WO2019125008A1 - Procédé de préparation d'un catalyseur au palladium pour la préparation de peroxyde d'hydrogène hautement dispersé dans un support de dioxyde de titane rutile et procédé de préparation de peroxyde d'hydrogène l'utilisant - Google Patents

Procédé de préparation d'un catalyseur au palladium pour la préparation de peroxyde d'hydrogène hautement dispersé dans un support de dioxyde de titane rutile et procédé de préparation de peroxyde d'hydrogène l'utilisant Download PDF

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WO2019125008A1
WO2019125008A1 PCT/KR2018/016334 KR2018016334W WO2019125008A1 WO 2019125008 A1 WO2019125008 A1 WO 2019125008A1 KR 2018016334 W KR2018016334 W KR 2018016334W WO 2019125008 A1 WO2019125008 A1 WO 2019125008A1
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hydrogen peroxide
palladium
catalyst
palladium catalyst
hydrogen
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Korean (ko)
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이관영
한상수
한근호
조영훈
윤지환
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고려대학교 산학협력단
한국과학기술연구원
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Priority claimed from KR1020180165959A external-priority patent/KR102233648B1/ko
Publication of WO2019125008A1 publication Critical patent/WO2019125008A1/fr

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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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/44—Palladium
    • 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
    • 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
    • B01J37/02—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
    • B01J37/16—Reducing
    • 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
    • B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B15/00—Peroxides; Peroxyhydrates; Peroxyacids or salts thereof; Superoxides; Ozonides
    • C01B15/01—Hydrogen peroxide
    • C01B15/029—Preparation from hydrogen and oxygen

Definitions

  • the present invention relates to a process for preparing a palladium catalyst for preparing hydrogen peroxide highly dispersed in a ruta-formalized titanic carrier and a process for producing hydrogen peroxide using the palladium catalyst.
  • Hydrogen peroxide is used as a bleaching agent for pulp and fiber, disinfectant disinfectant, semiconductor cleaning liquid, oxidizer for water treatment process, and environmentally friendly oxidizer for chemical reaction (propylene oxide synthesis). As of 2009, 2.2 million tons of hydrogen peroxide are being produced annually, and the demand for hydrogen peroxide is expected to rise along with the increase in propylene oxide demand.
  • Direct manufacturing process of synthesizing hydrogen peroxide by directly reacting hydrogen and oxygen has been attracting attention.
  • This direct manufacturing process has been studied as an alternative process of commercial process because water is produced as a reaction by-product and use of organic solvent is low.
  • the direct manufacturing process is simple in construction and can be manufactured where hydrogen peroxide is needed, thus greatly reducing the risk of explosion when storing and transporting hydrogen peroxide.
  • Pd or Pd alloy (Pd-Au, Pd-Pt) is mainly used as a catalyst for direct production of hydrogen peroxide.
  • the direct hydrogen peroxide reaction there is a side reaction in which water is generated in addition to the reaction in which hydrogen and oxygen meet to generate hydrogen peroxide. Since these side reactions are also voluntary, studies are underway to increase the selectivity of hydrogen peroxide using catalysts. In order to increase the selectivity of hydrogen peroxide in the case of palladium catalysts, many studies have been carried out to increase the selectivity of hydrogen peroxide by adding an acid and a halogen anion to the solvent.
  • the inventors of the present invention have found that when a method for producing hydrogen peroxide is used, a titania carrier having a rutile phase is used and a palladium catalyst is introduced into the titania carrier It has a high dispersion and surface area, and thus the production rate of hydrogen peroxide is greatly improved. Thus, the present invention has been completed.
  • the present invention provides a method for producing a palladium catalyst for producing hydrogen peroxide by preparing a ruta daily titanic carrier, introducing a sonic wave treatment process to the ruta titanic carrier, and providing a palladium catalyst for the production of hydrogen peroxide.
  • the present invention provides a method for producing hydrogen peroxide, which comprises reacting hydrogen and oxygen in a reactor including the catalyst and a solvent using the catalyst for hydrogen peroxide production.
  • the present invention also provides a method for producing a palladium catalyst for hydrogen peroxide.
  • the ruta daily titania carrier may be manufactured by firing titania at a temperature of 800 to 1400 ° C.
  • a Pd 4+ peak can be observed in an X-ray photoelectron spectrum (XPS) of the palladium catalyst for hydrogen peroxide production.
  • XPS X-ray photoelectron spectrum
  • the specific surface area of the rutile support may be 1 to 10 m 2 / g.
  • the sound wave processing in the step (c) may be performed for 3 to 10 hours at a frequency of 40-80 Hz.
  • the reduction in step (e) may be performed in a mixed gas atmosphere of hydrogen and nitrogen.
  • the amount of palladium supported on the catalyst may be 0.03 to 0.15 wt%.
  • the present invention also provides a palladium catalyst for the production of hydrogen peroxide produced by the above process.
  • the present invention also provides a method for producing hydrogen peroxide, which comprises reacting and reacting hydrogen and oxygen as reactants in a reactor comprising the palladium catalyst for producing hydrogen peroxide and a solvent.
  • the solvent may be one or more solvents selected from the group consisting of methanol, ethanol and water.
  • the solvent may further include at least one halogen compound selected from the group consisting of chlorine, bromine, and iodine.
  • the solvent may further include at least one acid selected from the group consisting of sulfuric acid, hydrochloric acid, phosphoric acid, and nitric acid.
  • the molar ratio of hydrogen and oxygen may be from 1: 5 to 1:15.
  • the reaction can be carried out at a pressure of from 1 to 40 atm and at a temperature of from 0 to 30 < 0 > C.
  • a palladium catalyst having a specifically high dispersion and surface area on a titania carrier by using a titania carrier having a rutile phase and introducing a sonic wave treatment process into the rutile titania carrier,
  • the yield and production rate of hydrogen peroxide can be greatly improved.
  • Example 3 is an image obtained by observing a palladium catalyst prepared according to Example 1 of the present invention with HAADF-STEM and mapping Pd.
  • FIG. 4 shows the results of X-ray photoelectron spectroscopy analysis of the palladium catalysts prepared according to Examples 1 to 4 and Comparative Examples 1 and 2 of the present invention.
  • FIG. 6 is a graph showing the rate of hydrogen peroxide generation when hydrogen peroxide is directly produced from hydrogen and oxygen using the palladium catalyst prepared according to Examples 1 to 2 and Comparative Examples 1 and 2 of the present invention.
  • FIG. 7 is a graph showing the results of the direct hydrogen peroxide synthesis experiment after controlling the hydrogen conversion by controlling the weight used in the direct hydrogen peroxide synthesis reaction for the catalysts prepared according to Examples 1 to 4 and Comparative Example 1 of the present invention to about 10% The results are shown.
  • FIG. 8 shows the results of X-ray photoelectron spectroscopy analysis of the palladium catalyst prepared according to Example 1 and Examples 5 to 6 of the present invention.
  • FIG. 9 shows the results of direct hydrogen peroxide synthesis experiments on catalysts prepared according to Example 1 and Examples 5 to 6 of the present invention.
  • the present invention relates to a process for preparing a ruta-formal titania carrier and introducing a sonication process to the ruta-lit titanic carrier for palladium loading, thereby producing a palladium catalyst for producing hydrogen peroxide.
  • the crystal phase and surface physical properties of the titania are changed.
  • the palladium dispersion degree The palladium catalyst for producing hydrogen peroxide can be obtained.
  • the present invention provides a method for preparing a rutile-TiO 2 carrier, comprising: (a) preparing a rutile-TiO 2 carrier; (b) mixing the ruthoric titania carrier with a palladium precursor solution; (c) sonicating the mixture; (d) washing and calcining the sonicated mixture; And (e) reducing the calcined mixture.
  • the present invention also provides a method for producing a palladium catalyst for hydrogen peroxide.
  • the ruta daily titania carrier is manufactured, and the ruta daily titania carrier is preferably manufactured by firing titania at a temperature of 800 to 1400 ° C.
  • the ruta daily titania carrier is preferably manufactured by firing titania at a temperature of 800 to 1400 ° C.
  • the titania baked at 400 ° C had a specific surface area of about 45 m 2 / g and an 80% anatase and 20% rutile phase.
  • the crystalline phase and the surface properties of the titania is rapidly changed according to the sintering temperature, such as pore volume and average pore diameter also decreases rapidly.
  • the firing temperature is 800 ° C or higher, all of the anatase phase is converted to a rutile phase having a stable and dense structure at a high temperature to obtain titania having a rutile phase of 100%.
  • the specific surface area of the prepared rutile support may be 1 to 10 m 2 / g.
  • the rutile-type titania carrier is mixed with the palladium precursor solution.
  • the palladium precursor is used as an active metal in the present invention, and any salt capable of providing palladium may be used without any particular limitation, and palladium nitrate or palladium chloride may be preferably used.
  • the mixture is subjected to sonic wave processing.
  • the sound wave processing is performed for 3 to 10 hours at a frequency of 40-80 Hz.
  • the palladium precursor remaining after the reaction is washed using distilled water, washed and dried at a temperature of 80 to 120 ° C for 10 to 48 hours, preferably for 12 to 24 hours .
  • the firing is preferably carried out at a temperature of 100 to 800 ° C., preferably 200 to 600 ° C., for 1 to 12 hours, more preferably 4 to 8 hours.
  • the calcined mixture is reduced using a mixed gas of hydrogen and nitrogen.
  • the reduction temperature is preferably 100 to 400 ° C. and the reduction time is 1 to 8 hours.
  • palladium catalyst for hydrogen peroxide production according to the present invention is finally prepared.
  • the palladium content of the catalyst is preferably 0.03 to 0.15 wt%.
  • the present invention also provides a palladium catalyst for the production of hydrogen peroxide supported on a titania carrier produced by the above production method.
  • the palladium catalyst according to the present invention is produced through sonication using a rutaic titania carrier and can achieve significantly improved palladium dispersion even though the specific surface area of the carrier itself is very low.
  • cavitation phenomenon occurs after the minute air bubbles are generated and finally disappears, and the process of bubble disappearing occurs very rapidly, and the temperature around the air bubble is rapidly decreased.
  • the growth of crystal nuclei is suppressed, and a small and uniform crystal nucleus appears.
  • the palladium catalyst according to the present invention has a peculiar electron state such as a Pd 4 + peak observed in an X-ray photoelectron spectrum (XPS).
  • the palladium catalyst according to the present invention has a wide palladium exposed area and dispersibility, and when it is applied to the direct synthesis of hydrogen peroxide, the hydrogen conversion and the hydrogen peroxide selectivity are improved and the production amount of hydrogen peroxide is remarkably improved.
  • the present invention also provides a method for producing hydrogen peroxide comprising the steps of supplying hydrogen and oxygen to a reactor containing the catalyst for producing hydrogen peroxide and a solvent and reacting the same.
  • the solvent may be one or more solvents selected from the group consisting of methanol, ethanol and water. Specifically, it may be methanol, ethanol or a mixture of water and alcohol, preferably a mixture of ethanol and water.
  • the solvent may further include a halogen compound, preferably a halogen compound including bromine (Br), chlorine (Cl) or iodine (I), more preferably a halogen containing bromine Compound. ≪ / RTI >
  • a halogen compound including bromine (Br), chlorine (Cl) or iodine (I), more preferably a halogen containing bromine Compound.
  • a halogen compound including bromine (Br), chlorine (Cl) or iodine (I), more preferably a halogen containing bromine Compound. ≪ / RTI >
  • the palladium (Pd) particles energetic atoms such as corners and edges are present. In these atoms, the reaction that hydrogen and oxygen meet to form water is dominant, and the generated hydrogen peroxide decomposes The reaction is dominant.
  • the halogen anion is thermodynamically adsorbed on the energetic atom of palla
  • the concentration of the halogen compound in a solvent is 0.01 mM to 0.1 M More preferably 0.05 mM to 2 mM.
  • the solvent may further include an acid.
  • an acid When an acid is added, the hydrogen peroxide yield can be largely increased by suppressing the decomposition of the produced hydrogen peroxide.
  • the acid may be sulfuric acid (H 2 SO 4 ), hydrochloric acid (HCl), phosphoric acid (H 3 PO 4 ), nitric acid (HNO 3 ) or the like, preferably phosphoric acid.
  • the concentration of the acid in the solvent may be 0.01 to 1 M, preferably 0.01 to 0.1 M.
  • the reactants, hydrogen and oxygen may be in a gaseous form and may be preferably fed directly to the solvent using a Dip Tube which may be contained in a solvent to improve the solubility in the solvent.
  • the hydrogen gas may be flowed at a flow rate of 1 to 4 mL / min, and the oxygen gas may be flowed at a flow rate of 10 to 40 mL / min. More preferably, the hydrogen gas may be maintained at 1.5 to 2.5 mL / min, and the oxygen gas may be maintained at 15 to 25 mL / min, and the hydrogen: oxygen molar ratio may be 1: 5 to 1:15.
  • the ratio of oxygen to hydrogen is 1: 1, when the concentration of hydrogen is high, there is a danger of explosion. When the concentration of oxygen is high, the yield of supplied hydrogen peroxide is low.
  • the reactor is further reacted by supplying nitrogen as a reactant.
  • nitrogen it is possible to deviate from the explosion range even if the ratio of hydrogen to oxygen is set to 1: 1, and there is an advantage that it can be used without additional nitrogen separation when using oxygen in the air in the future.
  • the entire reaction pressure is regulated using a BPR (Back Pressure Regulator), and the reaction pressure can be measured through a pressure gauge connected to the reactor.
  • the reaction pressure is preferably maintained at 1 to 40 atm, preferably at normal pressure, and it may be preferable to conduct the reaction while maintaining the reaction temperature at 0 to 30 ⁇ ⁇ .
  • Example 1 1000Pd / R-TiO 2 (R means rutile phase is 100%) catalyst preparation
  • Palladium catalyst for the production of hydrogen peroxide was prepared in the same manner as in Example 1, except that the calcination temperature of the titania (TiO 2 , P25, Degussa) before carrying the palladium was 800 ° C.
  • Palladium catalyst for the production of hydrogen peroxide was prepared in the same manner as in Example 1, except that the calcination temperature of the titania (TiO 2 , P25, Degussa) before carrying the palladium was 900 ° C.
  • Palladium catalyst for the production of hydrogen peroxide was prepared in the same manner as in Example 1, except that the calcination temperature of the titania (TiO 2 , P25, Degussa) before carrying the palladium was 1100 ° C.
  • Example 5 Catalyst preparation of 1000Pd / R-TiO 2 (R means 100% rutile phase) carrying 0.07 wt% palladium
  • Example 1 The procedure of Example 1 was repeated except that 0.01085 g of palladium nitrate hydrate (Pd (NO 3 ) * x H 2 O, Sigma-Aldrich) was used and the content of palladium supported on the catalyst was adjusted to 0.07 wt% To prepare a palladium catalyst for the production of hydrogen peroxide.
  • Pd (NO 3 ) * x H 2 O palladium nitrate hydrate
  • Palladium catalyst for the production of hydrogen peroxide was prepared in the same manner as in Example 1, except that the calcination temperature of the titania (TiO 2 , P25, Degussa) before palladium loading was 600 ° C.
  • Palladium catalyst for the production of hydrogen peroxide was prepared in the same manner as in Example 1, except that the calcination temperature of the titania (TiO 2 , P25, Degussa) before carrying the palladium was 400 ° C.
  • the measurement results showed that the higher the firing temperature, the lower the specific surface area, the pore volume, and the average pore diameter. As a result, it was confirmed that the pore structure collapsed as the firing temperature was higher and the measured value became lower.
  • Example 1 1000Pd / R-TiO 2 3.28 0.009 8.2
  • Example 2 800Pd / R-TiO 2 8.96 0.027 11.3
  • Example 3 900Pd / R-TiO 2 6.61 0.017 9.9
  • Example 4 1100Pd / R-TiO 2 2.92 0.008 7.9
  • Example 5 0.07 wt% 1000Pd / R-TiO 2 2.44 0.009 7.4
  • Example 6 0.03 wt% 1000Pd / R-TiO 2 1.76 0.008 4.6
  • the crystals of the catalysts of Examples 1 and 2 and Comparative Examples 1 and 2 were analyzed by XRD analysis and the results are shown in FIG. As a result, the ratio of anatase / rutile was more than 1 when the firing temperature was low at 400 °C and 600 °C, and the ratio of rutile phase increased from 20 to 42 at 600 °C compared with 400 °C. On the other hand, when the firing temperature was higher than 800 ° C., no peaks of the anatase phase were observed, and it was confirmed that the firing temperature was 100% rutile phase.
  • the palladium content of the catalysts of Examples 1 to 4 and Comparative Examples 1 and 2 was measured through ICP-OES analysis, and the area of palladium (Pd) exposure of the catalyst was measured through CO-Chemisorption analysis. Respectively.
  • the result of the hydrogen peroxide synthesis reaction may vary depending on the exposed palladium area. Since the present invention was used for the reaction with the same palladium weight when using the above catalysts, the exposed area of palladium was expressed as the exposed area per 1 g of palladium (m 2 / g Pd ).
  • Example 1 1000Pd / R-TiO 2 0.142 98.8 22.2
  • Example 3 900Pd / R-TiO 2 0.150 79.3 17.8
  • Example 4 1100Pd / R-TiO 2 0.145 97.6 21.9 Comparative Example 1 600Pd / TiO 2 0.149 24.9 5.4 Comparative Example 2 400Pd / TiO 2 0.149 24.6 5.3
  • the surface area and the degree of dispersion of palladium of the 1000Pd / R-TiO 2 catalyst according to Example 1 of the present invention were observed to be the highest.
  • the palladium exposed areas and dispersions of Comparative Examples 1 and 2 compared to Examples 1 to 4 were three times higher than those of Comparative Example 1 and Comparative Example 1, It was confirmed that sintering was suppressed and small size particles were retained because they were more strongly bonded to palladium under the same heat treatment conditions.
  • the present invention introduces a sonication process to obtain a high palladium dispersion degree, and it was confirmed that when the rutile support is used and the sonication process is introduced together, the palladium dispersion degree is remarkably improved.
  • the size of the palladium particles was smaller for a catalyst having a larger palladium dispersion degree.
  • the average size of the palladium particles was 20 nm for the catalyst of Comparative Example 2, 14 nm for the catalyst of Comparative Example 1,
  • the catalyst of Example 3 and the catalyst of Example 1 and Example 4 were about 6 nm and about 4 nm, respectively.
  • Comparative Examples 1 and 2 were about 10 to 20 nm, 4 was mainly observed in the size of 2 ⁇ 6 nm.
  • the reason for the difference in palladium size between CO-chemisorption results and STEM photographs is that some of the existing sintered palladium (> 20 nm) is present.
  • the catalysts of Examples 1 to 4 and Comparative Examples 1 and 2 were analyzed by X-ray photoelectron spectroscopy to confirm the electron exchange phenomenon between the palladium and the support after the preparation of the catalyst and to compare the electronic states of the palladium. Respectively.
  • the catalysts of Comparative Examples 1 and 2 exhibited the palladium electron state on a general TiO 2 support. Specifically, two peaks representing the electronic states of Pd 0 and Pd 2 + were observed, and they showed low binding energy due to partial supply of electrons from titania. On the other hand, in the catalysts of Examples 1 and 4, the overall palladium peak was shifted to a relatively high binding energy, and a characteristic Pd 4 + peak was also observed. The ratio of Pd 4 + peak was 25.0%, 21.6%, 22.4%, and 24.2% in Examples 1 to 4, respectively, which was the highest in Example 1.
  • the ratio of the electronic states of Pd 0 and Pd 2 + decreases and the ratio of the electronic state of Pd 4 + increases as the palladium loading decreases from 0.14 wt% (Example 1) to 0.03 wt% (Example 6) Respectively.
  • the ratio of Pd 4 + dispersed in an atomic unit increases as the amount of Pd supported decreases.
  • the catalysts of Examples 1 to 6 and Comparative Examples 1 and 2 were reduced at 150 DEG C for 1 hour and 30 minutes, and then a reaction solvent (ultrapure water, 120 mL; ethanol: 30 mL; 3 PO 4 ) 0.03 M and 0.3 mg of palladium, respectively, and the reaction was carried out for 1 hour and 30 minutes.
  • KBr as an additive was changed at 0 mM, 0.05 mM, 0.1 mM and 0.2 mM, respectively.
  • the reaction temperature was maintained at 20 ° C and the pressure was maintained at 1 atm.
  • the catalyst according to Examples 1 and 2 of the present invention exhibited a rapid increase in selectivity of hydrogen peroxide (about 95%) with a high hydrogen conversion rate, a maximum of 1500 mmol / g Pd * h and 2300 mmol / g Pd * h of hydrogen peroxide (Fig. 6).
  • Example 1 The low hydrogen peroxide selectivities of Examples 2 to 4 versus Comparative Example 1 are predictable, given the general fact that as the palladium particle size decreases, the ratio of energetic sites on the particle surface increases. However, the high selectivity of hydrogen peroxide (60%) in Example 1 is believed to be due to the high ratio of Pd 4 + observed by X-ray photoelectron spectroscopy.
  • the ratio of Pd 4 + electron state increases as the palladium loading decreases (FIG. 8), and the selectivity of hydrogen peroxide increases as the ratio of Pd 4 + electron state increases as a result of direct synthesis of hydrogen peroxide (Fig. 9).
  • the catalyst according to Example 6 having the highest ratio of Pd 4 + showed the highest hydrogen peroxide selectivity of 84.6%.
  • the ratio of Pd 0 which is capable of supplying hydrogen, was insufficient, showing a low hydrogen conversion rate of 1.23%, resulting in a hydrogen peroxide productivity of 4916 mmol H 2 O 2 / g Pd ⁇ h.
  • the catalyst according to Example 5 showed a hydrogen conversion of 5.22% and a high selectivity of hydrogen peroxide of 78.3%, and the hydrogen peroxide productivity was also found to be the highest at 7980 mmol H 2 O 2 / g Pd ⁇ h.

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Abstract

La présente invention concerne un procédé de préparation d'un catalyseur au palladium pour la préparation de peroxyde d'hydrogène hautement dispersé dans un support de dioxyde de titane rutile, et un procédé de préparation de peroxyde d'hydrogène à l'aide du catalyseur au palladium préparé. Selon la présente invention, il est possible de fournir un catalyseur au palladium possédant une zone dispersion et une surface particulièrement élevées dans un support en dioxyde de titane au moyen d'un support en dioxyde de titane ayant une phase rutile, et d'introduire un processus de traitement par ondes sonores lors de l'immersion du palladium dans le support en dioxyde de titane rutile. De même, lorsque le catalyseur au palladium est appliqué à un procédé de production directe de peroxyde d'hydrogène, le rendement et le taux de production de peroxyde d'hydrogène peuvent être considérablement améliorés.
PCT/KR2018/016334 2017-12-20 2018-12-20 Procédé de préparation d'un catalyseur au palladium pour la préparation de peroxyde d'hydrogène hautement dispersé dans un support de dioxyde de titane rutile et procédé de préparation de peroxyde d'hydrogène l'utilisant WO2019125008A1 (fr)

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Cited By (3)

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CN110681379A (zh) * 2019-09-03 2020-01-14 北京氦舶科技有限责任公司 单原子钯催化剂及其制备和在Suzuki反应中的应用
CN111871411A (zh) * 2020-07-27 2020-11-03 南京工业大学张家港产业学院 一种双氧水合成用复合氧化钛担载贵金属催化剂、制备方法及应用方法
CN114515571A (zh) * 2022-02-15 2022-05-20 北京化工大学 一种直接合成过氧化氢的负载型Pd催化剂及其制备方法

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