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WO2018212542A1 - Catalyseur pour le reformage de méthane à l'aide de dioxyde de carbone, et son procédé de préparation - Google Patents

Catalyseur pour le reformage de méthane à l'aide de dioxyde de carbone, et son procédé de préparation Download PDF

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WO2018212542A1
WO2018212542A1 PCT/KR2018/005528 KR2018005528W WO2018212542A1 WO 2018212542 A1 WO2018212542 A1 WO 2018212542A1 KR 2018005528 W KR2018005528 W KR 2018005528W WO 2018212542 A1 WO2018212542 A1 WO 2018212542A1
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catalyst
phosphorus
carbon dioxide
cobalt
reforming reaction
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Korean (ko)
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장태선
박지훈
허일정
박정현
유영우
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Korea Research Institute of Chemical Technology KRICT
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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
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/75—Cobalt
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
    • B01J27/18—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr with metals other than Al or Zr
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/613—10-100 m2/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/615—100-500 m2/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • 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
    • B01J37/08—Heat treatment
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
    • C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
    • C01B2203/0238—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a carbon dioxide reforming step
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041—Composition of the catalyst
    • C01B2203/1047—Group VIII metal catalysts
    • C01B2203/1052—Nickel or cobalt catalysts

Definitions

  • the present invention relates to a catalyst for methane reforming reaction using carbon dioxide and a method for preparing the same.
  • Synthetic gas produced can be reacted with high value-added chemicals such as oxoalcohol, dimethyl ether (DME), polycarbonate (PC) and acetic acid. It can be used as.
  • the carbon dioxide reforming reaction of the methane is shown in the following scheme.
  • This carbon dioxide reforming reaction is a very strong endothermic reaction.
  • the equilibrium conversion the theoretical maximum conversion at a given temperature, increases with increasing temperature, causing the reaction to occur at temperatures above 650 ° C., and usually at a high temperature of 850 ° C.
  • the reaction at high temperature easily sinters and oxidizes the catalyst particles (active component), thereby reducing the active point of the catalyst, causing carbon deposition, and seriously lowering the catalyst activity. Development is required.
  • Korean Patent No. 1164024 limits the content of the active ingredient to a specific ratio to optimize the content of the active ingredient and impregnate each active metal separately, followed by a carrier impregnated with the entire active metal.
  • a cobalt based catalyst for carbon dioxide reforming reaction of methane prepared by the process of firing is proposed.
  • Korean Patent No. 1366418 discloses an alumina (Al 2 O 3 ) catalyst support whose surface is modified with magnesium oxide (MgO); Nickel and cobalt as catalytically active ingredients; And calcium oxide, which is a catalyst enhancer, wherein the catalyst active ingredient and the catalyst enhancer are supported on the catalyst support, and the magnesium oxide proposes a catalyst for steam reforming of methane forming a spinel structure with alumina.
  • MgO magnesium oxide
  • Nickel and cobalt as catalytically active ingredients
  • calcium oxide which is a catalyst enhancer, wherein the catalyst active ingredient and the catalyst enhancer are supported on the catalyst support, and the magnesium oxide proposes a catalyst for steam reforming of methane forming a spinel structure with alumina.
  • a reforming catalyst for production, a syngas production method using the same, and a syngas production reactor are proposed.
  • U.S. Pat.No.57,444,19 supports the support of silica, alumina, zirconia, etc., which is pre-coated with nickel or cobalt with alkaline earth metals depending on the presence of precious metals in connection with steam reforming including oxygen reforming and carbon dioxide reforming.
  • This catalyst and U. S. Patent No. 4026823 disclose a zirconia supported nickel catalyst in which cobalt is added to nickel as a steam reforming catalyst for hydrocarbons.
  • An object of the present invention is to solve the above problems, by supporting the active ingredient on the surface-modified alumina support with phosphorus, sintering and formation of an inactive phase of the active ingredient even at high temperature due to the bonding between the alumina support and the active ingredient It is to provide a catalyst for the reforming reaction of methane using carbon dioxide and a method for producing the same, which can improve the activity stability of the catalyst by inhibiting.
  • the present invention also provides a method for producing a synthesis gas that can stably produce a synthesis gas having a high carbon monoxide content from a gas containing methane and carbon dioxide using the catalyst.
  • the cobalt in the catalyst for the methane reforming reaction using carbon dioxide, is supported as an active ingredient on the support, the support is phosphorus surface-modified phosphorus alumina surface It provides a catalyst for methane reforming reaction using carbon dioxide, characterized in that the alumina support.
  • the phosphorus-alumina support may be characterized in that it contains 0.5 to 5% by weight relative to the total weight of the phosphorus-alumina support.
  • the catalyst may be characterized in that the cobalt is supported by 1 to 10% by weight based on the total weight of the catalyst.
  • the alumina may be characterized in that the specific surface area of 10 m 2 / g ⁇ 300 m 2 / g.
  • Another embodiment of the present invention comprises the steps of (a) surface modification of alumina with a phosphorus precursor, followed by calcining to obtain a phosphorus-alumina support; And (b) supporting the cobalt precursor on the obtained phosphorus-alumina support, followed by calcining to provide a catalyst, thereby providing a catalyst for methane reforming reaction using carbon dioxide.
  • the phosphor precursor is phosphoric acid (H 3 PO 4 ), phosphorus oxychloride (POCl 3 ), phosphorus pentoxide (P 2 O 5 ), ammonium dihydrogen phosphate (NH 4 H 2 PO 4), dimethyl ammonium phosphate ((NH 4) 2 HPO 4 ), triethyl phosphate ((C 2 H 5) 3 PO 4) and at least one species selected from the group consisting of phosphorus trichloride (PCl 3) It may be characterized by.
  • the cobalt precursor Co (NO 3) 2, Co (OH) 2, CoCl 2, CoSO 4, Co 2 (SO 4) 3, CoF 3 and selected from the group consisting of CoCO 3 It can be characterized by one or more kinds.
  • the phosphorus-alumina support may be characterized in that it contains 0.5 to 5% by weight relative to the total weight of the phosphorus-alumina support.
  • the catalyst may be characterized in that the cobalt is supported by 1 to 10% by weight based on the total weight of the catalyst.
  • step (a) may be characterized in that performed for 1 to 12 hours at 300 °C ⁇ 900 °C.
  • step (b) may be characterized in that it is carried out for 1 to 12 hours at 300 °C ⁇ 900 °C.
  • Another embodiment of the present invention provides a method for preparing syngas using the catalyst to produce syngas from a gas comprising methane and carbon dioxide.
  • the reactor may be characterized in that it is selected from the group consisting of a fixed bed reactor, a fluidized bed reactor and a slurry reactor.
  • the catalyst for methane reforming reaction using carbon dioxide according to the present invention is prepared by supporting an active ingredient on an alumina support surface-modified with phosphorus, and thus, methane using carbon dioxide rather than a conventional catalyst for reforming reaction due to strong bonding between the alumina support and the active ingredient.
  • the sintering of the active ingredient is delayed, and the formation of the inactive phase of the cobalt aluminate phase is suppressed, thereby improving the activity stability of the catalyst.
  • the method for producing a synthesis gas according to the present invention generates a high carbon monoxide synthesis gas, which is a raw material for high value-added products such as oxo alcohol, dimethyl ether, polycarbonate, acetic acid, etc., thereby making it possible to resource carbon dioxide, a greenhouse gas. .
  • Figure 2 is a graph showing the carbon dioxide conversion and deactivation of the catalyst prepared in Examples 1 to 4 and Comparative Example 1.
  • Figure 4 is an image before and after the reforming reaction of the catalyst prepared in Example 2 and Comparative Example 1.
  • FIG. 5 is an X-ray diffraction graph after the reforming reaction of the catalysts prepared in Example 2 and Comparative Example 1.
  • FIG. 5 is an X-ray diffraction graph after the reforming reaction of the catalysts prepared in Example 2 and Comparative Example 1.
  • Figure 6 is a graph of the conversion rate of the reforming reaction time of the catalyst prepared in Example 2.
  • FIG. 7 is a graph of conversion rate versus reforming reaction time of the catalyst prepared in Comparative Example 1.
  • the present invention provides a catalyst for methane reforming reaction using carbon dioxide in which cobalt is supported as an active ingredient, wherein the support is a phosphorus-alumina support surface-modified with phosphorus on an alumina surface. It relates to a catalyst for the methane reforming reaction used.
  • the present invention (a) surface-modified alumina with a phosphorus precursor, and then calcined to obtain a phosphorus-alumina support; And (b) supporting the obtained cobalt precursor on the obtained phosphorus-alumina support, followed by calcining to prepare a catalyst, which relates to a method for preparing a catalyst for methane reforming reaction using carbon dioxide.
  • catalysts used in the reforming reaction of methane using carbon dioxide are known to use transition metals such as cobalt, nickel, zirconia as active ingredients, and alumina, silica and the like as support components.
  • transition metals such as cobalt, nickel, zirconia
  • alumina, silica and the like as support components.
  • the catalytic activity is completely different depending on the treatment method and the mixture of each component.
  • alumina which is a support component
  • alumina is surface-modified with a phosphorus precursor to obtain a phosphorus-alumina support, and after the cobalt precursor is supported on the obtained phosphorus-alumina support, the catalyst is calcined.
  • the alumina has a support component having a high specific surface area, and a specific surface area of 10 m 2 / g ⁇ 300 m 2 / g.
  • the specific surface area of the alumina is less than 10 m 2 / g, the reduction of specific surface area may occur greatly in the surface treatment process of phosphorus, which may cause a problem that the specific surface area of the surface-modified support with phosphorus may be excessively small. If it exceeds 300 m 2 / g it is preferable to maintain the above range because the phenomenon of clogging of the fine pores in the process of phosphorus is severe or the thermal stability is reduced.
  • Such alumina is surface modified with a phosphorus precursor to obtain a phosphorus-alumina support.
  • the phosphorus precursor is generally used in the art, and is not particularly limited. Specifically, phosphoric acid (H 3 PO 4 ), phosphorus oxychloride (POCl 3 ), phosphorus pentoxide (P 2 O 5 ), and ammonium di Hydrogen phosphate (NH 4 H 2 PO 4 ), diammonium phosphate ((NH 4 ) 2 HPO 4 ), triethyl phosphate ((C 2 H 5 ) 3 PO 4 ), phosphorus trichloride (PCl 3 ), etc. have.
  • the alumina surface modification of such phosphorus precursor can be carried out using a method such as commonly used impregnation method, coprecipitation method, spraying method, ion exchange method, etc., and calcined to obtain a phosphorus-alumina support.
  • the firing is carried out for 1 to 12 hours at 300 to 900 °C, preferably for 2 to 6 hours at 500 to 700 °C bar, if the firing temperature and time is less than 300 °C or 1 hour surface of the alumina by the phosphorus precursor
  • the effect of phosphorus addition may be reduced due to the slight modification effect, and the specific surface area of the support may be reduced due to the blockage of micropores due to the sintering phenomenon exceeding 900 ° C or 12 hours. It is good to keep.
  • the phosphorus-alumina support prepared by the above process contains 0.5 to 5% by weight of phosphorus based on the total weight of the phosphorus-alumina support, and the specific surface area is 10 to 300 m 2 / g, preferably 100 to 200 m 2 / g.
  • the phosphorus-alumina support With respect to the total weight of the phosphorus-alumina support, when the phosphorus is less than 0.5% by weight, the effect of changing the alumina surface property due to the addition of phosphorus is small, so that the effect of increasing the reactivity is insignificant. The clogging of fine pores may be serious and may cause a problem that the specific surface area of the catalyst is reduced.
  • the specific surface area of the phosphorus-alumina support is less than 10 m 2 / g, there is a problem in that the dispersibility of cobalt decreases during the surface modification process of the cobalt component, thereby decreasing the catalytic activity, and when it exceeds 300 m 2 / g.
  • the reactivity of the cobalt is reduced by reducing the reactivity of the cobalt.
  • the catalyst is baked for 1 to 12 hours at 300 to 900 ° C, preferably for 2 to 6 hours at 500 to 700 ° C.
  • the catalyst may be prepared by a method generally used in the art, and specifically, may be supported by carrying out a method such as impregnation and coprecipitation.
  • the impregnation method is carried out in an aqueous solution or an alcohol solution for 30 to 720 minutes at 20 ⁇ 90 °C, the precipitate prepared by the above process after drying for about 24 hours in an oven at 100 °C or more and used as a catalyst do.
  • the co-precipitation method co-precipitates the cobalt precursor in an aqueous solution of pH 7-8 on the slurry of the phosphorus-alumina support, and then matures in the range of 40-90 ° C. to filter and wash the precipitate so that the content of the cobalt component is the total weight of the catalyst. With respect to, it is prepared to contain from 1 to 10% by weight.
  • a pH of 7 to 8 may be used to maintain a basic precipitation agent.
  • the basic precipitant sodium carbonate, calcium carbonate, ammonium carbonate, ammonia water, or the like is preferably used.
  • the aging time of the catalyst is appropriately maintained at less than 0.1 to 10 hours, preferably 0.5 to 8 hours, since the formation of a support containing cobalt having good activity in the given aging time range is advantageous, and the aging time is If it is short, the dispersibility of cobalt decreases, which is disadvantageous in terms of catalytic activity, and if it exceeds 10 hours, the particle size of cobalt increases, which decreases the active point and the synthesis time, which is not economical.
  • the cobalt / phosphorus-alumina catalyst prepared by the above method is first washed and dried to prepare a cobalt / phosphorus-alumina catalyst carrying the final cobalt.
  • the precipitate prepared by the above method is subjected to a washing process and then dried in an oven at 80 ° C. or more for one day, and then the precipitate is directly used for catalyst synthesis, or calcined after further supporting additional active ingredients other than cobalt. Can be used.
  • the additional active ingredient may be nickel, copper, manganese, tungsten, zirconium and the like.
  • the cobalt precursor is not particularly restricted to be commonly used in the art, in particular Co (NO 3) 2, Co (OH) 2, CoCl 2, CoSO 4, Co 2 (SO 4) 3, CoF 3 and CoCO It may be at least one selected from the group consisting of 3 , preferably a nitrate precursor is generally used.
  • the solvent and precursor components used in the manufacturing process may remain in the catalyst, which may cause an increase in side reactions.
  • the particle size increases due to the sintering phenomenon of the active ingredient, thereby reducing the dispersibility of the active ingredient such as cobalt and at the same time decreasing the specific surface area of the support, thus adversely affecting the methane reforming reaction. It is desirable to maintain the catalyst preparation range.
  • the catalyst is supported by 1 to 10% by weight of cobalt based on the total weight of the catalyst. If the supported amount is less than 1% by weight, there is a problem in that the reactivity decreases because there is not enough active ingredient to show methane reforming reactivity using carbon dioxide. And, if it exceeds 10% by weight it is preferable to maintain the above range because the problem of economical efficiency is lowered due to the increase in the catalyst manufacturing cost.
  • the catalyst for methane reforming reaction using carbon dioxide prevents migration between the active ingredient at high temperature due to the strong bonding between the alumina support surface-modified with phosphorus and the active ingredient, thereby delaying the sintering phenomenon of the active ingredient, The formation of cobalt aluminate phases can be suppressed to improve the activity stability of the catalyst.
  • the present invention relates to a method for producing a synthesis gas for producing a synthesis gas from a gas containing methane and carbon dioxide using the catalyst described above in another aspect.
  • the reactor used in the carbon dioxide reforming reaction of methane is generally used in the art, but is not particularly limited. Specifically, a fixed gas phase fixed bed reactor, a fluidized bed reactor, or a slurry slurry may be used.
  • reaction raw material CH 4 / CO The molar ratio of 2 is maintained in the range of 0.5 to 2.0.
  • reaction temperature is less than 600 ° C, the reaction rate is not sufficient and no conversion occurs. If the reaction temperature exceeds 900 ° C, carbonization of the catalyst starts and the deactivation is early. As the reaction pressure increases, the activity of the catalyst is maintained stably, but it is not a largely applied variable, and the initial reactor installation cost is high at a pressure exceeding 2 MPa.
  • the space velocity of the gas mixture is less than 30,000 ml / g cat hr and is greater than the 120,000 ml / g cat hr and is the deactivation of the catalyst because the shorter the contact time of the reactants and catalyst.
  • the mixing ratio of the methane and carbon dioxide is out of the range it is inclined to one side conversion, which is an inefficient reaction, it is preferable to maintain the range.
  • the catalyst prepared according to the present invention improves the activity stability of the catalyst in the carbon dioxide reforming reaction of methane, so that the high conversion and especially the CO / H 2 Syngas having a high molar ratio can be produced.
  • the ⁇ -alumina was heat treated at 750 ° C. for 6 hours before being used as a support.
  • the ⁇ -alumina was heat treated at 750 ° C. for 6 hours before being used as a support.
  • ⁇ -Al 2 O 3 support In order to impregnate the ⁇ -Al 2 O 3 support, 1.266 g of phosphoric acid was added to 200 ml of distilled water to prepare a diluted phosphoric acid solution, and then 20 g of ⁇ -Al 2 O 3 was added to the prepared phosphoric acid solution. The mixture was stirred vigorously at room temperature for 1 hour. After stirring the ⁇ -Al 2 O 3 solution impregnated with phosphoric acid, the solvent used was removed using a vacuum distillation apparatus. The semi-dried phosphate-treated ⁇ -Al 2 O 3 support was dried in a drying oven at 100 ° C., and then calcined at 500 ° C. for 4 hours to be used as a phosphorus-alumina support for Co loading. At this time, the phosphorus content was 2 wt% based on the total weight of the phosphorus-alumina support.
  • the ⁇ -alumina was heat treated at 750 ° C. for 6 hours before being used as a support.
  • the phosphoric acid solution was diluted by the addition of phosphoric acid 1.898 g of distilled water 200 ml, and then added to the ⁇ -Al 2 O 3 20 g in the prepared acid solution to impregnate the person on ⁇ -Al 2 O 3 support, The mixture was stirred vigorously at room temperature for 1 hour. After stirring the ⁇ -Al 2 O 3 solution impregnated with phosphoric acid, the solvent used was removed using a vacuum distillation apparatus. The semi-dried phosphate-treated ⁇ -Al 2 O 3 support was dried in a drying oven at 100 ° C., and then calcined at 500 ° C. for 4 hours to be used as a phosphorus-alumina support for Co loading. At this time, based on the total weight of the phosphorus-alumina support, the phosphorus content was 3 wt%.
  • the ⁇ -alumina was heat treated at 750 ° C. for 6 hours before being used as a support.
  • the phosphoric acid solution was diluted by the addition of phosphoric acid 2.531 g of distilled water 100 ml, and then added to the ⁇ -Al 2 O 3 20 g in the prepared acid solution to impregnate the person on ⁇ -Al 2 O 3 support, The mixture was stirred vigorously at room temperature for 1 hour. After stirring the ⁇ -Al 2 O 3 solution impregnated with phosphoric acid, the solvent used was removed using a vacuum distillation apparatus. The semi-dried phosphate-treated ⁇ -Al 2 O 3 support was dried in a drying oven at 100 ° C. and then calcined at 500 ° C. for 4 hours to be used as a phosphorus-alumina support for Co loading. In this case, the phosphorus content was 4 wt% based on the total weight of the phosphorus-alumina support.
  • Example 1 In order to carry the active ingredient on the same alumina support as Example 1, 2.469 g of the same cobalt precursor as in Example 1 was added to 100 ml of distilled water to prepare a solution in which the active ingredient was dissolved, and then 10 g of the alumina support to the prepared cobalt solution. After the addition, the mixture was stirred vigorously at room temperature for 1 hour. The cobalt-supported solution was removed by distillation using a vacuum distillation apparatus and dried in a drying oven at a temperature of 100 ° C. The dried catalyst was calcined at a temperature of 500 ° C. for 4 hours to prepare a catalyst such that the content of cobalt supported on the alumina support was 5 wt%.
  • the reforming reaction of methane and carbon dioxide was carried out in the following manner, and the results are shown in FIGS. 1 and 2, respectively.
  • 0.3 g of a catalyst having an average particle size of 250 ⁇ m prepared by Examples 1 to 4 and Comparative Example 1 was filled using quartz wool.
  • the reactor used for the reforming reaction is a fixed bed reactor equipped with an external heating system, which is a tubular reactor of 1/4 inch diameter quartz.
  • the catalysts prepared in Examples 1 to 4 and Comparative Example 1 were reduced with 5% H 2 -Ar at 750 ° C. for 1 hour.
  • Catalytic reaction was performed by supplying a mixed gas of methane: carbon dioxide: nitrogen having a mixing molar ratio of 4: 4: 2 into the reactor at a space velocity of 60,000 ml / g cat ⁇ hr. At this time, the catalytic reaction was carried out at a reaction temperature condition of atmospheric pressure, 750 °C, the gas discharged after the reaction was analyzed using a gas chromatography system equipped with a thermal conductivity detector (Thermal conductivity detector).
  • Examples 1 to 4 and Comparative Example 1 carried out under the above reaction conditions are shown in Figures 1 and 2 the conversion rate and inactivity of methane and carbon dioxide.
  • the conversion rate of methane and carbon dioxide was quantified based on the reaction time of 20 hours, and the degree of deactivation was calculated by the difference between the conversion rate after 1 hour and the conversion rate after 20 hours.
  • the catalyst of Example 1 exhibited the highest conversion of methane and carbon dioxide, and the catalyst of Example 2 showed similar catalytic activity to the catalyst of Example 1, but with the least deactivation. The degree was shown.
  • the catalysts of Examples 3 and 4 not only the conversion rate of methane and carbon dioxide decreased but also the degree of deactivation also increased.
  • the catalyst of Comparative Example 1 showed a higher conversion rate than the catalyst of Example 4, but showed the greatest degree of deactivation. From the results of Examples 1 to 4, the activity and inactivation degree of the methane reforming catalyst proposed in the present invention were greatly influenced by the phosphorus content used for impregnation, and it can be interpreted that an optimum content exists. Comparison was made with Comparative Example 1 based on the catalyst of Example 2 with the least inactivation observed.
  • the degree of inactivation of the catalyst in the methane reforming reaction was most observed in Comparative Example 1, and the lowest degree of inactivation was shown in Example 2.
  • the degree of deactivation tended to increase.
  • the amount of carbon deposition was lowest in Comparative Example 1, and the largest in Example 2.
  • many studies have been carried out to solve this problem as sintering phenomenon and carbon deposition of the active metal in the reforming reaction is the biggest cause of catalyst deactivation.
  • the catalyst of the present invention showed a different behavior from the general cause of inactivation of the reforming reaction, and the catalyst of the present invention is thought to have other causes besides carbon deposition.
  • Example 2 showed stable catalytic activity during the reforming reaction of 50 hours, whereas the catalyst of Comparative Example 1 was deactivated and the conversion rate of methane and carbon dioxide was drastically decreased. .
  • the catalyst for methane reforming reaction using carbon dioxide according to the present invention is prepared by supporting an active ingredient on an alumina support surface-modified with phosphorus, and thus, methane using carbon dioxide rather than a conventional catalyst for reforming reaction due to strong bonding between the alumina support and the active ingredient. Even in the high temperature reforming reaction, there is an industrial applicability because it has the effect of delaying the sintering of the active ingredient, suppressing the formation of the inactive cobalt aluminate phase and improving the activity stability of the catalyst.
  • the method for producing a synthesis gas according to the present invention generates a high carbon monoxide synthesis gas, which is a raw material for high value-added products such as oxo alcohol, dimethyl ether, polycarbonate, acetic acid, etc. Therefore, there is industrial applicability.

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Abstract

La présente invention concerne un catalyseur pour le reformage de méthane à l'aide de dioxyde de carbone et son procédé de préparation et, plus spécifiquement, un catalyseur pour le reformage de méthane à l'aide de dioxyde de carbone et son procédé de préparation, le catalyseur étant configuré de telle sorte que : un ingrédient actif est supporté sur un support d'alumine qui a été modifié en surface avec du phosphore; en conséquence, la formation d'une phase inactive et le frittage du principe actif sont supprimés, même dans une réaction à haute température, du fait de la liaison entre le support d'alumine et le principe actif; et ainsi la stabilité d'activité du catalyseur peut être améliorée.
PCT/KR2018/005528 2017-05-18 2018-05-15 Catalyseur pour le reformage de méthane à l'aide de dioxyde de carbone, et son procédé de préparation Ceased WO2018212542A1 (fr)

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KR1020170061862A KR101933014B1 (ko) 2017-05-18 2017-05-18 이산화탄소를 이용한 메탄 개질 반응용 촉매 및 이의 제조방법
KR10-2017-0061862 2017-05-18

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WO2018212542A1 true WO2018212542A1 (fr) 2018-11-22

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CN113546627B (zh) * 2021-07-30 2022-12-09 宁夏大学 一种低温二氧化碳甲烷化催化剂及其制备方法、应用

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KR20180126870A (ko) 2018-11-28

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