WO2021214955A1 - エッグシェル型白金担持アルミナ触媒、その製造方法、及びその使用方法 - Google Patents

エッグシェル型白金担持アルミナ触媒、その製造方法、及びその使用方法 Download PDF

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WO2021214955A1
WO2021214955A1 PCT/JP2020/017564 JP2020017564W WO2021214955A1 WO 2021214955 A1 WO2021214955 A1 WO 2021214955A1 JP 2020017564 W JP2020017564 W JP 2020017564W WO 2021214955 A1 WO2021214955 A1 WO 2021214955A1
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platinum
catalyst
supported
egg
shell type
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French (fr)
Japanese (ja)
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佳巳 岡田
今川　健一
政志 斉藤
健太 福留
治人 小林
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Chiyoda Corp
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Chiyoda Corp
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Priority to EP20932812.9A priority Critical patent/EP4140578A4/en
Priority to PCT/JP2020/017564 priority patent/WO2021214955A1/ja
Priority to KR1020227040504A priority patent/KR20220158289A/ko
Priority to AU2020443246A priority patent/AU2020443246A1/en
Priority to JP2022516775A priority patent/JP7466634B2/ja
Priority to CN202080099978.1A priority patent/CN115485063A/zh
Priority to US17/918,661 priority patent/US20230148027A1/en
Priority to CA3176199A priority patent/CA3176199A1/en
Priority to TW110114573A priority patent/TW202144076A/zh
Publication of WO2021214955A1 publication Critical patent/WO2021214955A1/ja
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Definitions

  • the present invention relates to a metal catalyst used in a process using a catalyst such as chemical production, hydrogen production, fine chemical production, environmental purification such as exhaust gas treatment, and an egg-shell type platinum carrier in which platinum is supported on an alumina carrier.
  • the present invention relates to an alumina catalyst, a method for producing the same, and a method for using the same.
  • a platinum-supported alumina catalyst in which platinum or the like is supported on an alumina carrier undergoes a dehydrogenation reaction in which hydrogen is dehydrogenated with the corresponding aromatics from hydrogenated aromatics such as methylcyclohexane, cyclohexane, decalin, and dibenzyltoluene.
  • a dehydrogenation reaction in which hydrogen is dehydrogenated with the corresponding aromatics from hydrogenated aromatics such as methylcyclohexane, cyclohexane, decalin, and dibenzyltoluene.
  • a porous alumina carrier made of a metal oxide of alumina is prepared, and the obtained porous alumina carrier is prepared with an aqueous solution of platinum chloride, an aqueous solution of platinum ammonium chloride, acetylacetonato platinum, or the like.
  • a solution of a catalytic metal compound such as a solution of an organic platinum compound
  • drying to obtain a dried product carrying a catalytic metal compound, for example, under the conditions of 350 ° C. or higher and 800 ° C. or lower and 0.5 hours or longer and 24 hours or shorter. It is produced by firing, and if necessary, hydrogen-reducing the obtained catalyst metal compound-supported calcined product under the conditions of, for example, 250 ° C. or higher and 800 ° C. or lower and 0.5 hours or longer and 24 hours or lower.
  • the platinum atom has a large atomic weight of 195 and the mass, and the platinum compound is strongly adsorbed on the catalyst carrier of the platinum compound used as a platinum source. Therefore, the platinum compound is inside the alumina carrier. Since it is adsorbed and fixed only on the outer shell of the alumina carrier before it diffuses into the catalyst, when the dispersed state of the platinum metal is observed on the catalyst cross section, the platinum metal is supported only on the outer peripheral portion of the catalyst, and the carrier. It is known that it is a so-called egg shell type platinum-supporting catalyst in which no platinum metal is supported inside.
  • the molecules of the raw material diffuse into the catalyst even if the active metal platinum is supported inside the catalyst. It is known that the reaction preferentially occurs around the outer shell of the catalyst particles because the reaction does not proceed sufficiently due to the slow speed. In such a reaction, the egg shell type in which the active metal is present only in the outer shell of the catalyst is more advantageous.
  • the density of the active metal particles becomes high, so that the dispersion degree of the active metal particles cannot be sufficiently realized, and due to syntaring and coking. There is a risk that problems such as catalyst deterioration are likely to occur.
  • Patent Document 1 discloses an egg-shell type platinum-supported alumina catalyst in which the pore sizes of the platinum-supported alumina catalyst are uniform to the extent that the diffusion resistance does not increase and the platinum dispersion is good. Further, a catalyst in which platinum metal is well dispersed over the entire cross section of the catalyst has been developed so that the surface area of the carrier can be fully utilized in the reaction in which the diffusion resistance does not affect, and Patent Document 2 describes such a catalyst. A uniform platinum-supported alumina catalyst is disclosed.
  • the molecules of the raw material diffuse into the catalyst even if the active metal platinum is supported inside the catalyst. It is known that the reaction preferentially occurs around the outer shell of the catalyst particles because the reaction does not proceed sufficiently due to the slow speed. In such a reaction, the egg shell type in which the active metal is present only in the outer shell of the catalyst is more advantageous.
  • the density of the active metal particles becomes high, so that the dispersion degree of the active metal particles cannot be sufficiently realized, and due to syntaring and coking. There is a risk that problems such as catalyst deterioration are likely to occur.
  • Patent Document 1 discloses a platinum-supported alumina catalyst in which the pore sizes of the platinum-supported alumina catalyst are uniform to the extent that the diffusion resistance does not increase, and the platinum-supported alumina catalyst is well dispersed. Further, a catalyst in which platinum metal is well dispersed over the entire cross section of the catalyst has been developed so that the surface area of the carrier can be fully utilized in the reaction in which the diffusion resistance does not affect, and Patent Document 2 describes such a catalyst. A platinum-supported alumina catalyst is disclosed.
  • Platinum-supported alumina catalysts have long been used in catalytic processes in a wide range of fields, but in recent years they have been used in the organic chemical hydride method, which is one method of hydrogen energy carriers that has been attracting attention as a storage and transportation technology for hydrogen energy. ing. Development of platinum-supported alumina catalysts having higher performance than conventional platinum-supported alumina catalysts has been promoted, and Patent Documents 1 and 2 are required for the use of platinum-supported alumina catalysts in the organic chemical hydride method. It discloses its use in dehydrogenation reactions.
  • the organic chemical hydride method is a method of "storing" and “carrying” hydrogen as an organic chemical hydride compound (hydrogenated organic compound) in which hydrogen is incorporated into the molecular structure of a chemical product by a chemical reaction.
  • the organic chemical hydride method has been proposed since the 1980s, but it is difficult to carry out industrially because the life of the dehydrogenation catalyst that generates hydrogen from the compound of the organic chemical hydride that has taken in hydrogen is extremely short.
  • the key to technological development was the development of a new dehydrogenation catalyst with sufficient performance such as catalyst life that can be used industrially.
  • Non-Patent Documents 3 and 4 disclose the background of the development of such an organic chemical hydride method.
  • Japan has included a policy to promote the practical application and dissemination of hydrogen energy as a national policy from the 4th basic energy plan after the earthquake, and following the formulation of the hydrogen and fuel cell technology roadmap, the basic hydrogen strategy will be implemented in 2017. It has been decided by the Cabinet.
  • the above-mentioned organic chemical hydride method can provide a hydrogen energy carrier that "stores” and "carries” hydrogen energy on a large scale, and its practical application is included in the basic hydrogen strategy, and hydrogen supply by 2030.
  • the price target is 30 yen / Nm 3
  • the 2050 target is 20 yen / Nm 3 . Therefore, cost reduction by continuous development of improved technology is required, and improvement of catalyst performance, particularly catalyst life, has a great influence on cost reduction.
  • Japanese Patent No. 4652695 Japanese Patent No. 4142733 Yoshimi Okada, Energy / Resources, Vol.33, No. 3,168 (2016) Yoshimi Okada, Tokyo Metropolitan High Pressure Gas Association Bulletin, August 2019, September 2019 Agency for Natural Resources and Energy, Hydrogen Basic Strategy (December 2017)
  • the homogeneous platinum-supported alumina catalyst of Patent Document 2 has a relatively long catalyst life and is practically useful, but further improvement is desired. Since the dehydrogenation reaction in the organic chemical hydride method is an endothermic reaction and an equilibrium reaction in which the number of molecules increases due to the reaction, the higher the reaction conditions and the lower the pressure, the more efficient it is. On the other hand, the hydrogen produced is preferably at a high pressure depending on the intended use, so that a catalyst that can be used even at a higher reaction temperature may be required. However, when the reaction conditions are high, side reactions are likely to occur, so it is necessary to improve the selectivity of the catalyst. Further, when the reaction condition becomes high temperature, carbon is likely to be generated on the catalyst, and the catalyst is likely to be deteriorated.
  • the dehydrogenation reaction as described above, a reaction at a low pressure is preferable. Therefore, a catalyst having a small pressure loss is required, and a catalyst having a large particle size is advantageous. As the particle size of the catalyst increases, the gas diffusion into the catalyst decreases, so the egg shell type catalyst is advantageous in consideration of the efficiency of platinum used in the catalyst.
  • the present inventors have found that the catalyst life can be improved by adding a second component other than the alkali metal in the egg-shell type platinum-supported alumina catalyst.
  • an object of the present invention is to improve the catalytic activity and selectivity, particularly the catalyst life, in an egg-shell type platinum-supported alumina catalyst which is advantageous when the diffusion rate of the raw material in the catalyst pores is slow.
  • Another object of the present invention is to provide a method for producing an egg-shell type platinum-supported alumina catalyst having excellent catalytic activity and selectivity, particularly excellent performance in catalyst life, and a method for using the same.
  • One aspect of the present invention is an egg-shell type platinum-supported alumina catalyst, which is selected from the group of an alumina carrier, platinum dispersed and supported on the outer shell of the alumina carrier, and vanadium, chromium, molybdenum, and phosphorus. It has one kind or two or more kinds of second components. According to this aspect, the catalyst life can be improved.
  • the content of the platinum is preferably 0.05 wt% or more and 5.0 wt% or less as the platinum element.
  • the content of the second component is preferably 0.1 wt% or more and 5.0 wt% or less for each element.
  • the alumina carrier has pores having a surface area of 150 m2 / g or more, a pore volume of 0.40 cm3 / g or more, an average pore diameter of 40 ⁇ or more and 300 ⁇ or less, and an average pore diameter of ⁇ 30 ⁇ or less with respect to the total pore volume. The proportion should be 60% or more.
  • Another aspect of the present invention is a method for producing an egg-shell type platinum-supported alumina catalyst, which comprises one or more components selected from the group consisting of vanadium, chromium, molybdenum, and phosphorus in an alumina carrier.
  • a step of impregnating an aqueous solution of the compound and then drying and firing, a step of supporting platinum on the alumina carrier after firing in an egg shell type, and reducing the alumina carrier carrying platinum in a hydrogen atmosphere. has steps to do.
  • Another aspect of the present invention provides a method for dehydrogenating hydrogenated aromatics by using an egg shell type platinum-supported alumina catalyst to dehydrogenate hydrogenated aromatics.
  • the hydrogenated aromatics are one or two selected from the group consisting of hydrides of monocyclic aromatics, hydrides of bicyclic aromatics, and hydrides of compounds having three or more aromatic rings. The above mixture is preferable.
  • the hydrogenated aromatics are one or more selected from the group consisting of methylcyclohexane, cyclohexane, dimethylcyclohexane, tetralin, decalin, methyldecalin, biphenyl, diphenylmethyl, dibenzotriol and tetradecahydroanthracene. It should be a mixture.
  • the homogeneous catalyst is effective when the diffusion of the raw material into the catalyst is sufficiently performed, and the egg shell type catalyst is effective when the diffusion into the catalyst is restricted and is not sufficiently performed. Therefore, it is preferable to use these two types of catalysts properly according to the state of diffusion in the reaction field. Further, even in the same reaction, the diffusion state of the raw material into the catalyst may differ depending on the position in the reactor, and the concentration of the raw material becomes low near the outlet where the reaction has proceeded, so that the diffusion into the catalyst can be restricted. .. In such a case, it is preferable to use a homogeneous type and an egg shell type catalyst in combination in the reactor.
  • the degree of diffusion of the raw material into the catalyst is generally expressed by the catalyst effective coefficient, but the catalyst effective coefficient can be controlled by changing the size and shape of the catalyst pellets. From these, it is possible to produce platinum alumina catalysts having various catalyst effective coefficients by changing the size and shape of the catalyst pellets for both the uniform type and the egg shell type catalysts.
  • the alumina carrier in which platinum and the second component are present is preferably one in which the pore size is controlled as uniformly as possible.
  • the sulfur-containing porous metal oxide has a surface area of 150 m 2 / g or more, a pore volume of 0.4 cm 3 / g or more, an average pore diameter of 40 ⁇ or more and 300 ⁇ or less, and an average pore diameter with respect to the total pore volume.
  • a porous metal oxide in which the pores of ⁇ 30 ⁇ occupy 60% or more is preferable.
  • Patent Document 1 occupies pores having a surface area of 150 m 2 / g or more, a pore volume of 0.55 cm 3 / g or more, an average pore diameter of 90 ⁇ or more and 300 ⁇ or less, and a pore diameter of 90 ⁇ or more and 300 ⁇ or less with respect to the total pore volume.
  • a platinum-supported alumina catalyst is disclosed in which platinum is supported on a porous ⁇ -alumina carrier having a ratio of 60% or more. As described above, this catalyst is a general egg-shell type platinum-supported alumina catalyst, and Patent Document 1 also discloses a catalyst to which an alkali metal is added as a means for improving the catalyst life.
  • Patent Document 2 discloses a uniform platinum-supported alumina catalyst that improves the catalyst life by suppressing the decomposition reaction while making the dispersed form of the supported platinum uniform by containing sulfur in the alumina carrier. doing.
  • an alumina carrier containing sulfur or a sulfur compound it is considered that when an alumina carrier containing sulfur or a sulfur compound is used, the decomposition reaction suppressing effect is equal to or higher than that even if the acid spots are not masked with an alkali metal. Was done.
  • the sulfur element forms a composite oxide together with alumina and changes the residual acid point to a different structure in the case of alumina alone. At that time, it was considered that the form when the sulfur element formed a composite oxide with alumina was generally a sulfuric acid root form.
  • the increase in the number of steps for adding the second component causes an increase in cost, but the cost reduction effect due to the extension of the life of the catalyst according to the present invention is the cost of the catalyst production cost. It is extremely high compared to the up, and it is possible to extend the replacement life of the dehydrogenation catalyst from the conventional 1 to 2 years to 3 to 4 years depending on the method of using the catalyst in the reactor.
  • This catalyst is typically used as a dehydrogenation catalyst, but is used by filling the catalyst reaction tube of a heat exchange type reactor.
  • the number of catalytic reaction tubes may be several thousand in a large reactor, similar to a general heat exchanger.
  • the platinum-supported alumina catalyst used in such a reactor is extracted to replace it with a new catalyst when the catalyst life is reached, which is when its performance drops to a certain yield. Platinum is recovered from the extracted waste catalyst and recycled for the production of the next replacement catalyst. Since the extraction work requires several days and the filling of the new catalyst requires more work days, it takes about two weeks to replace the catalyst. During that time, production is stopped, so reducing the frequency of replacement greatly contributes to cost reduction.
  • the life of the catalyst disclosed in Patent Document 1 and Patent Document 2 is 1 to 2 years, but the life of the alkali-added uniform platinum-supported alumina catalyst according to the present invention is 4 years, and the catalyst replacement frequency is half. It can be reduced to the following.
  • the egg-shell type platinum-supported alumina catalyst of the present invention has higher catalytic performance than the egg-shell type platinum-supported alumina catalyst, and is particularly excellent in terms of catalyst life. Further, according to the production method of the present invention, these catalysts can be easily mass-produced in the existing catalyst production equipment. These catalysts can be used as a substitute for the existing platinum-supported alumina catalyst, and can also be suitably used as a dehydrogenation catalyst for methylcyclohexane or the like in the organic chemical hydride method, which is one of the hydrogen storage and transportation technologies.
  • the egg-shell type metal-supported catalyst refers to a state in which the metal species supported on the cross section of the molded catalyst are dispersed and supported only on the outer shell portion of the cross section. That is, a metal-supported portion 2 in which a metal species is supported is formed on the outer shell portion of the porous carrier 1.
  • the metal species are dispersed over the entire cross section of the catalyst, and the metal-supporting portion 2 on which the metal species is supported is formed throughout the inside of the molded body of the porous carrier 1. say.
  • the egg-shell type platinum-supported alumina catalyst is composed of an alumina carrier, platinum dispersed and supported on the outer shell of the alumina carrier, and one or more second components selected from the group of vanadium, chromium, molybdenum, and phosphorus. Has.
  • the alumina carrier has a surface area of 150 m 2 / g or more, a pore volume of 0.40 cm 3 / g or more, an average pore diameter of 40 ⁇ or more and 300 ⁇ or less, and an average pore diameter of ⁇ 30 ⁇ or less with respect to the total pore volume. Occupies more than 60%.
  • the alumina carrier is preferably a porous ⁇ -alumina carrier.
  • the alumina carrier for example, as disclosed in Japanese Patent Publication No. 6-72005, a slurry of aluminum hydroxide produced by neutralizing an aluminum salt is filtered and washed, and the obtained alumina hydrogel is dehydrated and dried, and then 400. It is preferably a porous ⁇ -alumina carrier obtained by firing at ° C. or higher and 800 ° C. or lower for about 1 to 6 hours, and more preferably, the pH value of the alumina hydrogel is set to the alumina hydrogel dissolved pH range and the boehmite gel precipitated pH range.
  • the porous ⁇ -alumina carrier obtained through this pH swing step has excellent uniformity of pore distribution, and there is little variation in physical properties even in the molded alumina carrier pellets, and the physical properties of each pellet are stable. It is excellent in that it is.
  • the amount of the second component added on the above alumina carrier is 0.1 wt% or more and 5.0 wt% or less, preferably 0.3 wt% or more and 3.0 wt% or less, and more preferably 0.5 wt% or more. It is 2.0 wt% or less. If the amount of the second component supported is less than 0.1 wt%, the catalyst life is short and the effect is low. On the contrary, if the amount of the second component supported is more than 5.0 wt%, the activity is lowered and the catalyst is catalyst. There is a problem that the life is shortened.
  • Examples of the compound of the second component used when adding the second component to the above alumina carrier include chloride, bromide, iodide, nitrate, sulfate, acetate, propionate and the like of the second component element.
  • Preferably water-soluble and / or soluble in an organic solvent such as acetone for example, vanadium chloride, vanadium bromide, vanadium iodide, ammonium metavanadate, vanadyl chloride, vanadyl sulfate, vanadium acetylacetate oxide.
  • examples thereof include inorganic phosphates and organic phosphate compounds.
  • the second component element when adding the second component element to the egg shell type platinum-supported alumina catalyst, after impregnating with the solution of the second component element compound, room temperature or more and 200 ° C. or less and 0.5 hours or more and 48 hours or less are preferable. After drying under the drying conditions of 50 ° C. or higher and 150 ° C. or lower and 0.5 hours or higher and 24 hours or lower, more preferably 80 ° C. or higher and 120 ° C. or lower and 0.5 hours or higher and 5 hours or lower, 350 ° C. or higher and 600 ° C. or lower and It is preferable to bake under the conditions of 0.5 hours or more and 48 hours or less, more preferably 350 ° C. or more and 450 ° C. or less, and 0.5 hours or more and 5 hours or less.
  • the amount of platinum supported on the alumina carrier carrying the second component is 0.05 wt% or more and 5.0 wt% or less, preferably 0.1 wt% or more and 3.0 wt% or less. If the amount of platinum supported is less than 0.05 wt%, there is a problem that the activity is low. On the contrary, if it is more than 5.0 wt%, the particle size of platinum becomes large, the selectivity is lowered, and sintering is easy. There is a problem that it is easily deteriorated.
  • the above alumina carrier may be impregnated with a solution of a platinum compound, dried, and then fired at a predetermined temperature.
  • the platinum compound include various complex compounds such as chloride, bromide, ammonium salt, carbonyl compound, amine and ammine complex of platinum and acetylacetonato complex.
  • Platinum compounds include, for example, platinum chloride, acetylacetonato platinum, ammonium platinum salt, platinum bromide, platinum dichloride, platinum tetrachloride hydrate, carbonyl platinum dichloride dichloride, dinitrodiamine platinum salt and the like. Platinum compound of.
  • the alumina carrier to which the platinum compound is attached is dried under the conditions of 50 ° C. or higher and 200 ° C. or lower and 0.5 hours or higher and 48 hours or lower, and then 350 ° C. or higher and 600. Baking is carried out under the conditions of ° C. or lower and 0.5 hours or more and 48 hours or less, more preferably 350 ° C. or higher and 450 ° C. or lower, and 0.5 hours or longer and 5 hours or shorter.
  • the calcined alumina carrier is hydrogenated under the atmosphere of hydrogen gas under reducing conditions of 350 ° C. or higher and 600 ° C.
  • the method for producing an egg-shell type platinum-supported alumina catalyst is to impregnate an alumina carrier with an aqueous solution of a compound consisting of one or more components selected from the group consisting of vanadium, chromium, molybdenum, and phosphorus, and then drying. It includes a step of performing firing, a step of supporting platinum in an egg shell type on the alumina carrier after firing, and a step of reducing the alumina carrier carrying platinum in a hydrogen atmosphere.
  • the physical properties of the alumina carrier are 150 m 2 / g or more in surface area, 0.40 cm 3 / g or more in pore volume, 40 ⁇ or more and 300 ⁇ or less in average pore diameter, and ⁇ 30 ⁇ in average pore diameter with respect to the total pore volume.
  • An egg-shell type platinum-supported alumina catalyst in which the following pores occupy 60% or more of an alumina carrier, and 0.1 or more and 3 wt% or less of platinum as a platinum element is dispersed and supported on the outer shell of the carrier cross section. The catalyst to which an alkali metal is added is disclosed.
  • the present invention comprises adding a component selected from vanadium, chromium, molybdenum, and phosphorus as a second component other than platinum to the egg shell type platinum-supported alumina catalyst disclosed in Patent Document 1, instead of an alkali metal.
  • the present invention has been completed by finding that it is superior in catalyst performance, particularly catalyst life performance, as compared with an alkali metal-added egg-shell type platinum-supported alumina catalyst.
  • the egg shell type platinum-supported alumina catalyst of the present invention is used, for example, as a dehydrogenation catalyst for hydrogenated aromatics used as a hydrogen energy carrier in the organic chemical hydride method, which is one of the methods for storing and transporting hydrogen energy.
  • the hydrogenated aromatics are one or more selected from the group consisting of hydrides of monocyclic aromatics, hydrides of bicyclic aromatics, and hydrides of compounds having three or more aromatic rings. It is preferable to be a mixture of.
  • the hydrogenated aromatics are one or a mixture of two or more selected from the group consisting of methylcyclohexane, cyclohexane, dimethylcyclohexane, tetralin, decalin, methyldecalin, biphenyl, diphenylmethyl, dibenzotriol, and tetradecahydroanthracene. It should be.
  • catalyst deterioration is observed in which the performance gradually deteriorates with the lapse of the reaction time.
  • the cause of catalyst deterioration is carbon precipitation called caulking.
  • Caulking is a phenomenon in which carbon precipitation occurs on the surface of platinum metal, which is an active metal, mainly due to a decomposition reaction of a raw material compound such as methylcyclohexane, and as a result, the effective active points of the active metal are covered and do not function.
  • Hydrogen has been attracting attention as a clean secondary energy since the 1970s, and in Japan, hydrogen production technology and hydrogen production technology were used in the 1974-1992 Sunshine Project, the 1978-1992 Moonlight Project, and the 1993-2001 New Sunshine Project. Research and development of fuel cells has been promoted.
  • the development of the liquefied hydrogen method was started in the WE-NET project from 1992 to 2002.
  • the development of the organic chemical hydride method has a long history, dating back to the Euro Quebec project implemented as an international research and development project by the Quebec government of Canada and 12 European countries in the 1980s. The plan was to use the abundant surplus hydroelectric power in Quebec to electrolyze water to produce hydrogen and transport the Atlantic Ocean for use in Europe.
  • a liquid hydrogen method is being studied as a first candidate, a liquid ammonia method as a second candidate, and an organic chemical hydride method as a third candidate.
  • the organic chemical hydride method was called the MCH method.
  • the Euro Quebec project was carried out for about 10 years until around 1992, but neither method was put into practical use and the plan was completed. Since then, the technology for storing and transporting hydrogen on a large scale has been put into practical use. Not converted.
  • the Organic Chemical Hydrolide Method is a saturated cyclic compound such as methylcyclohexane (MCH) that incorporates hydrogen into the molecule by hydrogenating hydrogen with an aromatic such as toluene (TOR).
  • MCH methylcyclohexane
  • TOR aromatic such as toluene
  • TOR is a fuel base material contained in high-octane gasoline in an amount of 10 wt% or more, and is also widely used as an industrial solvent. It is easy to procure in large quantities because it is a general-purpose chemical that is produced in the world with more than 20 million tons per year.
  • the first of this method is that it is a highly safe method that can reduce the potential risk of hydrogen storage and transportation on a large scale to the risk of conventional gasoline storage and transportation in principle. It is a feature and is the first reason why the applicant paid attention to this method.
  • storage in large tanks of TOR and MCH and transportation by chemical tankers and chemical lorries have been put into practical use as chemical substances for a long time.
  • Demand for gasoline and light oil automobile fuels is expected to decrease due to the trend toward electrification of automobiles in the future, and it is also a great merit that existing infrastructure such as these storage tanks can be diverted.
  • a repeated demonstration demonstration plant was constructed in 2013, and a total of about 10,000 hours of demonstration operation was carried out from April of the same year to November 2014, and it was confirmed that high performance as designed could be maintained stably, and the technology was established. Completed.
  • NEDO New Energy and Industrial Technology Development
  • Japan has included a policy to promote the practical application and dissemination of hydrogen energy as a national policy from the 4th basic energy plan after the earthquake, and following the formulation of the hydrogen and fuel cell technology roadmap, the basic hydrogen strategy will be implemented in 2017. It has been decided by the Cabinet.
  • the above-mentioned organic chemical hydride method is included in the basic hydrogen strategy as a hydrogen energy carrier that "stores” and "carries" hydrogen energy on a large scale, and its practical application is included in the hydrogen supply price target of 30 yen by 2030.
  • / Nm 3 , 20 ⁇ / Nm 3 is set as a target for 2030. From this, cost reduction by continuous development of improved technology is required, and improvement of catalyst performance is an important factor for cost reduction. Therefore, the present invention is effective in practical use of the organic chemical hydride method and is industrially effective. Is an invention with high utility.
  • the egg shell type platinum-supported alumina catalyst can be effectively used not only as a catalyst but also as an adsorbent and the like. It is also useful as a guard column filler for the purpose of pretreatment for adsorbing impurities and the like in a catalytic reaction process to which the catalyst of the present invention can be applied, such as application to the organic chemical hydride method.
  • the egg shell type platinum-supported alumina catalyst according to the present embodiment may be used together with a uniform alkali-added platinum-supported alumina catalyst.
  • the homogeneous alkali-added platinum-supported alumina catalyst includes an alumina carrier, sulfur or a sulfur compound dispersed over the entire cross section of the alumina carrier, platinum dispersed and supported over the entire cross section of the alumina carrier, and sodium and potassium. , And one or more alkali metals selected from the group of calcium.
  • the alumina carrier has a surface area of 150 m 2 / g or more, a pore volume of 0.40 cm 3 / g or more, an average pore diameter of 40 ⁇ or more and 300 ⁇ or less, and an average pore diameter of ⁇ 30 ⁇ or less with respect to the total pore volume. It is good that the ratio of is 60% or more.
  • the amount of sulfur contained in the carrier is preferably 0.15 wt% or more and 5 wt% or less, and more preferably 0.15 wt% or more and 3.0 wt% or less as the sulfur content. The most suitable sulfur content range is 0.15 wt% or more and 3.0 wt% or less.
  • the amount of platinum supported is preferably 0.05 wt% or more and 5.0 wt% or less, preferably 0.1 wt% or more and 3.0 wt% or less.
  • the amount of alkali added is preferably 0.1 wt% or more and 5 wt% or less, preferably 0.3 wt% or more and 3.0 wt% or less, and more preferably 0.5 wt% or more and 1.5 wt% or less.
  • Examples of the compound of the alkaline metal used when supporting the alkaline metal on the homogeneous platinum-supported alumina catalyst include chloride, bromide, iodide, nitrate, sulfate, acetate, propionate and the like of the alkaline metal, which is preferable.
  • Is water-soluble and / or soluble in an organic solvent such as acetone for example, sodium chloride, sodium bromide, sodium iodide, sodium nitrate, sodium sulfate, sodium acetate, sodium propionate, potassium chloride, etc.
  • an organic solvent such as acetone
  • examples thereof include potassium bromide, potassium iodide, potassium nitrate, potassium sulfate, potassium acetate, potassium propionate, calcium chloride, calcium bromide, calcium iodide, calcium nitrate, calcium sulfate, calcium acetate, calcium propionate and the like.
  • the egg shell type platinum-supported alumina catalyst and the uniform type alkali-added platinum-supported alumina catalyst may be filled in the same reactor.
  • the egg-shell type platinum-supported alumina catalyst and the homogeneous alkali-added platinum-supported alumina catalyst may be arranged in series or mixed with each other.
  • the egg shell type platinum-supported alumina catalyst can be suitably used for the dehydrogenation reaction of hydrogenated aromatics such as methylcyclohexane used as a hydrogen energy carrier, and the organic chemical hydride method hydrogen storage and transportation system can be put into practical use.
  • hydrogenated aromatics such as methylcyclohexane used as a hydrogen energy carrier
  • organic chemical hydride method hydrogen storage and transportation system can be put into practical use.
  • it has the potential to be widely applied to existing catalytic reaction processes in which platinum-supported alumina catalysts are used, and has extremely high industrial utility.
  • a suspension of aluminum hydroxide slurry (pH 10) was obtained by instantly adding an aqueous solution of sodium aluminate to hot dilute sulfuric acid with vigorous stirring, and this was used as seed aluminum hydroxide, and hot dilute sulfuric acid and aluminum were continuously stirred. The operation of alternately adding the aqueous acid soda solution at regular intervals was repeated to obtain a sulfuric acid-washed cake, which was extruded and dried, and then baked at 500 ° C. for 3 hours.
  • the alumina carrier thus obtained has a BET surface area of 257 m 2 / g, a pore volume of 0.66 cm 3 / g by the mercury intrusion method, and an average pore diameter of 9.3 nm, and most of the pores are near the average pore diameter. It has a sharp pore distribution concentrated in, and the volume occupied by pores with a pore diameter of 7-13 nm is 85% or more of the total pore volume, and the porous ⁇ -alumina obtained from this result.
  • the carrier has a surface area of 150 m 2 / g or more, a pore volume of 0.40 cm 3 / g or more, an average pore diameter of 40 ⁇ or more and 300 ⁇ or less, and pores having an average pore diameter of ⁇ 30 ⁇ with respect to the total pore volume.
  • the ratio meets the requirement of 60% or more.
  • Example 1 (Catalyst No. 5)] 20 g of the porous ⁇ -alumina carrier prepared by the method described in Carrier Preparation was impregnated with 33.2 mL of an aqueous solution prepared by adding the same weight of oxalic acid to 0.12 mol / L ammonium metavanadate and dissolving it. After leaving for 3 hours, the water was removed by an evaporator. Then, it was dried at 120 ° C. for 3 hours and then calcined in an air flow at 500 ° C. for 3 hours in a muffle furnace to obtain an alumina carrier containing 1.2 wt% of vanadium (V) as a second component.
  • V vanadium
  • Example 2 (Catalyst No. 6) 20 g of the porous ⁇ -alumina carrier prepared by the method described in Carrier Preparation was impregnated with 32.0 mL of a 0.12 mol / L chromium nitrate aqueous solution, left to stand for 3 hours, and then water was removed by an evaporator. Then, it was dried at 120 ° C. for 3 hours and then calcined in an air flow at 500 ° C. for 3 hours in a muffle furnace to obtain an alumina carrier containing 1.2 wt% of chromium (Cr) as a second component.
  • Cr chromium
  • Example 3 (Catalyst No. 7)
  • 20 g of the porous ⁇ -alumina carrier prepared by the method described in Carrier Preparation was impregnated with 32.0 mL of a 0.009 mol / L ammonium molybdate aqueous solution, left to stand for 3 hours, and then water was removed by an evaporator. .. Then, it was dried at 120 ° C. for 3 hours and then calcined in an air flow at 500 ° C. for 3 hours in a muffle furnace to obtain an alumina carrier containing 1.3 wt% of molybdenum (Mo) as a second component.
  • Mo molybdenum
  • Example 4 (Catalyst No. 8)
  • 20 g of the porous ⁇ -alumina carrier prepared by the method described in Carrier Preparation is impregnated with 32.0 mL of a 0.20 mol / L ammonium dihydrogen phosphate aqueous solution, left to stand for 3 hours, and then water is added by an evaporator. Removed. Then, it was dried at 120 ° C. for 3 hours and then calcined in an air flow at 500 ° C. for 3 hours in a muffle furnace to obtain an alumina carrier containing 0.9 wt% of phosphorus (P) as a second component.
  • P phosphorus
  • Examples 5 and 6 (catalyst Nos. 9 and 10)]
  • the concentration of the ammonium metavanadate aqueous solution was changed to prepare an alumina carrier containing 0.5 wt% and 2.0 wt% of vanadium (V) as the second component, and then the same method.
  • Eggshell type vanadium-added platinum-supported alumina catalyst (catalyst No. 9) supporting 0.5 wt% vanadium and 1.0 wt% platinum, 2.0 wt% vanadium and 1.0 wt
  • An egg-shell type vanadium-added platinum-supported alumina catalyst (catalyst No. 10) supporting% platinum was obtained.
  • Example 7 (Catalyst No. 11)
  • concentration of the ammonium metavanadate aqueous solution was changed to prepare an alumina carrier containing 0.5 wt% of vanadium (V) as the second component, and then the dinitrodiamine platinum aqueous solution was prepared in the same manner.
  • V vanadium
  • dinitrodiamine platinum aqueous solution was prepared in the same manner.
  • Example 8-10 (Catalyst No. 12-14)
  • concentration of the chromium nitrate aqueous solution was changed to prepare an alumina carrier containing 0.5 wt%, 2.0 wt%, and 3.0 wt% of chromium (Cr) as the second component, and then an alumina carrier containing 0.5 wt%, 2.0 wt%, and 3.0 wt% was prepared.
  • Eggshell type chromium-added platinum-supported alumina catalyst (catalyst No. 12) in which platinum was supported in the same manner and 0.5 wt% chromium and 1.0 wt% platinum were supported, 2.0 wt% chromium.
  • Eggshell type chromium addition carrying 1.0 wt% platinum and platinum-supported alumina catalyst (catalyst No. 13), and egg shell type chromium addition supporting 3.0 wt% chromium and 1.0 wt% platinum.
  • a platinum-supported alumina catalyst (catalyst No. 14) was obtained.
  • Examples 11 and 12 (catalyst Nos. 15 and 16)]
  • concentration of the aqueous solution of ammonium molybdenum was changed to prepare an alumina carrier containing 0.5 wt% and 2.0 wt% of molybdenum (Mo) as the second component, and then the same method.
  • Eggshell type molybdenum-added platinum-supported alumina catalyst (catalyst No. 15) supporting 0.5 wt% molybdenum and 1.0 wt% platinum, 2.0 wt% molybdenum and 1.0 wt
  • An egg-shell molybdenum-added platinum-supported alumina catalyst (catalyst No. 16) supporting% platinum was obtained.
  • the catalyst layer inlet temperature was set to 400 ° C.
  • the catalyst layer outlet temperature was set to 410 ° C.
  • the pressure was 0.3 MPa.
  • Gas was supplied to the reactor at a flow rate of 2.9 L / h (LHSV: 8h -1).
  • a cooler is provided on the outlet side of the reaction tube to cool the gas emitted from the reactor, and the liquid product such as liquefied toluene (TOR) and gas such as hydrogen gas are collected in a stainless steel container.
  • the liquid was separated.
  • the recovered liquid product and gas were each subjected to composition analysis by gas chromatography, and the MCH conversion rate (%) and TOR selectivity (%) from the start of the reaction to 140 hours later were calculated.
  • the catalyst after the reaction test was extracted, and the amount of carbon produced, which is a factor of catalyst deterioration, was measured by a carbon / sulfur analyzer.
  • the catalyst layer temperature was set to 380 ° C., and pretreatment reduction was performed under the condition of 15 hours under a hydrogen stream. After the pretreatment reduction is completed, the catalyst layer inlet temperature is set to 280 ° C., the catalyst layer outlet temperature is set to 380 ° C., and the reaction pressure is set to 0.55 MPa, and the MCH gas is reacted at a flow rate of 2.8 L / h (LHSV: 2.6 h -1). Supplied to the vessel.
  • a cooler for cooling the gas emitted from the reactor was provided on the outlet side of the reaction tube, and the mixture was collected in a stainless steel container to separate the liquefied liquid product such as toluene and the gas such as hydrogen gas into gas and liquid. ..
  • the recovered liquid product and gas were each subjected to composition analysis by gas chromatography, and the MCH conversion rate (%) and TOR selectivity (%) from the start of the reaction to 1400 hours later were calculated.
  • an egg-shell type platinum-supported alumina catalyst in which platinum of Comparative Example 1 (catalyst No. 1) was dispersed and supported only on the outer shell of the carrier, and an egg-shell type alkali addition of Comparative Example 2 (catalyst No. 2).
  • the sulfur of Comparative Example 3 (catalyst No. 3) was dispersed and supported on the entire alumina carrier, and platinum was dispersed and supported on the entire alumina carrier.
  • the MCH conversion rate (98.7% ⁇ 95.0%) and the TOR selectivity are both higher at the initial stage of the accelerated reaction test and after the 140-hour reaction, and the catalyst is excellent in stability and selectivity. You can see that there is.
  • the homogeneous sulfur-platinum-supported alumina catalyst of Comparative Example 3 exhibits excellent catalytic performance, but the amount of carbon produced after the reaction test is 2.6 wt%, which is that of Comparative Example 2 (catalyst No. 2). It can be seen that the amount is increased as compared with the egg shell type alkali-added platinum-supported alumina catalyst. From this result, in the catalyst of Comparative Example 3, platinum, which is a catalyst component, is uniformly dispersed on the carrier to improve the dispersibility and has a large number of active sites effective for the reaction, so that the amount of carbon precipitation increases. Even so, it is presumed that it still retains an active site that is effective for the reaction.
  • the improvement of the TOR selectivity is a difference of 0.1% as a numerical value, but since the amount of impurities generated is calculated by the following formula, the TOR selectivity is improved from 99.8% to 99.9%. This means that the amount of impurities produced is suppressed to about half.
  • Impurity production amount MCH supply amount x MCH conversion rate / 100 x (100-TOR selectivity) / 100
  • the egg-shell type platinum-supported alumina catalysts of Examples 1 to 4 show higher values in MCH conversion rate and TOR selectivity than those of the egg-shell type platinum-supported alumina catalysts to which sulfur and sodium of Comparative Example 4 are added. You can see that. From these, it can be seen that as the additive of the egg shell type platinum-supported alumina catalyst, vanadium, chromium, molybdenum, or phosphorus has higher MCH conversion rate and TOR selectivity than sodium, which is an alkali metal.
  • Example 7 in which the weight ratio of vanadium and platinum was maintained at 1: 1 and the amount of platinum was reduced to 0.5 wt%, the MCH conversion rate after 20 hours and 140 hours was Comparative Example 3. It can be seen that it is higher than (see Table 1).
  • Example 3 in which the weight ratio of vanadium and platinum was maintained at 1: 1 and the amount of platinum was reduced to 0.5 wt%, the MCH conversion rate after 20 hours and 140 hours was Comparative Example 3. It can be seen that it is higher than (see Table 1).
  • a second metal component it is possible to increase the amount of platinum on the outer periphery of the catalyst effective for the reaction and reduce the amount of expensive platinum supported. It has been shown to be.
  • Example 1 Catalyst No. 5, vanadium 1.2 wt%) and Comparative Example 3 in which the MCH conversion rate was relatively high and remained stable and the amount of carbon produced was small.
  • the results of the catalyst life test are shown in Table 5.
  • the egg-shell type platinum-supported alumina catalyst of Example 1 (catalyst No. 5) to which the second component was added reduced the MCH conversion rate by only 0.4% from 50 hours after the start of the reaction to 1200 hours after the start of the reaction.
  • the uniform platinum-supported alumina catalyst of Comparative Example 3 (catalyst No. 3)
  • the MCH conversion rate was reduced by 0.8%
  • the egg shell type second component-added platinum-supported alumina catalyst was a catalyst. Expected to have a long life.
  • the egg-shell type second component-added platinum-supported alumina catalyst maintained 99.9% from 50 hours after the start of the reaction to 1200 hours after the start of the reaction, and Comparative Example 3 (Catalyst No. 3).
  • the catalyst produces a small amount of impurities.
  • the amount of carbon produced after the 1200-hour reaction test was 2.7% in Comparative Example 3 and 1.1% in Example 1, and the stability of the catalyst was improved by suppressing the amount of carbon produced. It is suggested that the effect can be obtained.
  • the egg shell type platinum-supported alumina catalyst of the present invention can be suitably used for the dehydrogenation reaction of hydrogenated aromatics such as methylcyclohexane used as a hydrogen energy carrier, and can be used for practical use of an organic chemical hydride method hydrogen storage and transportation system. In addition to contributing, it has the potential to be widely applied to existing catalytic reaction processes in which platinum-supported alumina catalysts are used, and is an invention with extremely high industrial utility.

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PCT/JP2020/017564 2020-04-23 2020-04-23 エッグシェル型白金担持アルミナ触媒、その製造方法、及びその使用方法 Ceased WO2021214955A1 (ja)

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EP20932812.9A EP4140578A4 (en) 2020-04-23 2020-04-23 Eggshell type platinum-loaded alumina catalyst, method for producing same, and use of same
PCT/JP2020/017564 WO2021214955A1 (ja) 2020-04-23 2020-04-23 エッグシェル型白金担持アルミナ触媒、その製造方法、及びその使用方法
KR1020227040504A KR20220158289A (ko) 2020-04-23 2020-04-23 에그쉘형 백금 담지 알루미나 촉매, 그 제조 방법, 및 그 사용 방법
AU2020443246A AU2020443246A1 (en) 2020-04-23 2020-04-23 Egg shell-type platinum-loaded alumina catalyst, method of producing same, and method of using same
JP2022516775A JP7466634B2 (ja) 2020-04-23 2020-04-23 エッグシェル型白金担持アルミナ触媒、その製造方法、及びその使用方法
CN202080099978.1A CN115485063A (zh) 2020-04-23 2020-04-23 蛋壳型载铂氧化铝催化剂、其制备方法及其使用方法
US17/918,661 US20230148027A1 (en) 2020-04-23 2020-04-23 Egg shell-type platinum-loaded alumina catalyst, method of producing same, and method of using same
CA3176199A CA3176199A1 (en) 2020-04-23 2020-04-23 Egg shell-type platinum-loaded alumina catalyst, method of producing same, and method of using same
TW110114573A TW202144076A (zh) 2020-04-23 2021-04-22 蛋殼型鉑載持氧化鋁觸媒、其製造方法、及其使用方法

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CN117504867A (zh) * 2023-11-06 2024-02-06 中国科学院过程工程研究所 一种双金属催化剂及其制备方法和应用
CN117504868A (zh) * 2023-11-06 2024-02-06 中国科学院过程工程研究所 一种双金属催化剂及其制备方法和应用

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