WO2011111994A2 - Acroléine obtenue par la déshydratation en phase vapeur du glycérol, et son procédé de préparation - Google Patents

Acroléine obtenue par la déshydratation en phase vapeur du glycérol, et son procédé de préparation Download PDF

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Publication number
WO2011111994A2
WO2011111994A2 PCT/KR2011/001617 KR2011001617W WO2011111994A2 WO 2011111994 A2 WO2011111994 A2 WO 2011111994A2 KR 2011001617 W KR2011001617 W KR 2011001617W WO 2011111994 A2 WO2011111994 A2 WO 2011111994A2
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Prior art keywords
acrolein
glycerol
catalyst
zeolite
reaction
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Ceased
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PCT/KR2011/001617
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English (en)
Korean (ko)
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WO2011111994A3 (fr
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박은덕
정광덕
김용태
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Ajou University Industry Academic Cooperation Foundation
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Ajou University Industry Academic Cooperation Foundation
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Anticipated expiration legal-status Critical
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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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/65—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the ferrierite type, e.g. types ZSM-21, ZSM-35 or ZSM-38, as exemplified by patent documents US4046859, US4016245 and US4046859, respectively
    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/65—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the ferrierite type, e.g. types ZSM-21, ZSM-35 or ZSM-38, as exemplified by patent documents US4046859, US4016245 and US4046859, respectively
    • B01J29/655—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the ferrierite type, e.g. types ZSM-21, ZSM-35 or ZSM-38, as exemplified by patent documents US4046859, US4016245 and US4046859, respectively containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
    • C07C45/52—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition by dehydration and rearrangement involving two hydroxy groups in the same molecule

Definitions

  • the present invention relates to acrolein showing a high yield and selectivity by a vapor phase dehydration reaction in the presence of a zeolite catalyst having a H-ferrierite structure and a method for producing the same.
  • Acrolein is also known as 2-propenal, acrylaldehyde or acrylaldehyde.
  • Acrolein is highly reactive due to the incomplete reactor with simple unsaturated aldehydes.
  • it is an intermediate for the synthesis of synthetic proteins, such as acrylic acid, acrylic esters, superabsorbents, polymers, animal feed supplements, methionine.
  • Acrolein is a synthetic intermediate, because of the high toxicity that companies are trying to avoid storing and transporting the chemical.
  • acrolein In commercial processes, the production of acrolein can be produced through selective gas phase oxidation with atmospheric oxygen using propylene synthesized in the petroleum process as starting material.
  • propylene synthesized in the petroleum process as starting material.
  • methods for synthesizing acrolein using renewable raw materials that are not based on fossil fuels should be developed.
  • Glycerol can be produced as a byproduct of the process of synthesizing biodiesel as a natural product.
  • the market size of glycerol is increasing according to the production of biodiesel. Due to the price drop of glycerol, a method for industrial application of it has been studied.
  • glycerol is dehydrated to obtain it in the form of a mixture of acrolein.
  • the reaction should proceed in an acidic state. Also, the hydration reaction prefers low temperature while the dehydration reaction prefers high temperature as endothermic reaction. In addition, the development of a catalyst system that improves the reactivity and selectivity to acrolein through sufficient temperature, pressure and / or concentration of glycerol, as the various functional groups of the reactants and products may impede the yield of acrolein with side reaction products. This is required.
  • the dehydration of glycerol to acrolein can be prepared using mineral acids or acid catalysts in liquid and gaseous phases.
  • acrolein is synthesized using an acid catalyst in the liquid phase, low glycerol conversion must be maintained to obtain high acrolein selectivity.
  • Disadvantages of the liquid phase reaction can be compensated when the reaction proceeds in the high temperature and supercritical region, but the corrosion of the reactor in the process conditions and the stability of the process requires improvement in the commercial process.
  • Japanese Laid-Open Patent Publication No. 2008-290815 discloses a method for synthesizing acrolein using a batch reactor and using various aqueous sulfates (potassium sulfate, hydrogenosulfate) as a catalyst under atmospheric pressure.
  • Synthesis method proposed in the patent is a method of recovering in the aqueous solution of the hydroquinone, a polymerization inhibitor by vaporizing the synthesized acrolein. Using this process can improve the acrolein selectivity up to 82% at a conversion rate of 97%, but there are disadvantages in the process being too complex and not a continuous process for commercial application.
  • US Pat. No. 2,042,224 shows a yield of about 49% when the aqueous solution of glycerol is dehydrated using a sulfuric acid solution as a mineral acid catalyst.
  • Japanese Patent Application Laid-Open No. 2007-268363 discloses a phosphoric acid catalytic compound supported on silica (SiO 2 ) in the gas phase, specifically P, P-Mn, P-Zr, P-Cu, P-Fe, P-Al, or MnP 2 . Supported silica (SiO 2 ) is illustrated.
  • Japanese Laid-Open Patent Publication No. 2007-268364 exemplifies a phosphoric acid catalytic compound supported on silica (SiO 2 ) in the gas phase, specifically P-Na, P-Cs, and PK.
  • Dehydration of glycerol with acid catalysts includes alcohols, aldehydes, ketones, aromatic compounds, specifically hydroxypropanone, propanealdehyde, acetaldehyde, acetone, allyl alcohol, acrolein, methanol and glycerol oligomer adducts, glycerol multicondensation products And cyclic glycerol ethers and the like and cause side reactions with substances such as phenols and polyaromatic compounds. This not only reduces the selectivity of the target but also causes deactivation of the catalyst due to carbon deposition.
  • a zeolite catalyst having a specific structure using glycerol as a starting material in particular, an H-peririte structure It was found that the gas phase dehydration reaction in the presence of the catalyst of the zeolite having a zeolite can exhibit high yield and selectivity over a wide temperature range.
  • an object of the present invention to provide an acrolein prepared by gas phase dehydration reaction in the presence of a catalyst of a zeolite having an H-peririte structure using glycerol as a starting material.
  • Another object of the present invention is to provide a method for preparing acrolein that can minimize the production of by-products during the reaction process.
  • the present inventors have previously reported the use of a zeolite having a specific silica-alumina molar ratio to prepare acrolein by reacting a glycerol containing water as a starting material with a zeolite catalyst having an H-peririte structure, and thus using the catalyst.
  • Zeolite catalysts such as H-ZSM-5, Hb, HY, and H-mordernite and low-silica-alumina (SiO 2 -Al 2 O 3 ) molar ratios with acid content and gamma alumina (g-Al 2 O 3 ), amorphous
  • silica-alumina SiO 2 -Al 2 O 3
  • silica SiO 2
  • the technical solution of the present invention is specifically to provide acrolein prepared by the dehydration reaction of glycerol in the presence of a catalyst comprising a zeolite having an H- ferrierite structure.
  • the present invention provides a method for preparing acrolein comprising the step of dehydrating a glycerol in the presence of a catalyst comprising a zeolite having an H-peririte structure.
  • the zeolite having the H-ferrierite structure is characterized in that the molar ratio of silica-alumina is 1000: 1 to 10: 1.
  • the content of the zeolite having the H-ferrierite structure is characterized in that it comprises 1 to 100% by weight of the total catalyst.
  • the zeolite having the H-ferrierite structure is characterized in that it further comprises the step of heat treatment (pretreatment) NH 4 -ferrilite at a reaction temperature of 200 to 900 °C.
  • the H-ferrierite is characterized in that at least one selected from the group consisting of alkali metals, alkaline earth metals and lanthanide metals are ion exchanged.
  • the alkali metal is at least one selected from the group consisting of potassium (K), lithium (Li), sodium (Na), rubidium (Rb), cesium (Cs) and Fr (franium), and the alkaline earth metal is beryllium ( Be), magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba) and radium (Ra) is one or more selected from the group consisting of, the lanthanum-based metal is lanthanum (La), cerium ( Ce, Praseodymium (Pr), Neodymium (Nd), Promethium (Pm), Samarium (Sm), Europium (Eu), Gadolinium (Gd), Terbium (Tb), Dysprosium (Dy), Holmium (Ho), Erbium ( Er), thulium (TM), ytterbium (Yb), and lutetium (Lu).
  • the dehydration reaction is characterized in that it is carried out in a continuous gas phase, fluidized bed gas phase or batch liquid phase mode.
  • the dehydration reaction is characterized in that the molar ratio of glycerol: water is 1: 0.5 to 1: 100.
  • the dehydration reaction is characterized in that it is carried out at a temperature of 220 to 380 °C.
  • the method for producing acrolein according to the present invention is H- having a low silica-alumina mole ratio having a high acid content, which has been reported in the past by using a catalyst having a zeolite having an H-peririte structure having a specific silica-alumina mole ratio in the zeolite catalyst.
  • Zeolite catalysts such as ZSM-5, Hb, HY, H-mordernite and gamma alumina (g-Al 2 O 3 ), amorphous silica-alumina (SiO 2 -Al 2 O 3 ), silica (SiO 2 ) as catalyst It has been found that improved acrolein yields and selectivities can be achieved over a wide range of reaction temperature ranges compared to those used, and in particular, improved effects such as minimizing the production of by-products during the reaction process, high acrolein yields and selectivities. Therefore, it is expected that the method of the present invention can effectively replace the conventional acrolein manufacturing process in the gas phase.
  • the present invention relates to acrolein prepared by dehydration reaction of glycerol in the presence of a catalyst comprising a zeolite having an H-ferrierite structure.
  • the present invention also relates to a method for producing acrolein comprising the step of subjecting glycerol to a gas phase dehydration reaction in the presence of a catalyst comprising a zeolite having an H-ferrierite structure.
  • the silica-alumina mole ratio of the catalyst including the zeolite having the H-ferrierite structure is adjusted to a level of about 1000: 1 to 10: 1, preferably about 150: 1 to 25: 1. It is advantageous in terms of the surface, and a target product of acrolein can be obtained at high production rate.
  • the molar ratio of silica-alumina exceeds 1000: 1, there is a problem in that the reactivity is lower, whereas when less than 10: 1, acrolein selectivity due to side reactions may be lowered.
  • the content of the catalyst including the zeolite having the H-peririte structure of the present invention may be included in 1 to 100% by weight of the total catalyst.
  • the higher the content of the zeolite having the structure of H-peririte the more advantageous, but alumina, silica, or other layered inorganic materials may be further included for catalyst molding.
  • the content of the zeolite having the structure of H- ferrierite is less than 1% by weight of the total catalyst, the reactivity required by the present invention is greatly lowered, which is not preferable.
  • the H-ferrierite may be used by itself, and typically includes a step of heat-treating (pretreatment) NH 4 -ferrierite, the heat treatment process is not limited to a special gas composition but helium , Nitrogen, or air is preferable but the heat treatment temperature may be performed in the range of about 200 to 900 °C.
  • alkali metal, alkaline earth metal or lanthanum-based metal may be ion-exchanged in order to enhance the performance of H-ferrierite.
  • the element is potassium (K), lithium (Li), sodium (Na), rubidium (Rb), cesium (Cs), Fr (franchis), beryllium (Be), magnesium (Mg), calcium ( Ca), Strontium (Sr), Barium (Ba), Radium (Ra), Lanthanum (La), Cerium (Ce), Praseodymium (Pr), Neodymium (Nd), Promethium (Pm), Samarium (Sm), Europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (TM), ytterbium (Yb), and lutetium (Lu)
  • K potassium
  • K potassium
  • the catalyst can not only broaden the reaction temperature range compared to the prior art, but also can be used to prepare the target product in high yield and high selectivity over the reaction temperature range.
  • reaction in order to maximize the yield of acrolein, by-product alcohols, aldehydes, ketones, aromatic compounds, preferably hydroxypropanone, acetaldehyde, propanealdehyde, acetone, allyl alcohol, methanol and glycerol oligomer adducts, and glycerol multicondensation
  • the reaction may proceed while removing products such as products, cyclic glycerol ethers, and the like, phenols and polyaromatic compounds, out of the reaction system.
  • the reaction for dehydration in the starting material glycerol may be carried out in a continuous gas phase, fluidized bed gas phase or batch liquid phase, preferably a continuous gas phase reaction, but is not limited thereto.
  • the addition ratio of the starting material glycerol and water can be determined according to the desired product, in a ratio of about 1: 0.5 to 1: 100, preferably about 1: 9 to 1:12 on a molar basis. Can be added. In particular, adjusting to a level of about 1:11 is advantageous for improving the yield and selectivity, and the target acrolein can be obtained at a high production rate.
  • the addition ratio of glycerol: water may increase the content of water in order to increase the selectivity of acrolein, but when the addition ratio of glycerol: water exceeds 1: 12, a problem of energy consumption for vaporizing water may occur. have. This problem can be overcome by using a fluidized bed reactor, and the heat recovered due to the combustion of carbon deposited on the catalyst can be used for vaporization of the liquid phase.
  • the hydrophobicity of the catalyst can control the reaction rate of the rate step of the glycerol dehydration reaction
  • the space velocity of the glycerol (mol glycerol ⁇ g cat. -1 ⁇ h -1) is adjusted to 10 to 10,000, preferably 100 to 5,000 range.
  • the space velocity of glycerol is determined by the amount of catalyst and the flow rate. If the space velocity of glycerol is less than 10, there is a problem that the reactor becomes too large. If the space velocity of glycerol is greater than 10,000, the conversion ratio of glycerol is too low and the recycle ratio is Too high can cause problems with low economic efficiency.
  • the reaction temperature may be carried out at a temperature of about 220 to 380 °C, preferably about 260 to 350 °C.
  • reaction temperature is less than 220 °C the reaction activity is low, the reaction time or contact time also increases, so the yield of acrolein is lowered, if it exceeds 380 °C the by-products can be increased to increase the carbon deposition, the above range It is advantageous to carry out the reaction in the production of the desired acrolein with high yield and high selectivity.
  • a quartz tubular reactor having a length of 23.5 cm and an internal diameter of 9.5 mm was charged to the catalyst under atmospheric pressure and used to carry out the reaction. This reactor is located perpendicular to the furnace maintained at the reaction temperature.
  • 0.3 g of NH 4 Perilight (NH) 4 -ferrierite) catalyst was loaded into the reactor at 600 Pretreatment was carried out with a helium at a flow rate of 30 ml / min at the reaction temperature to obtain H-ferrilite.
  • a quartz tubular reactor having a length of 23.5 cm and an internal diameter of 9.5 mm was charged to the catalyst under atmospheric pressure and used to carry out the reaction. This reactor is located perpendicular to the furnace maintained at the reaction temperature.
  • 0.3 g of NH 4 Perilight (NH) 4 -ferrierite) catalyst was loaded into the reactor at 600 Pretreatment was carried out with a helium at a flow rate of 30 ml / min for 1 hour at the reaction temperature to obtain H-ferrilite with a silica-alumina molar ratio of 55.
  • the molar concentration of 8.3 mol% glycerol was fixed in the presence of helium and the water content was varied to allow it to pass through the reactor.
  • the reaction was allowed to evaporate at a temperature of at least 265 ° C. before passing through the reactor to prevent partial condensation of the reactants.
  • the average flow rate of the liquid glycerol was maintained to 23.4 mmol / h.
  • the product obtained was recovered during the initial 2 hours after the start of the reaction.
  • the product was subjected to a dehydration reaction of glycerol through the process of recovering through a trap maintained at a temperature of -5 °C, the results are shown in Table 2 below.
  • a quartz tubular reactor having a length of 23.5 cm and an internal diameter of 9.5 mm was charged to the catalyst under atmospheric pressure and used to carry out the reaction. This reactor is located perpendicular to the furnace maintained at the reaction temperature. 0.3g of NH 4 - ferrierite (NH 4 -ferrierite) and to the catalyst loaded in the reactor, performing the pre-processing at a flow rate of helium to 30ml / min each for 1 hour at 600 °C, silica - alumina molar ratio of 55 Perry H- I got an Alight.
  • NH 4 - ferrierite NH 4 -ferrierite
  • the reactor was passed through a concentration of 8.3 mol% glycerol and 91.7 mol% moisture.
  • the reaction was evaporated at a temperature of at least 265 ° C. before passing through the reactor to prevent partial condensation of the reactants.
  • the average flow rate of the liquid glycerol was maintained to 23.4 mmol / h.
  • the product obtained was recovered during the initial 2 hours after the start of the reaction.
  • the product was subjected to a dehydration reaction of glycerol through a process of recovering through a trap maintained at a temperature of -5 °C, the results are shown in Table 3 below.
  • Acrolein was synthesized by dehydrating glycerol in the same manner as in Example 1, except that 8 mol% K was used as a catalyst in a zeolite catalyst having an H-peririte structure having a silica-alumina molar ratio of 20. The method was carried out. The results are shown in Table 4 below.
  • silica (SiO 2 ), alumina (g-Al 2 O 3 ), and amorphous silica alumina (SiO 2 -Al 2 O 3 ) forming a framework of zeolite were used as a catalyst.
  • Dehydration of glycerol was carried out to synthesize acrolein. The results are shown in Table 6 below.
  • Acrolein was synthesized by dehydrating glycerol in the same manner as in Example 1, using H-ZSM-5 catalyst having a high conversion ratio of silica-alumina mole ratio of 25 and H-ZSM-5 catalyst having a silica-alumina mole ratio of 150. Reaction was carried out. However, in order to compare the selectivity, by adjusting the amount of catalyst, the conversion rate was fixed in the same manner as the conversion rate of the zeolite catalyst having the H-peririte structure shown in Table 1. The catalyst amount was 0.1 g for H-b and 0.03 g for H-ZSM-5 and the average flow rate of glycerol was maintained at 23.4 mmol / h. The results are shown in Table 7 below.
  • Hb and silica-alumina having a silica-alumina mole ratio of 25 compared to the reaction using a zeolite having a H-peririte structure having a silica-alumina mole ratio of 55 as a catalyst see Example 1.
  • H-ZSM-5 with a molar ratio of 150 was used as a catalyst, it showed low acrolein selectivity.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

La présente invention a pour objet un procédé de préparation de l'acroléine, et plus particulièrement un procédé de préparation d'acroléine avec un taux de rendement élevé et avec une sélectivité élevée sur la totalité d'une large zone de température réactionnelle par la réalisation d'une déshydratation en phase vapeur sur du glycérol contenant de l'humidité en présence d'un catalyseur de type zéolithe ayant une structure spécifique.
PCT/KR2011/001617 2010-03-09 2011-03-09 Acroléine obtenue par la déshydratation en phase vapeur du glycérol, et son procédé de préparation Ceased WO2011111994A2 (fr)

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KR10-2010-0020694 2010-03-09
KR1020100020694A KR101148995B1 (ko) 2010-03-09 2010-03-09 글리세롤의 기상 탈수화 반응을 통한 아크롤레인 및 이의 제조방법

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KR102237601B1 (ko) 2013-10-31 2021-04-08 삼성전자주식회사 자석 매립형 모터 및 자석 매립형 모터를 가지는 압축기

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DE4238493C1 (de) * 1992-11-14 1994-04-21 Degussa Verfahren zur Herstellung von Acrolein und dessen Verwendung
FR2882053B1 (fr) 2005-02-15 2007-03-23 Arkema Sa Procede de deshydratation du glycerol en acrolene
FR2882052B1 (fr) 2005-02-15 2007-03-23 Arkema Sa Procede de deshydratation du glycerol en acroleine
WO2007132926A1 (fr) 2006-05-12 2007-11-22 Nippon Shokubai Co., Ltd. Procédé de production d'acroléine
WO2008066082A1 (fr) * 2006-12-01 2008-06-05 Nippon Shokubai Co., Ltd. Procédé permettant de produire une composition contenant de l'acroléine et de la glycérine

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