WO2016145619A1 - Procédé de préparation et d'application de mordénite ayant des mésopores et des micropores - Google Patents

Procédé de préparation et d'application de mordénite ayant des mésopores et des micropores Download PDF

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WO2016145619A1
WO2016145619A1 PCT/CN2015/074419 CN2015074419W WO2016145619A1 WO 2016145619 A1 WO2016145619 A1 WO 2016145619A1 CN 2015074419 W CN2015074419 W CN 2015074419W WO 2016145619 A1 WO2016145619 A1 WO 2016145619A1
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mordenite
sio
mesopores
hours
micropores
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PCT/CN2015/074419
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Chinese (zh)
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袁扬扬
田鹏
刘中民
杨虹熠
王林英
刘琳
杨淼
李冰
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中国科学院大连化学物理研究所
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Publication of WO2016145619A1 publication Critical patent/WO2016145619A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
    • C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
    • C01B39/26—Mordenite type
    • 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
    • B01J29/18—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type

Definitions

  • the present application belongs to the field of chemistry and chemical industry, and in particular to a method for synthesizing mordenite having mesopores and micropores and an application thereof.
  • Mordenite is a two-dimensional pore structure whose structure was determined by Meier in 1961.
  • the pore structure of the molecular sieve consists of a twelve-membered ring channel of 0.67*0.70 nm and an eight-membered ring channel of 0.34*0.48 nm. Since the pores of the eight-membered ring are too small for many molecules to enter, it is generally considered that the mordenite is a one-dimensional pore molecular sieve. Due to the unique pore structure and acidity of mordenite, it has important applications in catalytic cracking, toluene disproportionation and transalkylation, aromatic alkylation, xylene isomerization, dimethyl ether carbonylation and the like.
  • a method for synthesizing a mordenite having mesopores and micropores which has the advantages of simple process, easy separation, and easy industrialization on a large scale, and the mordenite synthesized by the method avoids
  • the defects of single channel structure have broad application prospects in adsorption and catalysis.
  • the method for synthesizing mordenite having mesopores and micropores characterized in that a mixture containing a templating agent R, a silicon source, an alkali source and water is precrystallized at 50 to 120 ° C for not less than 2 hours. Adding an aluminum source and crystallization at 120-220 ° C for not less than 12 hours, the mordenite having mesopores and micropores;
  • the templating agent R is selected from the group consisting of tetraethylammonium hydroxide (abbreviated as TEAOH), tetraethylammonium chloride (abbreviated as TEACl), tetraethylammonium bromide (abbreviated as TEABr), tetraethylammonium fluoride ( At least one of TEAF), tetraethylammonium iodide (abbreviated as TEAF), and hexamethyleneimine (abbreviated as HMI);
  • TEAOH tetraethylammonium hydroxide
  • TEACl tetraethylammonium chloride
  • TEABr tetraethylammonium bromide
  • HMI hexamethyleneimine
  • the alkali source is sodium hydroxide and/or potassium hydroxide.
  • the method comprises at least the following steps:
  • step b) pre-crystallizing the mixture I obtained in step a) at 50-120 ° C for 2 to 12 hours to obtain a precursor II;
  • step b) adding an aluminum source and water to the precursor II obtained in step b) to form a mixture III having the following molar ratio:
  • Al 2 O 3 /SiO 2 0.01 to 0.25;
  • M 2 O/SiO 2 0.10 to 0.40, wherein M is Na and/or K;
  • the solid product is separated and dried to obtain the mordenite having mesopores and micropores.
  • the number of moles of silicon source is SiO 2 , which is equal to the number of moles of silicon in the system;
  • the number of moles of aluminum source is 1/2 of Al 2 O 3 , which is equal to 1/2 of the mole of aluminum in the system;
  • microporous template agent R to the number of moles of moles of R per se;
  • the number of moles of M 2 O an alkali metal M of all raw materials (silicon source, an aluminum source, an alkali source) contained in the metal oxide corresponding to the number of moles of M 2 O It is equal to 1/2 of the moles of the alkali metal element M in all the raw materials.
  • the moisture in the feedstock is a two-part addition system in which a portion of the water is used alone to dissolve the aluminum source to produce an aluminum source solution, and the remaining water is mixed with a silicon source, sodium hydroxide (potassium), and templating agent R to form a mixture I.
  • a silicon source sodium hydroxide (potassium)
  • templating agent R to form a mixture I.
  • the templating agent R in the step a) is hexamethyleneimine.
  • the templating agent R in the step a) is hexamethyleneimine.
  • the lower limit of the molar ratio range of Al 2 O 3 /SiO 2 in the mixture III of the step c) is selected from 0.01, 0.0125, 0.013, 0.015, 0.016, 0.02, 0.025, 0.03, and the upper limit is selected from 0.075, 0.10, 0.25. .
  • the lower limit of the molar ratio range of M 2 O/SiO 2 in the mixture III of the step c) is selected from 0.10, 0.15, 0.20, and the upper limit is selected from 0.27, 0.29, 0.33, 0.35, 0.36, 0.38, 0.40.
  • the molar ratio M 2 O/SiO 2 in the mixture III of the step c) is from 0.2 to 0.33, wherein M is Na and/or K.
  • the lower limit of the molar ratio range of H 2 O/SiO 2 in the mixture III of the step c) is selected from 20, 30, 40, and the upper limit is selected from the group consisting of 50, 55, 60, 70, 80, 90, 100. Further preferably, the molar ratio H 2 O/SiO 2 in the mixture III of the step c) is 30 to 60.
  • the lower limit of the molar ratio range of R/SiO 2 in the mixture III of the step c) is selected from the group consisting of 0.01, 0.02, 0.03, 0.04, 0.06, and 0.08, and the upper limit is selected from the group consisting of 0.24, 0.27, 0.28, 0.30, 0.45, and 0.50.
  • the molar ratio R/SiO 2 of the mixture III of the step c) is 0.02 to 0.45.
  • the molar ratio R/SiO 2 in the mixture III of the step c) is from 0.03 to 0.30.
  • the step c) first dissolving the aluminum source in water to obtain a solution IV, and then adding the solution IV to the precursor II in the step b) and stirring, to form the following molar Proportioned mixture III:
  • Al 2 O 3 /SiO 2 0.01 to 0.25;
  • M 2 O/SiO 2 0.10 to 0.40, wherein M is Na and/or K;
  • R/SiO 2 0.01 to 0.50.
  • the H 2 O/SiO 2 ratio in the mixture III is the total amount of water and the molar ratio of SiO 2 .
  • the two parts are added to the system, and the first part is the mixing of the raw materials in the step a);
  • the second part is the step c) water for dissolving the aluminum source.
  • the amount of water used in the second part is determined by the dissolution of the aluminum source. Those skilled in the art can determine the appropriate amount of water in the step c) according to the actual source of aluminum and the amount thereof, in order to completely dissolve the aluminum source.
  • the amount of water in the first portion can then be obtained based on the total amount of water in the target mixture in mixture III.
  • the silicon source in the step a) is at least one selected from the group consisting of silica sol, silicone gel, methyl orthosilicate, tetraethyl orthosilicate, white carbon, and water glass.
  • the aluminum source in the step c) is at least one selected from the group consisting of aluminum isopropoxide, aluminum oxide, aluminum hydroxide, aluminum chloride, aluminum sulfate, aluminum nitrate, and sodium aluminate.
  • the lower limit of the pre-crystallization temperature range in the step b) is selected from the group consisting of 50 ° C, 60 ° C, 70 ° C, 80 ° C, 90 ° C, and 100 ° C, and the upper limit is selected from 100 ° C, 110 ° C, and 120 ° C.
  • the lower limit of the time range of the pre-crystallization in the step b) is selected from 2 hours, 4 hours, and 6 hours, and the upper limit is selected from 6 hours, 8 hours, 10 hours, and 12 hours. Further preferably, the step b) is pre-crystallized for 2 to 12 hours.
  • the lower limit of the crystallization temperature range in the step d) is selected from the group consisting of 120 ° C, 125 ° C, and 130 ° C
  • the upper temperature range is selected from the group consisting of 145 ° C, 150 ° C, 155 ° C, 160 ° C, 170 ° C, 178 ° C, 180 °C, 200 ° C, 220 ° C.
  • the crystallization temperature in the step d) is from 125 to 180 °C.
  • the lower limit of the time range for crystallization in the step d) is selected from 12 hours and 24 hours, and the upper limit is selected from the group consisting of 120 hours, 144 hours, 150 hours, 168 hours, and 216 hours. Further preferably, the crystallization time in the step d) is 12 to 168 hours.
  • the mesopores Preferably, in the mordenite having mesopores and micropores, the mesopores have a pore diameter of 5 to 40 nm.
  • the pore volume ratio of mesopores to micropores is from 1 to 4.7:1.
  • the manner of crystallization in the step b) and/or the step c) may be static crystallization or dynamic crystallization.
  • the term "static crystallization" means that during the crystallization, the kettle containing the initial gel mixture is placed in an oven and the mixture in the synthesis kettle is not stirred.
  • dynamic crystallization means that the synthesis kettle containing the initial gel mixture is in a non-stationary state during crystallization, such as inversion, rotation, etc.; or in the crystallization process, the mixture inside the synthesis kettle Stir.
  • step c) After the step c) is dried, it is calcined to obtain a mordenite containing both micropores and mesopores.
  • a mordenite having mesopores and micropores the mordenite being a nanoparticle having a large outer specific surface area while avoiding defects of a single pore structure, in adsorption and Catalyst has broad application prospects.
  • the mordenite having mesopores and micropores is prepared by any of the above methods.
  • the mordenite has an external specific surface area of from 100 m 2 /g to 160 m 2 /g.
  • the mordenite has mesopores having a pore diameter of 5 nm to 40 nm.
  • the pore volume ratio of mesopores to micropores is from 1 to 4.7.
  • mordenite having mesopores and micropores prepared according to any of the above methods and/or a mordenite having mesopores and micropores according to any of the above, in adsorption separation and/or Application in catalytic reactions.
  • a dimethyl ether carbonylation catalyst having the advantages of high conversion of dimethyl ether, high selectivity of methyl acetate, and long life, the catalysis
  • the mordenite having mesopores and micropores prepared by any of the above methods and/or any of the above-mentioned mordenite having mesopores and micropores is obtained by ammonium ion exchange and calcination in air at 400 to 700 °C.
  • the preparation method of the mordenite provided by the present application has a simple process and is advantageous for large-scale industrial production.
  • the mordenite prepared according to the method provided by the present invention has micropores and mesopores, avoids defects of a single channel, and has broad application prospects in macromolecular adsorption and catalysis.
  • the mordenite prepared according to the method provided by the present application has obvious advantages in terms of diffusion and life as adsorbents and catalysts.
  • the mordenite prepared according to the method provided by the present invention has the advantages of high conversion rate, good selectivity and long life as a dimethyl ether carbonylation catalyst.
  • Figure 1 is an X-ray diffraction pattern of sample 1 # .
  • Figure 2 is a scanning electron micrograph of sample 1 # .
  • Figure 3 is a nitrogen physico-desorption desorption isotherm for sample 1 # .
  • Figure 5 is a scanning electron micrograph of sample D2 # in Comparative Example 2.
  • the elemental composition was determined using a Philips Magix 2424X ray fluorescence analyzer (XRF).
  • the scanning electron microscope (SEM) test was performed on a Hitachi SU8020 field emission scanning electron microscope with an acceleration voltage of 2 kV.
  • the pore structure of the sample was characterized by low temperature nitrogen physisorption, and the instrument used was Micromeritics ASAP2020 physical adsorption instrument.
  • silica sol 20 g of silica sol, 0.55 g of sodium hydroxide, 34.55 g of water and 0.59 g of tetraethylammonium hydroxide (TEAOH, 25%) were mixed, stirred, pre-crystallized at 50 ° C for 2 h, and then alumina acid was added dropwise thereto.
  • An aqueous solution of sodium (0.467 g of sodium aluminate dissolved in 5.4 g of water) was stirred until a homogeneous gel formed. The gel was transferred to a stainless steel reaction vessel with a PTFE liner and crystallized at 130 ° C for 168 h.
  • sample 1 # a nano mordenite having mesopores and micropores, which was designated as sample 1 # .
  • Sample # 1 gel prepared in the ratio and type of feedstock, the pre-crystallization temperature and time, crystallization temperature and time were as shown in Table 1. Sample # 1 shown in FIG.
  • a silicon source (0.1 mol in terms of SiO 2 ), water, sodium hydroxide (potassium), and a templating agent R were mixed and stirred uniformly to form a mixture I.
  • the resulting mixture I was precrystallized to form a precursor II.
  • the dissolved aluminum source aqueous solution (the aluminum source in Example 2 was dissolved in 27 g of water; the aluminum sources in Examples 3 to 25 were all dissolved in 10 g of water) was added to the precursor II, and stirred until a uniform initial gel mixture was formed.
  • the mixture III was transferred to a PTFE-lined stainless steel reaction vessel for hydrothermal crystallization, and the obtained solid product was centrifuged, washed with deionized water to neutrality, dried at 110 ° C in air, and finally The nano mordenite having mesopores and micropores was obtained by calcination in a muffle furnace at 550 ° C for 6 h, and was designated as sample 2 # ⁇ 25 # .
  • the raw material type and ratio, pre-crystallization temperature and time, crystallization mode, crystallization temperature and time in the initial gel mixture III of the prepared sample 2 # to 25 # are shown in Table 1, respectively.
  • the silicon source a silica sol; Silica B; C orthosilicate; D n-methyl silicate; silica gel E; F water glass.
  • Aluminum Source sodium aluminate I; II aluminum chloride; III aluminum hydroxide; aluminum sulfate IV; V alumina; VI aluminum isopropoxide; VII aluminum nitrate.
  • Na 2 O and K 2 O is added for its ratio of an aluminum source, a silicon source and an alkali metal oxide source contained Na 2 O and K 2 O is calculated.
  • the specific steps, raw material ratio and experimental conditions are the same as in the first embodiment, except that an aqueous solution of sodium aluminate (0.467 g of sodium aluminate dissolved in 10 g of water) is added dropwise before pre-crystallization, and stirred until uniformity is formed.
  • the gel gel was placed in a stainless steel reaction vessel with a PTFE liner, pre-crystallized at 50 ° C for 2 h, and further crystallized at 130 ° C for 168 hours.
  • the obtained solid product was centrifuged and washed with deionized water until Neutral, dried in air at 110 ° C, and finally calcined at 550 ° C for 5 h in a muffle furnace, and the obtained sample was recorded as sample D2 # .
  • Example 26 Silicon to aluminum ratio of sample 1 # ⁇ 25 # , D1 # and D2 #
  • Example 27 XRD Characterization of Sample 1 # ⁇ 25 # , D1 # and D2 #
  • XRD characterization was performed on samples 1 # to 25 # , D1 # and D2 # .
  • the XRD patterns of sample 1 # ⁇ 25 # , D1 # and D2 # are consistent with the characteristic spectra of standard mordenite zeolite molecular sieves, that is, the main diffraction peaks have the same position and shape, and the relative peak intensity is ⁇ 5% depending on the synthesis conditions. Fluctuations within the range indicate that samples 1 # to 25 # , D1 # and D2 # are both mordenite.
  • a typical XRD pattern is represented by sample 1 # , as shown in Figure 1, and the XRD diffraction peak data are shown in Table 3.
  • Example 28 Scanning electron microscopy characterization of sample 1 # ⁇ 25 # , D1 # and D2 #
  • sample 1 # is an aggregate of small particles of 20 to 50 nm.
  • sample D1 # A scanning electron microscope image of sample D1 # is shown in FIG. As can be seen from the figure, the sample is a 20 um disc-shaped crystal.
  • sample D2 # A scanning electron microscope image of sample D2 # is shown in FIG. As can be seen from the figure, the sample is a disk-shaped crystal of 1 to 2 um.
  • Example 29 Characterization of pore structure of sample 1 # ⁇ 25 # , D1 # and D2 #
  • Pore structure characterization was performed on samples 1 # ⁇ 25 # , D1 # and D2 # using low temperature nitrogen physics.
  • the adsorption desorption isotherms showed obvious hysteresis loops.
  • the typical nitrogen adsorption desorption isotherms were represented by sample 1 #, as shown in Figure 3.
  • the pore structure characterization results of sample 1 # ⁇ 25 # , D1 # and D2 # are shown in Table 4.
  • Samples 1 # ⁇ 25 # both have larger mesoporous pore volume and micropore pore volume, ie sample 1 # ⁇ 25 # has mesopores and micropores.
  • Samples D1 # and D2 # are predominantly microporous and contain almost no mesopores.
  • Example 30 Sample 1 # ⁇ 25 # , D1 # and D2 # for dimethyl ether carbonylation reaction
  • Samples 1 # ⁇ 25 # , D1 # and D2 # were separated by NH 4 NO 3 ion exchange to remove sodium ions, and calcined in air at 600 ° C for 4 h, then compressed and crushed to 40-60 mesh, respectively, as catalyst C1 # ⁇ C25 # , DC1 # and DC2 # .
  • 1.0 g of catalysts C1 # C25 # , DC1 # and DC2 # were weighed separately, and dimethyl ether (abbreviated as DME) carbonylation reaction was evaluated in a fixed bed reactor. At the beginning of the reaction, the reaction was carried out by a nitrogen gas activation at 550 ° C for 1 h, followed by cooling to 200 ° C.
  • DME dimethyl ether
  • the mixture gas (DME/CO/N 2 2/14/84, volume ratio), the gas space velocity was 1500 ml g -1 h -1 (STP), and the reaction pressure was 2.0 MPa. After a 2 h induction period, samples were taken to obtain the conversion of DME and the selectivity of methyl acetate in the product.
  • the catalysts C1 # to C25 # were all stable, and no significant deactivation occurred within 25 hours.
  • the conversion rates and lifetimes of catalysts C1 # C25 # are generally higher than those of catalysts DC1 # and DC2 # .
  • the conversion of DME, the selectivity of methyl acetate in the product, and the life of the catalyst are shown in Table 5, wherein the deactivation standard is that the conversion rate is reduced to 50% of the highest conversion.

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Abstract

L'invention concerne un procédé de synthèse de mordénite ayant des mésopores et des micropores, et un produit et l'application de celui-ci. Le procédé comprend la précristallisation, entre 50°C et 120°C pendant pas moins de 2 heures, d'un mélange contenant un agent structurant, une source de silicium, une source alcaline et de l'eau, puis l'adjonction d'une source d'aluminium, puis la cristallisation entre 120°C et 220°C pendant pas moins de 12 heures. Le procédé ne nécessite pas l'addition d'un agent de formation de matrice mésoporeuse, et la mordénite obtenue possède à la fois des micropores et des mésopores; la mordénite obtenue a une excellente performance d'adsorption et de catalyse, et peut être appliquée à des catalyseurs de réaction de carbonylation de méthoxyméthane.
PCT/CN2015/074419 2015-03-17 2015-03-17 Procédé de préparation et d'application de mordénite ayant des mésopores et des micropores WO2016145619A1 (fr)

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CN112601800A (zh) * 2018-09-25 2021-04-02 禾大国际股份公开有限公司 催化剂及其在脂肪酸异构化中的用途
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CN114229864B (zh) * 2021-12-24 2023-07-18 山西大学 一种薄片状丝光沸石分子筛的合成方法

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CN109835914A (zh) * 2017-11-28 2019-06-04 中国科学院大连化学物理研究所 一种通过热分散和碱处理结合制备多级孔分子筛的方法
CN109835914B (zh) * 2017-11-28 2022-02-11 中国科学院大连化学物理研究所 一种通过热分散和碱处理结合制备多级孔分子筛的方法
CN112601800A (zh) * 2018-09-25 2021-04-02 禾大国际股份公开有限公司 催化剂及其在脂肪酸异构化中的用途
CN112601800B (zh) * 2018-09-25 2023-06-02 禾大国际股份公开有限公司 催化剂及其在脂肪酸异构化中的用途
CN112934251A (zh) * 2019-12-11 2021-06-11 中国科学院大连化学物理研究所 一种催化正庚烷加氢异构化的双功能催化剂及其制备方法
CN112934251B (zh) * 2019-12-11 2023-06-06 中国科学院大连化学物理研究所 一种催化正庚烷加氢异构化的双功能催化剂及其制备方法
CN114516641A (zh) * 2020-11-18 2022-05-20 中国科学院大连化学物理研究所 一种丝光沸石分子筛及其制备方法、应用
CN114516641B (zh) * 2020-11-18 2023-06-06 中国科学院大连化学物理研究所 一种丝光沸石分子筛及其制备方法、应用
CN115818662A (zh) * 2021-09-16 2023-03-21 中国科学院大连化学物理研究所 一种丝光沸石分子筛及制备方法和应用
CN115818662B (zh) * 2021-09-16 2024-04-16 中国科学院大连化学物理研究所 一种丝光沸石分子筛及制备方法和应用
CN114229864B (zh) * 2021-12-24 2023-07-18 山西大学 一种薄片状丝光沸石分子筛的合成方法

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