WO2017160071A1 - Procédé de préparation de catalyseur pour déshydrogénation oxydative - Google Patents

Procédé de préparation de catalyseur pour déshydrogénation oxydative Download PDF

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WO2017160071A1
WO2017160071A1 PCT/KR2017/002778 KR2017002778W WO2017160071A1 WO 2017160071 A1 WO2017160071 A1 WO 2017160071A1 KR 2017002778 W KR2017002778 W KR 2017002778W WO 2017160071 A1 WO2017160071 A1 WO 2017160071A1
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catalyst
aqueous solution
oxidative dehydrogenation
precursor
dehydrogenation reaction
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Korean (ko)
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한준규
고동현
차경용
서명지
황선환
김성민
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LG Chem Ltd
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LG Chem Ltd
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Priority claimed from KR1020170030425A external-priority patent/KR101973614B1/ko
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Priority to CN201780002342.9A priority Critical patent/CN107847923B/zh
Priority to US15/744,721 priority patent/US10926246B2/en
Priority to EP17766972.8A priority patent/EP3308855B1/fr
Publication of WO2017160071A1 publication Critical patent/WO2017160071A1/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
    • B01J21/10—Magnesium; 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
    • B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
    • 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
    • B01J23/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of zinc, cadmium or mercury
    • 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
    • B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
    • 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
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/32—Manganese, technetium or rhenium
    • B01J23/34—Manganese
    • 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
    • B01J23/72—Copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/745—Iron
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • 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
    • B01J37/04—Mixing

Definitions

  • the present invention relates to a method for preparing a catalyst for an oxidative dehydrogenation reaction, and more particularly, by maintaining a constant pH of the coprecipitation solution through a double drop precipitation method to adjust the content of alpha-iron oxide in the catalyst to a certain range,
  • the present invention relates to a method for preparing a catalyst for oxidative dehydrogenation which has excellent selectivity and yield of conjugated diene according to oxidative dehydrogenation.
  • 1,3-Butadiene is an intermediate of petrochemical products, and its demand and value are gradually increasing all over the world.
  • the 1,3-butadiene is produced using naphtha cracking, direct dehydrogenation of butene, oxidative dehydrogenation of butene, and the like.
  • the naphtha cracking process has a high energy consumption due to the high reaction temperature, and because it is not a sole process for producing 1,3-butadiene alone, there is a problem that other basic oils other than 1,3-butadiene are produced in excess. .
  • the oxidative dehydrogenation of butene is a reaction of butene and oxygen in the presence of a metal oxide catalyst to produce 1,3-butadiene and water, which has a thermodynamically advantageous advantage because stable water is produced.
  • a metal oxide catalyst to produce 1,3-butadiene and water, which has a thermodynamically advantageous advantage because stable water is produced.
  • it is exothermic, so that a higher yield of 1,3-butadiene can be obtained at lower reaction temperatures than direct dehydrogenation, and 1,3-butadiene is not required because no additional heat supply is required. It can be an effective standalone production process that can meet demand.
  • the metal oxide catalyst is generally synthesized by a precipitation method, in which the pH of the metal oxide precursor aqueous solution, the pH of the basic aqueous solution, and the pH of the coprecipitation solution act as important synthetic variables.
  • This synthesis parameter affects the phase of the coprecipitate, and the catalyst prepared therefrom can affect the selectivity and yield of 1,3-butadiene according to its phase, thus stably maintaining the pH during synthesis. Maintaining skills is important. Therefore, there is a need for a method for preparing a catalyst that can maintain a pH more stably during the preparation of a metal oxide catalyst by precipitation.
  • Patent Document 1 JP2015-167886 A
  • the present invention in order to overcome the problems of the prior art, by maintaining a constant pH of the coprecipitation solution through a double drop precipitation method to adjust the content of alpha-iron oxide in the catalyst to a certain range, according to the oxidative dehydrogenation reaction It is an object of the present invention to provide a method for producing a catalyst for oxidative dehydrogenation reaction, which has excellent selectivity and yield of conjugated diene.
  • the present invention is to prepare a precursor aqueous solution by dissolving (a) trivalent cationic iron (Fe) precursor and divalent cationic metal (A) precursor in water in a molar ratio (Fe / A) 2 to 10 step; (b) dropping the precursor aqueous solution into a coprecipitation bath in which a basic aqueous solution is prepared, and maintaining the pH of the coprecipitation solution by dropping the same or another basic aqueous solution together with the basic aqueous solution; And (c) filtering the coprecipitation solution to obtain a coprecipitate.
  • a precursor aqueous solution by dissolving (a) trivalent cationic iron (Fe) precursor and divalent cationic metal (A) precursor in water in a molar ratio (Fe / A) 2 to 10 step; (b) dropping the precursor aqueous solution into a coprecipitation bath in which a basic aqueous solution is prepared, and maintaining the pH of the coprecipitation solution by
  • the selectivity and yield of the conjugated diene according to the oxidative dehydrogenation reaction is All have the effect of providing an excellent method for producing a catalyst for oxidative dehydrogenation reaction.
  • FIG. 2 is a graph showing the relative content (wt%) of the catalyst prepared according to Examples 1 to 5 and Comparative Example 2 of the present invention (phase).
  • Figure 3 is a graph showing the butene conversion, butadiene selectivity and yield in the production of butadiene using the catalyst prepared according to Examples 1 to 5 and Comparative Example 2 of the present invention.
  • the inventors of the present invention when preparing a metal oxide catalyst for oxidative dehydrogenation reaction by precipitation method, when the metal oxide precursor aqueous solution and the basic aqueous solution are added dropwise to the coprecipitation prepared with a basic aqueous solution adjusted to a specific pH, the pH of the coprecipitation solution is more than By stably controlling the phase of the metal oxide catalyst prepared therefrom, it was confirmed that the selectivity and yield of the conjugated diene were improved, thereby completing the present invention.
  • the catalyst preparation method for the oxidative dehydrogenation reaction is prepared by dissolving (a) the trivalent cation iron (Fe) precursor and the divalent cation metal (A) precursor in water at a molar ratio (Fe / A) 2 to 10 to prepare a precursor aqueous solution. Doing; (b) dropping the precursor aqueous solution into a coprecipitation bath in which a basic aqueous solution is prepared, and maintaining the pH of the coprecipitation solution by dropping the same or another basic aqueous solution together with the basic aqueous solution; And (c) filtering the coprecipitation solution to obtain a coprecipitate.
  • the water may be, for example, distilled water or purified water, and preferably distilled water.
  • the trivalent cationic iron (Fe) precursor and the divalent cationic metal (A) precursor of step (a) are not particularly limited as long as they are commonly used in the art, for example, trivalent cationic iron (Fe) precursor and It may be a metal salt comprising a divalent cation metal (A) component, specifically, it may be a nitrate, ammonium salt, sulfate or chloride of the metal component, preferably chloride It may be chloride or nitrate.
  • the divalent cation metal (A) may be at least one selected from the group consisting of, for example, divalent cation metals, and specific examples include copper (Cu), radium (Ra), barium (Ba), strontium (Sr), and calcium ( Ca), beryllium (Be), zinc (Zn), magnesium (Mg), manganese (Mn) and cobalt (Co) may be one or more selected from the group consisting of, preferably zinc (Zn), magnesium (Mg) , Manganese (Mn) and cobalt (Co) may be one or more selected from the group consisting of, more preferably zinc (Zn) or manganese (Mn).
  • the trivalent cationic iron (Fe) precursor and the divalent cationic metal (A) precursor may be included in, for example, a molar ratio (Fe / A) of 2 to 10, 2 to 6, or 2 to 5 with respect to the precursor aqueous solution.
  • a molar ratio (Fe / A) of 2 to 10, 2 to 6, or 2 to 5 with respect to the precursor aqueous solution.
  • the precursor aqueous solution may have a pH of 6 to 12, 6 to 10, or 8 to 10, and has an effect of obtaining high activity and yield for preparing 1,3-butadiene within this range.
  • the precursor aqueous solution may be 5 wt% to 10 wt% concentration, 5 wt% to 8 wt% concentration, or 6 wt% to 7 wt% concentration, and is reactive as an oxidative dehydrogenation catalyst within this range. Can be improved.
  • the precursor aqueous solution is, for example, at least 4 wt% to less than 10 wt%, 4 wt% to 7 wt%, or 4.5 to 6.5 wt%, and at least 0.5 wt% of a divalent cation iron precursor.
  • a divalent cation iron precursor To less than 10% by weight, 0.5% to 6.5% by weight, or 0.5 to 6.2% by weight in more than 80% by weight to 95.5% by weight of distilled water, 86.5% to 95.5% by weight, or 87.3% to 95.0% by weight I can prepare it.
  • the precursor aqueous solution may have a pH of 0 to 4, 1 to 3, or 1 to 2, and has an effect of stably generating a desired active ingredient when synthesizing a catalyst within this range.
  • the basic aqueous solution prepared in the co-precipitation step (b) and the basic aqueous solution in the co-precipitation bath may be an aqueous solution having the same concentration and same pH, or an aqueous solution having a different concentration or different pH, and may be a different basic aqueous solution.
  • Specific examples of the basic aqueous solution may be at least one selected from the group consisting of potassium hydroxide, ammonium carbonate, ammonium bicarbonate, sodium hydroxide aqueous solution, sodium carbonate and ammonia aqueous solution, respectively, preferably an aqueous ammonia solution, in which case the catalyst particles Large and phase is suitable for the purpose of the present invention and has the effect of easy cleaning.
  • the pH of the basic aqueous solution may be, for example, more than 8 to less than 11, 9 to 10, or 9 to 9.5, and within this range by adjusting the content of alpha-iron oxide in the catalyst to a certain range, oxidative dehydrogenation reaction The selectivity and yield of the conjugated diene according to the excellent effect.
  • the basic aqueous solution may have a concentration of 10 to 50 wt%, 15 to 40 wt%, or 25 to 30 wt%, respectively.
  • the basic aqueous solution to be dipped is for maintaining a constant pH of the coprecipitation solution that is changed due to the precursor aqueous solution to be dropped into the coprecipitation bath, may not be dripping within the range of maintaining the pH of the coprecipitation solution, the precursor aqueous solution Together with, or only the basic aqueous solution may be independently.
  • the precursor aqueous solution and the basic aqueous solution may be respectively dripping from separate jets, and in this case, the pH of the coprecipitation solution that is changed due to the precursor aqueous solution that is dipped in the coprecipitation is controlled by adjusting the drop amount of the basic aqueous solution. It is effective to let.
  • the precursor aqueous solution may be dropped into the coprecipitation at a rate of 20 g / min or more, 20 g / min to 50 g / min, or 40 g / min or more and 50 g / min, and oxidatively within this range.
  • the selectivity and yield of butadiene according to the dehydrogenation reaction are excellent.
  • the pH of the coprecipitation solution of step (b) may be, for example, more than 8 to less than 11, 9 to 10, or 9 to 9.5, and within this range, by adjusting the content of alpha-iron oxide in the catalyst to a certain range, oxidation The selectivity and yield of conjugated diene according to the dehydrogenation reaction are excellent.
  • the step (b) may further include the step of stirring the coprecipitation solution of the drop of the precursor aqueous solution is completed, in this case, there is an effect that the coprecipitation of the precursor is sufficiently made in the coprecipitation solution.
  • the stirring may be performed for 30 minutes to 3 hours, 30 minutes to 2 hours, or 30 minutes to 1 hour 30 minutes.
  • Filtration in the step (c) is not particularly limited as long as it is a filtration method commonly used in the art, for example, may be a reduced pressure filtration, a specific example may be a method of filtering under reduced pressure using a vacuum pump, In this case, there is an effect of separating washing and moisture from the catalyst.
  • the method for preparing a catalyst for the oxidative dehydrogenation reaction includes, for example, drying the co-precipitate obtained in the step (c); Firing; Or drying and firing; may be further included.
  • the filtered coprecipitate may be dried for 12 to 20 hours, 14 to 20 hours, or 14 to 18 hours at 60 to 100 ° C., 70 to 100 ° C., or 80 to 100 ° C. using a conventional dryer, for example. have.
  • the filtered coprecipitate may be calcined for 1 to 10 hours, 3 to 8 hours, or 5 to 7 hours at 400 to 800 ° C, 500 to 800 ° C, or 550 to 750 ° C, for example, using a conventional firing furnace. have.
  • the filtered coprecipitate may be dried at 60 to 100 ° C., 70 to 100 ° C., or 80 to 100 ° C. for 12 to 20 hours, 14 to 20 hours, or 14 to 18 hours using a conventional dryer.
  • the dried coprecipitate may be calcined for 1 to 10 hours, 3 to 8 hours, or 5 to 7 hours at 400 to 800 ° C, 500 to 800 ° C, or 550 to 750 ° C, for example, using a conventional firing furnace. Can be.
  • the firing method may be a heat treatment method commonly used in the art.
  • the catalyst for the oxidative dehydrogenation reaction prepared according to the method for preparing the catalyst for the oxidative dehydrogenation reaction may include, for example, spinel ferrite (AFe 2 O 4 ) and alpha-iron oxide ( ⁇ -Fe 2 O 3 ).
  • the alpha-iron oxide may be included, for example, in an amount of 15 to 80 wt%, and the selectivity and yield of the conjugated diene according to the oxidative dehydrogenation reaction are excellent in this range.
  • the catalyst for oxidative dehydrogenation of the present invention comprises an AFe 2 O 4 structure; And Fe 2 O 3 structure, wherein A is copper (Cu), radium (Ra), barium (Ba), strontium (Sr), calcium (Ca), beryllium (Be), zinc (Zn), magnesium ( Mg), manganese (Mn) and cobalt (Co) at least one member selected from the group consisting of 38 to 85% by weight, 66 to 85% by weight of AFe 2 O 4 content.
  • A is copper (Cu), radium (Ra), barium (Ba), strontium (Sr), calcium (Ca), beryllium (Be), zinc (Zn), magnesium ( Mg), manganese (Mn) and cobalt (Co) at least one member selected from the group consisting of 38 to 85% by weight, 66 to 85% by weight of AFe 2 O 4 content.
  • the AFe 2 O 4 structure is a peak having a first peak having a maximum peak intensity in a range of 34.5 ° to 35.5 ° when measured by XRD diffraction analysis, and a second peak having a second peak intensity exists in a range of 29.5 ° to 30.5 °. It is a peak, and the third peak having a third peak intensity may be one having a peak present in the range of 62 ° to 63 °.
  • the AFe 2 O 4 structure may be, for example, ZnFe 2 O 4 or MnFe 2 O 4 .
  • the Fe 2 O 3 structure is a peak having a first peak having a maximum peak intensity in a range of 33 ° to 34 ° when measured by XRD diffraction analysis, and a second peak having a second peak intensity exists in a range of 35 ° to 36 °. And a third peak having a third peak intensity may have a peak present in a range of 53.5 ° to 54.5 °.
  • the Fe 2 O 3 structure may be ⁇ -Fe 2 O 3 as an example.
  • the catalyst has, for example, a crystallite size D measured by XRD of 50 nm or more, 60 nm or more, 70 nm or more, 50 to 80 nm, 60 to 80 nm, or 70 to 80 nm, within this range.
  • Excellent catalyst activity in the phase (phase) is in accordance with the purpose of the present invention and there is an effect that is easy to wash.
  • the catalyst may have a BET surface area of at least 4.0 m 2 / g, at least 4.7 m 2 / g, 4.0 to 8.0 m 2 / g, and 4.5 to 7.0 m 2 / g, as measured by a conventional BET method. Within this range, the catalytic activity is excellent.
  • the catalyst is very versatile as a catalyst applicable to fixed bed reactors, moving bed reactors and fluidized bed reactors for oxidative dehydrogenation.
  • aqueous metal precursor solution in which 12.019 g of zinc chloride (ZnCl 2 ) and 47.662 g of ferric chloride (FeCl 3 ) were dissolved in distilled water was prepared (aqueous precursor concentration: 6.67% by weight%).
  • aqueous precursor concentration: 6.67% by weight%) 12.019 g of zinc chloride (ZnCl 2 ) and 47.662 g of ferric chloride (FeCl 3 ) were dissolved in distilled water was prepared (aqueous precursor concentration: 6.67% by weight%).
  • the metal precursor aqueous solution outlet and the basic aqueous solution outlet are respectively installed in a coprecipitation tank prepared with ammonia aqueous solution having a pH of 9.5 and a concentration of 28 wt% at room temperature, and the prepared metal precursor aqueous solution is discharged through the metal precursor aqueous solution outlet.
  • aqueous ammonia solution of the same pH and concentration as the ammonia aqueous solution of the coprecipitation bath was dropped through the basic aqueous solution outlet to keep the pH of the coprecipitation solution in the coprecipitation bath constant at 9.5. .
  • the coprecipitation solution was stirred for 1 hour so that the coprecipitation was sufficient, and the phases were separated by leaving the stirring for 1 hour at room temperature so that all the precipitates settled down.
  • the coprecipitation solution was filtered under reduced pressure using a vacuum filter to obtain a coprecipitate.
  • the coprecipitate was dried at 90 ° C. for 16 hours, and the dried co-precipitate was put into a calcination furnace for 6 hours at a temperature of 650 ° C.
  • a zinc ferrite catalyst The contents of the spinel phase ferrite (ZnFe 2 O 4 ) and alpha-iron oxide ( ⁇ -Fe 2 O 3 ) of the prepared zinc ferrite catalyst were measured by XRD (see FIGS. 1 and 2) and are shown in Table 1 below.
  • Example 1 In the first step of Example 1, by dissolving 8.593 g of zinc chloride (ZnCl 2 ) and 51.118 g of ferric chloride (FeCl 3 ) in distilled water with an aqueous metal precursor solution, the molar ratio of the metal components included in the aqueous metal precursor solution was Fe: Zn.
  • the contents of the spinel phase ferrite (ZnFe 2 O 4 ) and alpha-iron oxide ( ⁇ -Fe 2 O 3 ) of the prepared zinc ferrite catalyst were measured by XRD (see FIGS. 1 and 2) and are shown in Table 1 below.
  • Example 1 In the first step of Example 1, 5.469 g of zinc chloride (ZnCl 2 ) and 54.222 g of ferric chloride (FeCl 3 ) were dissolved in distilled water with an aqueous metal precursor solution, and the molar ratio of the metal components included in the aqueous metal precursor solution was Fe: Zn. The same procedure as in Example 1 was carried out except that 895.391 g of an aqueous metal precursor solution having a ratio of 5: 1 was used. The contents of the spinel phase ferrite (ZnFe 2 O 4 ) and alpha-iron oxide ( ⁇ -Fe 2 O 3 ) of the prepared zinc ferrite catalyst were measured by XRD (see FIGS. 1 and 2) and are shown in Table 1 below.
  • aqueous 28% by weight aqueous ammonia solution was added to 892.18 g of the metal precursor aqueous solution to adjust the pH of the coprecipitation solution to 9.5, and after the pH was stabilized, the coprecipitation solution was sufficiently prepared for 1 hour. After stirring for a while (pH 9.5), the stirring was stopped and the phases were separated by standing at room temperature for 1 hour to allow all the precipitate to sink.
  • the coprecipitation solution was filtered under reduced pressure using a vacuum filter to obtain a coprecipitate.
  • the coprecipitate was dried at 90 ° C. for 16 hours, and the dried co-precipitate was put into a calcination furnace for 6 hours at a temperature of 650 ° C. To prepare a zinc ferrite catalyst.
  • the contents of the spinel phase ferrite (ZnFe 2 O 4 ) and alpha-iron oxide ( ⁇ -Fe 2 O 3 ) of the prepared zinc ferrite catalyst were measured by XRD (see FIGS. 1 and 2) and are shown in Table 1 below.
  • Example 1 In the first step of Example 1, it was carried out as Example 1, but was dissolved in distilled water only ferric chloride (FeCl 3) 59.681 g of a metal precursor solution was used to form the metal precursor solution 895.181 g.
  • FeCl 3 ferric chloride
  • Example 1 2 1 85 15 - Example 2 3: 1 70 30 - Example 3 4: 1 52 48 - Example 4 5: 1 46 54 - Example 5 6: 1 38 62 - Comparative Example 1 2: 1 86 14 - Comparative Example 2 2: 1.5 96 - 4 Comparative Example 3 1: 0 - 100 - Comparative Example 4 2: 1 100 -
  • Butadiene was prepared by the following method using the catalyst for oxidative dehydrogenation reaction prepared in Examples 1 to 5 and Comparative Examples 1 to 4, and the results are shown in Table 2 below.
  • a reaction a mixture of 1-butene, trans-2-butene and cis-2-butene and oxygen were used, and additionally nitrogen and steam were introduced together.
  • a metal tubular reactor was used as the reactor. The ratio of the reactants was set at a molar ratio of oxygen / butene 1, steam / butene 4 and nitrogen / butene 12, and gas hourly space velocity (GHSV) 500 h ⁇ 1 .
  • GHSV gas hourly space velocity
  • the catalysts prepared in Examples and Comparative Examples were charged to a fixed bed reactor, and the volume of the catalyst bed contacted with the reactants was fixed at 75 cc. Steam was injected in the form of water, but vaporized with steam at 150 ° C. using a vaporizer to be mixed with the reactant butene mixture and oxygen to enter the reactor. The amount of butene mixture was controlled using a mass flow controller for liquids, oxygen and nitrogen were controlled using a mass flow controller for gas, and the amount of steam was controlled using a liquid pump.
  • the reaction temperature was maintained at 340 ° C. and the reaction pressure was maintained at atmospheric pressure, and after the reaction the product was analyzed using gas chromatography (GC), conversion of butene mixture, conversion of each butene in the mixture, 1,3-butadiene selectivity And 1,3-butadiene yield was calculated according to the following equations 1 to 3 through the results measured by gas chromatography.
  • GC gas chromatography
  • Comparative Example 1 prepared according to the conventional method of adjusting the pH of the coprecipitation solution by adding a basic aqueous solution, butene conversion, butadiene selection, despite having the same Fe: Zn molar ratio as Example 1 of the present invention It was confirmed that the degree and yield are poor.
  • Comparative Example 3 in which the catalyst was prepared using only the iron precursor aqueous solution, and a zinc ferrite catalyst in the form of pellets generally used for oxidative dehydrogenation reaction. Also in the case of Comparative Example 4 using the, although having the same Fe: Zn molar ratio as Example 1 of the present invention, it was confirmed that the butene conversion, butadiene selectivity and yield are poor.
  • Butadiene was synthesized in the same manner as above using the catalysts prepared in Example 6 and Comparative Example 5.
  • the butene conversion was 22.66%
  • the 1-butene conversion was 27.36%
  • the trans-2-butene conversion was 20.27%
  • the cis-2-butene conversion was 23.15%
  • the 1,3-butadiene selectivity was 28.68 %
  • the yield of 1,3-butadiene was 6.50%.
  • the butene conversion was 17.31%
  • the 1-butene conversion was 20.38%
  • the trans-2-butene conversion was 14.72%
  • the cis-2-butene conversion was 19.54%
  • the 1,3-butadiene selectivity was 15.22. %
  • the yield of 1,3-butadiene was 2.63%.
  • the inventors of the present invention when preparing the metal oxide catalyst for oxidative dehydrogenation reaction by precipitation method, the pH of the coprecipitation solution is more stable by double dropping the metal oxide precursor aqueous solution and the basic aqueous solution into the coprecipitation prepared with a basic aqueous solution adjusted to a specific pH. It was confirmed that it can be controlled to control the phase of the metal oxide catalyst prepared therefrom, thereby implementing a catalyst for oxidative dehydrogenation reaction in which the selectivity and yield of conjugated diene are improved.
  • butadiene was synthesized in the same manner as described above except that it was set to 0.75 molar ratio of oxygen / butene, 15 molar ratio of steam / butene, and molar ratio of nitrogen / butene 3 as the ratio of reactants in the experimental conditions. The results are shown in Table 3 below.
  • butadiene was prepared in the same manner as in the present experimental conditions using the catalyst prepared in Example 1 for comparison with Example 7 below, and is also described in Table 3 below.
  • Example 7 using a nitrate-based metal precursor rather than chloride, butene conversion and 1,3- compared to Example 1 using a chloride-based metal precursor Butadiene yield was found to fall slightly.
  • Example 2 In the second step of Example 1, except that pH 9.0, 28% by weight of ammonia aqueous solution was used and the pH of the coprecipitation solution in the coprecipitation tank was maintained at 9.0, the same method as in Example 1 was performed.
  • a catalyst for dehydrogenation reaction was prepared. Butadiene was synthesized in the same manner as described above except that the prepared catalyst was set at a molar ratio of oxygen / butene 0.75 mole ratio, steam / butene 15 molar ratio, and nitrogen / butene 3 as the ratio of reactants in the experimental conditions, wherein the butene conversion was 83.2%.

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  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
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Abstract

La présente invention concerne un procédé de préparation d'un catalyseur pour une déshydrogénation oxydative. Selon la présente invention, le pH d'une solution de co-précipitation est maintenu à un niveau constant à l'aide d'une technique de décantation de type à double goutte pour réguler la teneur en oxyde de fer alpha dans le catalyseur, en présentant ainsi l'avantage consistant à fournir le procédé de préparation du catalyseur pour une déshydrogénation oxydative ayant un excellent rendement et une excellente sélectivité de diène conjugué.
PCT/KR2017/002778 2016-03-18 2017-03-15 Procédé de préparation de catalyseur pour déshydrogénation oxydative Ceased WO2017160071A1 (fr)

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CN201780002342.9A CN107847923B (zh) 2016-03-18 2017-03-15 氧化脱氢用催化剂的制备方法
US15/744,721 US10926246B2 (en) 2016-03-18 2017-03-15 Method of preparing catalyst for oxidative dehydrogenation
EP17766972.8A EP3308855B1 (fr) 2016-03-18 2017-03-15 Procédé de préparation de catalyseur pour déshydrogénation oxydative

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KR20160032647 2016-03-18
KR10-2016-0032647 2016-03-18
KR1020170030425A KR101973614B1 (ko) 2016-03-18 2017-03-10 산화적 탈수소화 반응용 촉매 제조방법
KR10-2017-0030425 2017-03-10

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* Cited by examiner, † Cited by third party
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CN111655369A (zh) * 2018-04-10 2020-09-11 株式会社Lg化学 金属络合物催化剂的制备方法和由此制备的金属络合物催化剂
CN111655369B (zh) * 2018-04-10 2024-01-30 株式会社Lg化学 金属络合物催化剂的制备方法和由此制备的金属络合物催化剂

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