 3 ) 3 · 9H 2 O), nickel nitrate (Ni (NO 3 ) 2 · 6H 2 O) and aluminum nitrate (Al) as shown in the following table, respectively. (NO 3 ) 3 .9H 2 O) 50 g, 1.81 g and 20.34 g, respectively, were dissolved in 200 ml of distilled water to prepare a precursor solution.
상기 전구체 용액은 99.5 %의 탄산칼륨(K2CO3) 38 g과 300 ml의 증류수가 섞인 용액에 격렬한 교반하에서 첨가하여 침전 슬러리를 80 ℃에서 3 시간 동안 교반한 후, 생성된 침전물을 여과하고 증류수 1,000 ml로 여러 차례 나누어 세척하였다. 상기 과정으로 생성된 수산화철 cake는 함수율이 55%가 될 때까지 여과 및 건조하였다. 건조된 수산화철 cake는 건조오븐에서 110 ℃에서 12 시간 동안 건조 후, 소성로에서 air 분위기 하에, 각각 450℃, 500℃, 550℃, 600℃, 700 ℃에서 4 시간 동안 소성하였다.The precursor solution was added to a solution containing 38 g of 99.5% potassium carbonate (K 2 CO 3 ) and 300 ml of distilled water under vigorous stirring to stir the precipitate slurry at 80 ° C. for 3 hours, and then the resulting precipitate was filtered The solution was washed several times with 1,000 ml of distilled water. Iron hydroxide cake produced by the above process was filtered and dried until the water content is 55%. The dried iron hydroxide cake was dried at 110 ° C. for 12 hours in a drying oven, and then calcined at 450 ° C., 500 ° C., 550 ° C., 600 ° C., and 700 ° C. for 4 hours in an air atmosphere in a kiln.
상기에서 제조된 철-니켈 이종금속 촉매의 X-선 형광분석 (XRF), X-선 회절분석(XRD), 승온-환원 특성분석(TPR) 및 BET 기공특성분석 결과를 각각 하기 표 4(조성에 따른 Fe-Ni 촉매의 XRF 분석 결과), 도 3, 도 4, 및 도 5에 나타내었다.X-ray fluorescence (XRF), X-ray diffraction (XRD), temperature-reduction characterization (TPR) and BET pore characteristics of the iron-nickel dissimilar metal catalyst prepared above are shown in Table 4 (composition). XRF analysis results of Fe-Ni catalyst according to the present invention is shown in FIGS. 3, 4, and 5.
소성온도(℃)Firing temperature (℃) 전체 금속 비율 (wt%)Total metal ratio (wt%) 활성금속 비율 (wt%)Active metal ratio (wt%)
Fe Fe Ni Ni AlAl Fe Fe NiNi
실시예2Example 2 450450 79.279.2 4.24.2 16.716.7 95.095.0 5.05.0
실시예3Example 3 500500 79.279.2 4.24.2 16.716.7 95.095.0 5.05.0
실시예4Example 4 550550 79.279.2 4.24.2 16.716.7 95.095.0 5.05.0
실시예5Example 5 600600 79.279.2 4.24.2 16.716.7 95.095.0 5.05.0
비교예4Comparative Example 4 700700 79.279.2 4.24.2 16.716.7 95.095.0 5.05.0
제조된 촉매는 상기 표 4과 같이 XRF 분석 결과와 상기 디자인 한 촉매조성이 일치하였으며, 소성온도에 따른 변화는 관찰되지 않았다. 이로부터 상기 촉매 제조방법에 의하여, 촉매 소성온도에 따른 변화 없이, 디자인 된 촉매조성과 일치하게 제조할 수 있음을 확인하였다.The prepared catalyst was consistent with the XRF analysis result and the designed catalyst composition as shown in Table 4, and no change was observed with the calcination temperature. From this it was confirmed that by the catalyst preparation method, it can be produced in accordance with the designed catalyst composition, without a change according to the catalyst firing temperature.
도 3의 XRD 분석 결과, 활성메탈 비율의 대부분을 차지하는 Fe의 산화물인 Fe2O3 및 Fe3O4 peak가 주로 나타났으며, NiO peak 및 Fe와 Ni의 aluminate peak이 관찰되었다. 소성온도 550 ℃ 이상에서 crystal size 증가에 의하여 peak intensity가 두드러지게 증가하였다. As a result of XRD analysis of FIG. 3, Fe 2 O 3 and Fe 3 O 4 , which are oxides of Fe, account for most of the active metal ratio. peak The NiO peak and aluminate peaks of Fe and Ni were observed. Peak intensity markedly increased with increasing crystal size at firing temperature above 550 ℃.
환원 후 촉매의 XRD peak 중 Fe2O3 peak는 관찰되지 않거나 intensity가 크게 감소하였으며, 대부분이 Fe3O4를 나타내는 peak가 주된 peak로 나타났다. 그 외에도 촉매 환원에 의하여 iron metal peak 및 Fe-Ni alloy peak이 관찰되었으며, 촉매 소성온도의 증가에 따라 intensity가 증가하였다. After reduction, the Fe 2 O 3 peak was not observed or the intensity was greatly decreased among the XRD peaks of the catalyst, and the peak indicating the Fe 3 O 4 was the main peak. In addition, iron metal peak and Fe-Ni alloy peak were observed by catalytic reduction, and intensity increased with increasing catalyst firing temperature.
도 4의 승온-환원 특성분석(TPR) 결과, 소성온도가 증가할수록 Fe-Ni bimetallic oxide 및 aluminate 형성이 증가되어, Fe2O3 →Fe3O4 환원 peak (340 → 400 ℃), Fe3O4 → Fe & aluminate 환원 peak (470 → 700 ℃)가 고온으로 shift 되었다. As a result of the temperature-reduction characterization (TPR) of FIG. 4, as the firing temperature is increased, Fe-Ni bimetallic oxide and aluminate formation are increased, resulting in Fe 2 O 3 → Fe 3 O 4 reduction peak (340 → 400 ℃), Fe 3 O 4 → Fe & aluminate reduction peak (470 → 700 ℃) was shifted to a high temperature.
도 5의 BET 기공특성 분석 결과, 촉매 소성온도의 증가에 따라 활성성분의 소결에 의한 기공성 감소로 인하여, 촉매 N2 흡착량이 감소하였으며, hysteresis의 분포가 상대압이 높은 쪽으로 shift되었다. 하기 표 5(소성온도에 따른 95Fe-5Ni-20Al 촉매의 기공특성)의 비표면적 및 기공부피는 촉매 소성온도에 따라 감소하는 경향을 보였으며, 특히, 550 ℃ 이상에서 비표면적이 크게 감소하였다. 기공크기는 촉매 소성온도에 따라 증가하였으며, 도 5의 기공분포도에서 각 실시예에 의한 촉매의 기공분포는 소성온도 증가에 따라 주로 2~6 nm 의 분포에서 6~12 nm로 shift 되었다. As a result of analyzing the BET pore characteristics of FIG. 5, the adsorption amount of catalyst N 2 decreased due to the decrease in porosity due to the sintering of the active ingredient with increasing catalyst firing temperature, and the distribution of hysteresis shifted to a higher relative pressure. The specific surface area and pore volume of Table 5 (pore characteristics of 95Fe-5Ni-20Al catalyst according to firing temperature) showed a tendency to decrease with the catalyst firing temperature, and in particular, the specific surface area was greatly decreased above 550 ° C. The pore size increased with the catalyst firing temperature, and the pore distribution of the catalyst according to each example in the pore distribution diagram of FIG. 5 was shifted to 6-12 nm in the distribution of 2-6 nm mainly with increasing the firing temperature.
SSAa(m2/g)SSA a (m 2 / g) Pore volume(cm3/g)Pore volume (cm 3 / g) Pore size(nm)Pore size (nm)
실시예2Example 2 204.5204.5 0.2710.271 4.074.07
실시예3Example 3 175.7175.7 0.2380.238 4.054.05
실시예4Example 4 148.0148.0 0.2290.229 4.794.79
실시예5Example 5 89.089.0 0.1970.197 6.926.92
비교예4Comparative Example 4 65.065.0 0.2000.200 9.259.25
a: Specific surfacearea a: Specific surfacearea
제조된 촉매는 1/2인치 스테인레스 고정층 반응기에 1 g의 실시예 및 비교예에서 제조된 촉매를 장입하고, 400 ℃의 H2 분위기 하에서 6시간 동안 환원 처리한 후에, 반응온도, 350 ℃, 반응압력 30 bar, 공간속도 6,000 ml/gcat·h의 조건에서 반응물인 합성가스는 H2/CO 비를 3으로 고정하여 반응기로 주입하여 SNG 합성반응을 수행하였다. The prepared catalyst was charged with 1 g of the catalyst prepared in Examples and Comparative Examples in a 1/2 inch stainless fixed bed reactor and reduced for 6 hours under an H 2 atmosphere of 400 ° C., followed by reaction temperature, 350 ° C., and reaction. The reactant syngas was reacted at a pressure of 30 bar and a space velocity of 6,000 ml / g cat.h , and injected into the reactor with the H 2 / CO ratio set at 3 to perform the SNG synthesis reaction.
하기 도 6에 실시예 및 비교예에 의한 전환율 및 탄화수소 선택도를 나타내었다.6 shows conversion and hydrocarbon selectivity according to Examples and Comparative Examples.
95Fe-5Ni-20Al 촉매의 CO 전환율은 700 ℃ 소성촉매를 제외하고 소성온도에 관계없이 100%에 근접하였으나, 700 ℃ 소성 촉매의 경우 metal-aluminate 형성에 의하여, 다른 촉매에 비하여 CO 전환율이 크게 감소되었으며, WGS 활성이 매우 높았다. 550 ℃ 소성촉매의 경우 CO to CO2 전환율 및 C5+ 선택도가 가장 낮았다. The CO conversion of 95Fe-5Ni-20Al catalyst was close to 100% regardless of the firing temperature except the 700 ° C firing catalyst, but the 700 ° C firing catalyst greatly reduced the CO conversion compared to other catalysts due to metal-aluminate formation. WGS activity was very high. In the case of the firing catalyst at 550 ℃, the CO to CO 2 conversion and C 5+ selectivity were the lowest.
탄화수소 선택도의 경우, 촉매 소성온도의 증가에 따라 550 ℃까지 CH4 선택도가 증가하였으며, paraffin 선택도는 소성온도 550 ℃ 이상에서 모두 100%를 나타내었다. 700 ℃ 소성 촉매의 경우 높은 C2-C4 선택도롤 나타내어, 발열량이 높을 것으로 예상되지만, 낮은 CO 전환율 및 높은 WGS 활성으로 인하여 SNG 합성반응에는 적합하지 않은 것으로 판단된다.In the case of hydrocarbon selectivity, CH 4 selectivity increased up to 550 ℃ with increasing catalyst firing temperature, and paraffin selectivity showed 100% at above 550 ℃. In the case of the calcination catalyst at 700 ° C., a high C 2 -C 4 selectivity is shown, and the calorific value is expected to be high, but due to the low CO conversion and the high WGS activity, it is not suitable for SNG synthesis.
하기 도 7에 실시예 및 비교예에 의한 SNG 발열량 및 수율을 나타내었다.7 shows the SNG calorific value and yield according to Examples and Comparative Examples.
발열량은 촉매 소성 온도의 증가에 따라 550 ℃ 까지 10,600 Kcal/Nm3에서 10,350 Kcal/Nm3까지 감소하는 경향을 보였으며, 600 ℃ 이상에서는 다시 11,500 Kcal/Nm3 까지 증가하는 경향을 보였다. SNG 수율은 발열량과 반대 경향을 보였으며, 550 ℃ 소성 촉매에서 70% 이상으로 가장 높았다.The amount of calorific value decreased from 10,600 Kcal / Nm 3 to 10,350 Kcal / Nm 3 up to 550 ° C, and increased to 11,500 Kcal / Nm 3 above 600 ° C. The yield of SNG showed the opposite trend of calorific value and was the highest with more than 70% at 550 ° C calcination catalyst.
따라서 촉매의 소성온도가 450도 이하에서는 제조 과정에 사용된 용매 및 유기 불순물이 소성에 의해 완전히 제거하기가 어렵고, 활성성분과 증진제의 균일한 분산이 저하되며, 촉매 강도가 약하기 때문에 고발열량 SNG 합성용 촉매로서 적합하지 않고, 650도를 초과할 경우 Fe-aluminate 및 Ni-Aluminate의 과도한 형성으로 인한 환원도 감소 및 활성저하, 소결에 의한 기공구조 형성의 미흡에 의하여 고발열량 SNG 합성 촉매로서 적합하지 않다.Therefore, if the calcination temperature of the catalyst is less than 450 degrees, it is difficult to completely remove the solvent and organic impurities used in the manufacturing process by calcination, the uniform dispersion of the active ingredient and the enhancer is lowered, and the catalyst strength is weak, so that high calorific value SNG synthesis is performed. It is not suitable as a catalyst for high calorific value SNG synthesis by reducing the reduction degree and deactivation due to excessive formation of Fe-aluminate and Ni-Aluminate and insufficient pore structure formation by sintering. not.
<< 실시예Example 6~7> Fe- 6 ~ 7> Fe- NiNi 이종금속 촉매의 합성가스 H2/CO ratio에 따른 SNG 합성 반응 특성 Characteristics of SNG Synthesis by Different Gas H2 / CO Ratios of Dissimilar Metal Catalysts
실시예 4의 95Fe-5Ni-20Al, 550℃ 소성촉매를 1/2인치 스테인레스 고정층 반응기에 1 g 장입하고, 400 ℃의 H2 분위기 하에서 6시간 동안 환원 처리한 후에, 반응온도, 350 ℃, 반응압력 30 bar, 공간속도 6,000 ml/gcat·h의 조건에서 반응물인 합성가스는 H2/CO 비를 1 내지 3으로 하여 반응기로 주입하여 SNG 합성반응을 수행하였다. 1 g of the 95Fe-5Ni-20Al, 550 ° C. calcining catalyst of Example 4 was charged to a 1/2 inch stainless fixed bed reactor and reduced for 6 hours under an H 2 atmosphere of 400 ° C., followed by reaction temperature, 350 ° C., and reaction. The reactant syngas was reacted at a pressure of 30 bar and a space velocity of 6,000 ml / g cat.h with an H 2 / CO ratio of 1 to 3.
촉매조성Catalyst composition 소성온도 (℃)Firing temperature (℃) H2/CO ratioH 2 / CO ratio
비교예5Comparative Example 5 95Fe-5N-20Al95Fe-5N-20Al 550550 1One
실시예6Example 6 22
실시예7Example 7 33
하기 도 8에 실시예 및 비교예 의한 전환율 및 탄화수소 선택도를 나타내었다.8 shows conversion and hydrocarbon selectivity according to Examples and Comparative Examples.
CO 전환율 및 CO to HC 전환율은 H2/CO ratio 증가에 따라 증가하였으며, CO to CO2 전환율은 WGS 활성 감소에 의하여 감소하였다. H2/CO ratio가 1.5 미만에서는 CO to CO2 전환율이 40% 이상으로 매우 높아 SNG 수율이 CO to HC 전환율이 낮아 SNG 합성에 적합하지 않음을 확인할 수 있다.CO conversion and CO to HC conversion increased with increasing H 2 / CO ratio, and CO to CO 2 conversion decreased with decreasing WGS activity. When the H 2 / CO ratio is less than 1.5, the CO to CO 2 conversion rate is very high, such as 40% or more, and thus the SNG yield is low, and thus it is not suitable for SNG synthesis.
H2/CO ratio 증가에 따라 CH4 선택도 및 paraffin 선택도가 증가하였으며, C2-C4 선택도는 감소하였다. H2/CO ratio가 1.5 미만에서는 paraffin 선택도가 낮아 고열량 SNG 합성에 적합하지 않음을 확인할 수 있다.CH 4 selectivity and paraffin selectivity increased with increasing H 2 / CO ratio, and C2-C4 selectivity decreased. When the H 2 / CO ratio is less than 1.5, the paraffin selectivity is low, and thus it is not suitable for high calorie SNG synthesis.
이상에서와 같이 본 발명을 상기의 실시예를 통해 설명하였지만 본 발명이 반드시 여기에만 한정되는 것은 아니며 본 발명의 범주와 사상을 벗어나지 않는 범위 내에서 다양한 변형실시가 가능함은 물론이다. 따라서, 본 발명의 보호범위는 특정 실시 형태로 국한되는 것이 아니며, 본 발명에 첨부된 특허청구의 범위에 속하는 모든 실시 형태를 포함하는 것으로 해석되어야 한다.Although the present invention has been described through the above embodiments as described above, the present invention is not necessarily limited thereto, and various modifications can be made without departing from the scope and spirit of the present invention. Therefore, the protection scope of the present invention should not be limited to the specific embodiments, but should be construed as including all embodiments falling within the scope of the claims appended to the present invention.

Claims (20)

  1. 메탄 : C2-C4 파라핀 (몰비) = 1 : 0.05 ~ 0.5 로 고발열량을 발휘하는 조성의 합성천연가스를 제조하는 방법에 있어서,In the method for producing a synthetic natural gas having a composition exhibiting a high calorific value of methane: C2-C4 paraffin (molar ratio) = 1: 0.05 to 0.5,
    활성금속인 철과 니켈 100 중량부를 기준으로, 철 및 니켈이 각각 80 내지 95 중량부 및 5 내지 20 중량부이고 스피넬 구조의 magnetite를 함유하는 Ni 및 Fe 함유 촉매 존재 하에, 일산화탄소로부터 메탄 및 C2-C4 파라핀 함유 합성천연가스를 제조하는 a단계를 포함하는 것이 특징인 방법.Based on 100 parts by weight of the active metals iron and nickel, methane and C2- from carbon monoxide in the presence of a Ni and Fe-containing catalyst containing 80 to 95 parts by weight and 5 to 20 parts by weight respectively and containing a spinite-structured magnetite C4 paraffin-containing synthetic natural gas comprising the step of preparing a.
  2. 제1항에 있어서, a단계는 상기 촉매에 의해 Fischer-Tropsh 합성반응 및 메탄화 반응이 동시에 일어나는 것이 특징인 방법.The method of claim 1, wherein the step a is characterized in that the Fischer-Tropsh synthesis reaction and the methanation reaction occurs simultaneously by the catalyst.
  3. 제1항에 있어서, 상기 촉매 중 활성금속은 철산화물, 니켈산화물, 철, 니켈, 철-니켈 합금 또는 이의 혼합물인 것이 특징인 방법.The method of claim 1, wherein the active metal in the catalyst is iron oxide, nickel oxide, iron, nickel, iron-nickel alloy or a mixture thereof.
  4. 제3항에 있어서, 활성금속인 철산화물은 Fe2O3, Fe3O4, 또는 둘다이고, 니켈산화물은 NiO, Ni2O3, 또는 둘다인 것이 특징인 방법. The method according to claim 3, wherein the iron oxide which is an active metal is Fe 2 O 3 , Fe 3 O 4 , or both, Nickel oxide is NiO, Ni 2 O 3 , or both.
  5. 제1항에 있어서, a단계 이전 또는 이후에, 300 ∼ 600 ℃의 온도 범위의 수소 분위기에서 촉매를 환원하는 단계를 더 포함하는 것이 특징인 방법.The method of claim 1, further comprising reducing the catalyst in a hydrogen atmosphere in a temperature range of 300 to 600 ° C. before or after step a.
  6. 제1항에 있어서, 상기 촉매는 비표면적이 75 내지 150 m2/g이고 기공의 평균입경이 4 내지 8 nm인 것이 특징인 방법.The method of claim 1, wherein the catalyst has a specific surface area of 75 to 150 m 2 / g and an average particle diameter of pores of 4 to 8 nm.
  7. 제1항에 있어서, 상기 촉매는 350 ℃, 30 기압 및 6000 ml/gcat·h 공간속도의 반응 조건에서 전환율이 90 ∼ 100 카본 몰% 범위인 것이 특징인 방법.The method of claim 1, wherein the catalyst has a conversion rate in the range of 90 to 100 carbon mol% at a reaction condition of 350 ° C., 30 atmospheres, and 6000 ml / g cat.h space velocity.
  8. 제1항에 있어서, a단계에서 메탄의 선택도는 33~82 카본 몰 % 이고, C2-C4 탄화수소의 선택도는 3~17 카본 몰 % 범위이며, C2-C4 탄화수소 중 파라핀의 비율이 90 ~ 100 카본몰 % 범위인 것이 특징인 방법.The method of claim 1, wherein in step a, the selectivity of methane is 33-82 carbon mole%, the selectivity of C2-C4 hydrocarbon is in the range of 3-17 carbon mole%, and the ratio of paraffins in C2-C4 hydrocarbon is 90-90. Characterized in that in the range of 100 carbon mole%.
  9. 제1항에 있어서, 합성천연가스는 9,000 Kcal/Nm3 ~ 13,000 Kcal/Nm3의 고발열량을 발휘하는 조성을 가진 것이 특징인 방법.The method of claim 1, wherein the synthetic natural gas is 9,000 Kcal / Nm 3 A method characterized by having a composition exhibiting a high calorific value of ˜13,000 Kcal / Nm 3 .
  10. 제1항에 있어서, a단계에서 공급가스(feed gas) 중 H2/CO 비는 1.5 내지 3.5 인 것이 특징인 방법. The method of claim 1, wherein the H 2 / CO ratio in the feed gas in step a is 1.5 to 3.5.
  11. 제1항에 있어서, a단계에서 반응 압력은 20 ∼ 40 bar이고, 반응 온도는 300 ∼ 400 ℃이고, 공간속도는 1000 ml/gcat·h ∼ 10000 ml/gcat·h 인 것이 특징인 방법.The method of claim 1, wherein the reaction pressure in step a is 20 to 40 bar, the reaction temperature is 300 to 400 ℃, the space velocity is 1000 ml / g cat h ~ 10000 ml / g cat h .
  12. 제1항에 있어서, a단계의 일산화탄소 함유 공급가스는 석탄, 바이오매스, 또는 탄소 함유 폐기물을 가스화하여 생산된 합성가스 또는 이로부터 정제된 가스인 것이 특징인 방법.The method of claim 1, wherein the carbon monoxide-containing feed gas of step a is a syngas produced by gasifying coal, biomass, or carbon-containing waste or a gas purified therefrom.
  13. 메탄 : C2-C4 파라핀 (몰비) = 1 : 0.05 ~ 0.5 로 고발열량을 발휘하는 조성의 합성천연가스 생산용 촉매로서, Methane: C2-C4 paraffin (molar ratio) = 1: 0.05 ~ 0.5 as a catalyst for the production of synthetic natural gas with a high calorific value composition,
    활성금속인 철과 니켈 100 중량부를 기준으로, 철 및 니켈이 각각 80 내지 95 중량부 및 5 내지 20 중량부이며, 스피넬 구조의 magnetite를 함유하는 것이 특징인 Ni 및 Fe 함유, FT 합성 및 메탄화 동시 반응용 촉매.Based on 100 parts by weight of the active metals iron and nickel, iron and nickel are 80 to 95 parts by weight and 5 to 20 parts by weight, respectively, and contain Ni and Fe, FT synthesis and methanation, which contain a spinel-structured magnetite. Catalyst for simultaneous reaction.
  14. 제13항에 있어서, 일산화탄소로부터 메탄 및 C2-C4 파라핀 함유 합성천연가스 제조용인 것이 특징인 촉매.The catalyst according to claim 13, which is for producing synthetic natural gas containing methane and C2-C4 paraffin from carbon monoxide.
  15. 제13항에 있어서, 활성금속은 철산화물, 니켈산화물, 철, 니켈, 철-니켈 합금 또는 이의 혼합물인 것이 특징인 촉매.The catalyst of claim 13 wherein the active metal is iron oxide, nickel oxide, iron, nickel, iron-nickel alloy or mixtures thereof.
  16. 제15항에 있어서, 활성금속인 철산화물은 Fe2O3, Fe3O4, 또는 둘다이고, 니켈산화물은 NiO, Ni2O3, 또는 둘다인 것이 특징인 촉매. The method according to claim 15, wherein the iron oxide which is the active metal is Fe 2 O 3 , Fe 3 O 4 , or both, Nickel oxide is a catalyst characterized in that NiO, Ni 2 O 3 , or both.
  17. 제13항에 있어서, 상기 촉매는 비표면적이 75 내지 150 m2/g이고 기공의 평균입경이 4 내지 8 nm인 것이 특징인 방법.The method of claim 13, wherein the catalyst has a specific surface area of 75 to 150 m 2 / g and an average particle diameter of pores of 4 to 8 nm.
  18. 제13항에 있어서, 상기 촉매는 350 ℃, 30 기압 및 6000 ml/gcat·h 공간속도의 반응 조건에서 전환율이 90 ∼ 100 카본 몰% 범위인 것이 특징인 촉매.The catalyst according to claim 13, wherein the catalyst has a conversion rate in the range of 90 to 100 carbon mol% at reaction conditions of 350 ° C., 30 atmospheres, and 6000 ml / g cat.h space velocity.
  19. 메탄 : C2-C4 파라핀 (몰비) = 1 : 0.05 ~ 0.5 로 고발열량을 발휘하는 조성의 합성천연가스 생산용 Ni 및 Fe 함유 촉매를 제조하는 방법에 있어서,In the process for producing Ni and Fe-containing catalysts for the production of synthetic natural gas having a composition exhibiting a high calorific value of methane: C 2 -C 4 paraffin (molar ratio) = 1: 0.05 to 0.5,
    철과 니켈 100 중량부를 기준으로, 철 및 니켈이 각각 80 내지 95 중량부 및 5 내지 20 중량부가 되도록 Fe계 전구체 및 Ni계 전구체를 혼합하여 전구체 용액을 제조하는 제1단계; A first step of preparing a precursor solution by mixing Fe-based precursors and Ni-based precursors such that iron and nickel are 80 to 95 parts by weight and 5 to 20 parts by weight, respectively, based on 100 parts by weight of iron and nickel;
    침전제와 증류수의 혼합용액을 제조하는 제2단계; A second step of preparing a mixed solution of a precipitant and distilled water;
    상기 제1단계에서 얻어진 용액을 상기 제2단계에서 얻어진 용액과 혼합하는 제3단계; A third step of mixing the solution obtained in the first step with the solution obtained in the second step;
    상기 제3단계에서 얻어진 혼합용액을 침전여과하는 제4단계; 및A fourth step of precipitating and filtering the mixed solution obtained in the third step; And
    제4단계에서 얻어진 여과물을 건조 및 450 내지 650 ℃에서 소성하여, 스피넬 구조의 magnetite를 함유하면서 비표면적이 75 내지 150 m2/g이고 기공의 평균입경이 4 내지 8 nm인 촉매를 제조하는 제5단계를 포함하는 것이 특징인 촉매 제조방법.The filtrate obtained in the fourth step was dried and calcined at 450 to 650 ° C. to prepare a catalyst containing a spinel-structured magnetite with a specific surface area of 75 to 150 m 2 / g and an average particle diameter of 4 to 8 nm. Catalyst production method comprising a fifth step.
  20. 제19항에 있어서, 제4단계에서 얻어진 여과물의 함수율이 50 내지 80 % 인 것이 특징인 촉매 제조방법.The method of claim 19, wherein the water content of the filtrate obtained in the fourth step is 50 to 80%.
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