WO2016145618A1 - 一种具有介孔和微孔的丝光沸石的合成方法、产品及其应用 - Google Patents

一种具有介孔和微孔的丝光沸石的合成方法、产品及其应用 Download PDF

Info

Publication number
WO2016145618A1
WO2016145618A1 PCT/CN2015/074417 CN2015074417W WO2016145618A1 WO 2016145618 A1 WO2016145618 A1 WO 2016145618A1 CN 2015074417 W CN2015074417 W CN 2015074417W WO 2016145618 A1 WO2016145618 A1 WO 2016145618A1
Authority
WO
WIPO (PCT)
Prior art keywords
bromide
mordenite
hours
mesopores
micropores
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/CN2015/074417
Other languages
English (en)
French (fr)
Inventor
袁扬扬
田鹏
刘中民
杨虹熠
王林英
刘琳
杨淼
李冰
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dalian Institute of Chemical Physics of CAS
Original Assignee
Dalian Institute of Chemical Physics of CAS
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dalian Institute of Chemical Physics of CAS filed Critical Dalian Institute of Chemical Physics of CAS
Priority to PCT/CN2015/074417 priority Critical patent/WO2016145618A1/zh
Publication of WO2016145618A1 publication Critical patent/WO2016145618A1/zh
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Images

Classifications

    • 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 relates to a mordenite, a preparation method thereof 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 the mordenite having mesopores and micropores is characterized in that the templating agent SAA is dissolved in a sodium hydroxide and/or potassium hydroxide solution, and an aluminum source and a silicon source are sequentially added at 80 ° C to 100 After pre-crystallization at °C for not less than 2 hours, crystallization at 120 ° C ⁇ 220 ° C for not less than 12 hours;
  • the templating agent SAA is selected from at least one of surfactants.
  • the method for synthesizing the mordenite having mesopores and micropores comprises at least the following steps:
  • Al 2 O 3 /SiO 2 0.01 to 0.1;
  • M 2 O/SiO 2 0.10 to 0.40, wherein M is Na and/or K;
  • step b) the initial gel mixture obtained in step a) is pre-crystallized at 80 ° C ⁇ 100 ° C for not less than 2 hours, and then crystallized at 120 ° C ⁇ 220 ° C for not less than 12 hours;
  • the solid product is separated and dried to obtain the mordenite having mesopores and micropores.
  • the number of moles of the silicon source is SiO 2 , which is equal to the number of moles of silicon in the system;
  • the number of moles of the aluminum source is Al 2 O 3 , which is equal to 1/2 of the mole of aluminum in the system;
  • the number of moles of the microporous templating agent R is in terms of the number of moles of R itself;
  • the number of moles of the mesoporous sizing agent SAA is in terms of the number of moles of SAA itself;
  • the number of moles of M 2 O all the raw materials (silicon source, aluminum source, alkali source)
  • the number of moles of the metal oxide M 2 O corresponding to the alkali metal M contained in the ) is equal to 1/2 of the moles of the alkali metal element M in all the raw materials.
  • the surfactant is selected from at least one of ionic surfactants.
  • the surfactant is selected from the group consisting of octadecyltrimethylammonium bromide (abbreviated as C18), cetyltrimethylammonium bromide (abbreviated as C16), tetradecyltrimethyl Ammonium bromide (abbreviated as C14), dodecyltrimethylammonium bromide (abbreviated as C12), ethylene dihexadecyldimethylammonium bromide (abbreviated as C16-2-16), ethylene Ditetradecyldimethylammonium bromide (abbreviated as C14-2-14), ethylene bis-dodecyldimethylammonium bromide (abbreviated as C12-2-12), propylene dihexadecane Methyl dimethyl ammonium bromide (abbreviated as C16-3-16), propylene ditetradecyl dimethyl ammonium bromide (abbreviated as C14), propy
  • the surfactant is composed of octadecyltrimethylammonium bromide, cetyltrimethylammonium bromide, tetradecyltrimethylammonium bromide, dodecyl group.
  • Trimethylammonium bromide ethylene dihexadecyldimethylammonium bromide, ethylene ditetradecyldimethylammonium bromide, ethylene dodecyldimethylammonium bromide, C Dihexadecyldimethylammonium bromide, propylene ditetradecyl di Ammonium methyl bromide, propylene didodecyl dimethyl ammonium bromide, butyl hexadecyl dimethyl ammonium bromide, butyl ditetradecyl dimethyl ammonium bromide, butadiene Di-dodecyldimethylammonium bromide, hexamethylenebis-hexadecyldimethylammonium bromide, hexamethylenetetradecyldimethylammonium bromide, hexamethylenedidecyldimethyl At least one composition of ammonium bromide.
  • the surfactant is at least one of octadecyltrimethylammonium bromide, cetyltrimethylammonium bromide, and dodecyltrimethylammonium bromide. Composition.
  • the surfactant is composed of ethylene dihexadecyldimethylammonium bromide, ethylene ditetradecyldimethylammonium bromide, ethylene bis-dodecyl group Ammonium methyl bromide, propylene dihexadecyl dimethyl ammonium bromide, propylene didodecyl dimethyl ammonium bromide, butyl hexadecyl dimethyl ammonium bromide, hexa At least one of ditetradecyldimethylammonium bromide.
  • the lower limit of the molar ratio range of Al 2 O 3 /SiO 2 in the initial gel mixture in the step a) is selected from the group consisting of 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, 0.25.
  • the lower limit of the molar ratio range of M 2 O/SiO 2 in the initial gel mixture in the step a) is selected from the group consisting of 0.10, 0.15, and 0.20, and the upper limit is selected from the group consisting of 0.27, 0.29, 0.33, 0.35, 0.36, 0.38, and 0.40.
  • the lower limit of the molar ratio range of H 2 O/SiO 2 in the initial gel mixture in step a) is selected from 10, 20, 23, 30, and the upper limit is selected from 50, 55, 60, 70, 80, 90, 100. .
  • 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 a) 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 80 ° C, 85 ° C, and 90 ° C, and the upper limit is selected from the group consisting of 90 ° C and 100 ° 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 the group consisting of 8 hours, 9 hours, 10 hours, 11 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 b) 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, 160 ° C, 170 ° C, 178 ° C, 180 ° C, 200. °C, 220 °C.
  • the crystallization temperature in the step b) is from 120 to 180 °C.
  • the crystallization temperature in the step b) is from 125 to 145 °C.
  • the lower limit of the time range for crystallization in the step b) 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 step b) is crystallization for 12 to 168 hours.
  • the initial gel mixture obtained in the step b) is precrystallized at 80 to 100 ° C for 2 to 12 hours, and then crystallized at 125 to 145 ° C for not less than 12 to 168 hours.
  • the pore diameter of the mesopores is 2 to 40 nm.
  • the pore volume ratio of mesopores to micropores is from 1.12 to 5.71:1.
  • 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 outer specific surface area of from 100 m 2 /g to 240 m 2 /g.
  • the mordenite has mesopores having a pore diameter of from 2 nm to 40 nm.
  • the pore volume ratio of mesopores to micropores is from 1.12 to 5.71.
  • 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 Application in separation and / or catalytic reactions.
  • a dimethyl ether carbonylation catalyst having the advantages of high conversion of dimethyl ether, high selectivity of methyl acetate, and long life, and the catalyst is obtained by any of the above methods.
  • the prepared mordenite having mesopores and micropores 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 low templating agent, which 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 partial enlargement of a scanning electron micrograph of sample 1 # .
  • Figure 4 is a nitrogen physico-desorption desorption isotherm for sample 1 # .
  • Figure 5 is a scanning electron micrograph of sample D1 # in Comparative Example 1.
  • 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.
  • C12 dodecyltrimethylammonium bromide
  • a sodium hydroxide solution (0.55 g of NaOH dissolved in 40 g of deionized water)
  • 0.467 g of sodium aluminate was added, and stirred until completely dissolved.
  • 20 g of silica sol was added thereto and stirring was continued at room temperature until a uniform initial gel was formed.
  • the gel was placed in a stainless steel reaction vessel with a PTFE liner, preheated to 80 ° C for 4 h, and then heated to 130 ° C for 168 hours.
  • the obtained solid product was centrifuged and washed with deionized water to the middle.
  • sample # # 1 The initial gel as prepared in the material type and ratio, and time of the pre-crystallization temperature, crystallization temperature and time are as shown in Table 1. Sample # 1.
  • the surfactant is first dissolved in a sodium hydroxide and/or potassium hydroxide solution, added to an aluminum source, stirred until completely dissolved, and then added to a silicon source, and stirring is continued at room temperature until a uniform initial gel is formed.
  • the gel is placed in a stainless steel reaction vessel with a PTFE inner liner, heated to 80-100 ° C for pre-crystallization for 2 to 12 h, and then heated to 120-220 ° C for crystallization for 12-168 hours to obtain a solid product.
  • 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 the pre-crystallization is not performed.
  • the initial gel was directly heated to 130 ° C and crystallized for 168 hours.
  • the obtained solid product was centrifuged, washed with deionized water to neutrality, dried in air at 110 ° C, and calcined at 550 ° C for 5 h in a muffle furnace.
  • the sample is recorded as sample D1 # .
  • Example 26 Silica-aluminum ratio of sample 1 # ⁇ 25 # and D1 #
  • Samples # 1 and # 25 ⁇ # Dl characterized XRF for measuring elemental composition calculated molar ratio of SiO 2 / Al 2 O 3, and shown in Table 2.
  • Example 27 XRD Characterization of Sample 1 # ⁇ 25 # and D1 #
  • XRD characterization was performed on samples 1 # to 25 # and D1 # .
  • the XRD patterns of sample 1 # ⁇ 25 # and D1 # 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 intensities fluctuate within ⁇ 5% depending on the synthesis conditions. , indicating that samples 1 # to 25 # and D1 # are both mordenite.
  • a typical XRD pattern is represented by sample 1 # , as shown in Figure 1, and its XRD diffraction peak data is shown in Table 3.
  • Example 28 Scanning electron microscopy characterization of sample 1 # ⁇ 25 # and D1 #
  • FIG. 5 A scanning electron microscope image of sample D1 # is shown in Fig. 5. It can be seen from the figure that the sample is a particle aggregate of 200 to 300 nm.
  • Example 29 Characterization of pore structure of sample 1 # ⁇ 25 # and D1 #
  • Pore structure characterization of samples 1 # ⁇ 25 # and D1 # was performed using low temperature nitrogen physics.
  • the adsorption desorption isotherms showed obvious hysteresis loops.
  • the typical nitrogen adsorption desorption isotherms are represented by sample 1 #, as shown in Figure 4.
  • the pore structure characterization results of sample 1 # ⁇ 25 # and D1 # are shown in Table 4.
  • Samples 1 # ⁇ 25 # both have a large mesoporous pore volume and a micropore pore volume, that is, sample 1 # ⁇ 25 # has Mesopores and micropores.
  • Sample D1 # is dominated by micropores and contains almost no mesopores.
  • Example 30 Sample 1 # ⁇ 25 # and D1 # for dimethyl ether carbonylation reaction
  • Samples 1 # ⁇ 25 # and D1 # 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 # and DC1 # .
  • 1.0 g of catalysts C1 # C25 # and DC1 # 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 rate and lifetime of the catalyst C1 # to C25 # are generally higher than the catalyst DC1 # .
  • 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.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Catalysts (AREA)

Abstract

提供一种具有介孔和微孔的丝光沸石的合成方法、产品及其应用。方法包括：将模板剂溶解于氢氧化钠和/或氢氧化钾溶液中，依次加入铝源、硅源，于80-100℃下预晶化不少于2小时后，再于120-220℃下晶化不少于12小时。该方法得到的丝光沸石同时具备微孔和介孔，在吸附和催化方面表现出优异的性能和稳定性。

Description

一种具有介孔和微孔的丝光沸石的合成方法、产品及其应用 技术领域
本申请属于化学化工领域，具体而言，涉及一种丝光沸石、其制备方法及其应用。
背景技术
丝光沸石是具有二维孔道，其结构由Meier于1961年确定，该分子筛的孔道结构由0.67*0.70nm的十二元环孔道和0.34*0.48nm的八元环孔道组成。由于八元环的孔道太小，很多分子无法进入，所以通常认为丝光沸石为一维孔道的分子筛。由于丝光沸石独特的孔道结构和酸性，在催化裂化,甲苯歧化与烷基转移反应，芳烃烷基化，二甲苯异构化，二甲醚羰基化等反应中具有重要的应用。
但在实际应用中，由于其相对狭窄的孔道结构会制约芳香烃等大分子在其中的扩散，容易造成催化剂失活。另一方面，由于严重的扩散限制，使得大量的活性位点很难接触到，从而严重影响催化剂的活性。所以，制备含有介孔的丝光沸石，改善丝光沸石的传质性能，对于提高催化剂的催化性能具有重要的价值。同时，减小晶粒尺寸可以有效缩短扩散路径，有助于反应物和产物的扩散，提高其催化性能，所以合成纳米尺度的分子筛和含有介孔的分子筛是目前研究的热点。
发明内容
根据本申请的一个方面，提供了一种具有介孔和微孔的丝光沸石的合成方法，所述方法具有过程简单、容易分离、易于大规模工业化的优势，所述方法合成的丝光沸石避免了单一孔道结构的缺陷，在吸附和催化方面有广阔的应用前景。
所述具有介孔和微孔的丝光沸石的合成方法，其特征在于，将模板剂SAA溶解于氢氧化钠和/或氢氧化钾溶液中，依次加入铝源、硅源，于80℃～100℃预晶化不少于2小时后，再于120℃～220℃晶化不少于12小时；
所述模板剂SAA选自表面活性剂中的至少一种。
优选地，所述具有介孔和微孔的丝光沸石的合成方法至少包括如下步骤：
a)将模板剂SAA溶解于氢氧化钠和/或氢氧化钾溶液中，得到溶液I；将铝源加入溶液I，溶解后得到溶液II；将硅源加入溶液II中，混合均匀，形成具有如下摩尔配比的初始凝胶混合物：
Al2O3/SiO2＝0.01～0.1；
M2O/SiO2＝0.10～0.40，其中M为Na和/或K；
H2O/SiO2＝10～100；
SAA/SiO2＝0.01～0.30；
b)将步骤a)得到的所述初始凝胶混合物于80℃～100℃预晶化不少于2小时后，再于120℃～220℃晶化不少于12小时；
c)待步骤b)晶化完成后，固体产物经分离、干燥，即得所述具有介孔和微孔的丝光沸石。
初始凝胶混合物中，硅源的摩尔数以SiO2计，与体系中硅元素的摩尔 数相等；铝源的摩尔数以Al2O3计，等于体系中铝元素摩尔数的1/2；微孔模板剂R的摩尔数以R本身的摩尔数计；介孔模板剂SAA的摩尔数以SAA本身的摩尔数计；M2O摩尔数，以所有原料(硅源、铝源、碱源)中包含的碱金属M所对应的金属氧化物M2O的摩尔数计，等于所有原料中碱金属元素M摩尔数的1/2。
优选地，所述表面活性剂选自离子型表面活性剂中的至少一种。
进一步优选地，所述表面活性剂选自十八烷基三甲基溴化铵(简写为C18)、十六烷基三甲基溴化铵(简写为C16)、十四烷基三甲基溴化铵(简写为C14)、十二烷基三甲基溴化铵(简写为C12)、乙撑双十六烷基二甲基溴化铵(简写为C16-2-16)、乙撑双十四烷基二甲基溴化铵(简写为C14-2-14)、乙撑双十二烷基二甲基溴化铵(简写为C12-2-12)、丙撑双十六烷基二甲基溴化铵(简写为C16-3-16)、丙撑双十四烷基二甲基溴化铵(简写为C14-3-14)、丙撑双十二烷基二甲基溴化铵(简写为C12-3-12)、丁撑双十六烷基二甲基溴化铵(简写为C16-4-16)、丁撑双十四烷基二甲基溴化铵(简写为C14-4-14)、丁撑双十二烷基二甲基溴化铵(简写为C12-4-12)、己撑双十六烷基二甲基溴化铵(简写为C16-6-16)、己撑双十四烷基二甲基溴化铵(简写为C14-6-14)、己撑双十二烷基二甲基溴化铵(简写为C12-6-12)中的至少一种。
作为一个优选的实施方式，所述表面活性剂由十八烷基三甲基溴化铵、十六烷基三甲基溴化铵、十四烷基三甲基溴化铵、十二烷基三甲基溴化铵、乙撑双十六烷基二甲基溴化铵、乙撑双十四烷基二甲基溴化铵、乙撑双十二烷基二甲基溴化铵、丙撑双十六烷基二甲基溴化铵、丙撑双十四烷基二 甲基溴化铵、丙撑双十二烷基二甲基溴化铵、丁撑双十六烷基二甲基溴化铵、丁撑双十四烷基二甲基溴化铵、丁撑双十二烷基二甲基溴化铵、己撑双十六烷基二甲基溴化铵、己撑双十四烷基二甲基溴化铵、己撑双十二烷基二甲基溴化铵中的至少一种组成。
作为一个更优选的实施方式，所述表面活性剂由十八烷基三甲基溴化铵、十六烷基三甲基溴化铵、十二烷基三甲基溴化铵中的至少一种组成。
作为一个更优选的实施方式，所述表面活性剂由乙撑双十六烷基二甲基溴化铵、乙撑双十四烷基二甲基溴化铵、乙撑双十二烷基二甲基溴化铵、丙撑双十六烷基二甲基溴化铵、丙撑双十二烷基二甲基溴化铵、丁撑双十六烷基二甲基溴化铵、己撑双十四烷基二甲基溴化铵中的至少一种组成。
优选地，所述步骤a)初始凝胶混合物中Al2O3/SiO2的摩尔比值范围下限选自0.01、0.0125、0.013、0.015、0.016、0.02、0.025、0.03，上限选自0.075、0.25。进一步优选地，所述步骤a)初始凝胶混合物中摩尔比Al2O3/SiO2＝0.015～0.075。
优选地，所述步骤a)初始凝胶混合物中M2O/SiO2的摩尔比值范围下限选自0.10、0.15、0.20，上限选自0.27、0.29、0.33、0.35、0.36、0.38、0.40。进一步优选地，所述步骤a)初始凝胶混合物中摩尔比M2O/SiO2＝0.2～0.33，其中M为Na和/或K。
优选地，所述步骤a)初始凝胶混合物中H2O/SiO2的摩尔比值范围下限选自10、20、23、30，上限选自50、55、60、70、80、90、100。进一步优选地，所述步骤a)初始凝胶混合物中摩尔比H2O/SiO2＝20～60。
优选地，所述步骤a)初始凝胶混合物中SAA/SiO2的摩尔比值范围下 限选自0.01、0.02、0.04、0.06、0.08、0.10，上限选自0.15、0.16、0.20、0.30。进一步优选地，所述步骤a)初始凝胶混合物中摩尔比SAA/SiO2＝0.01～0.15。
优选地，所述步骤a)中硅源选自硅溶胶、硅凝胶、正硅酸甲酯、正硅酸乙酯、白炭黑、水玻璃中的至少一种。
优选地，所述步骤a)中铝源选自异丙醇铝、氧化铝、氢氧化铝、氯化铝、硫酸铝、硝酸铝、铝酸钠中的至少一种。
优选地，所述步骤b)中的预晶化温度范围下限选自80℃、85℃、90℃，上限选自90℃、100℃。
优选地，所述步骤b)中预晶化的时间范围下限选自2小时、4小时、6小时，上限选自8小时、9小时、10小时、11小时、12小时。进一步优选地，所述步骤b)中预晶化2～12小时。
优选地，所述步骤b)中的晶化温度范围下限选自120℃、125℃、130℃，温度范围上限选自145℃、150℃、160℃、170℃、178℃、180℃、200℃、220℃。进一步优选地，所述步骤b)中的晶化温度为120～180℃。更进一步优选地，所述步骤b)中的晶化温度为125～145℃。
优选地，所述步骤b)中晶化的时间范围下限选自12小时、24小时，上限选自120小时、144小时、150小时、168小时、216小时。进一步优选地，所述步骤b)中晶化12～168小时。
更进一步优选地，所述步骤b)得到的初始凝胶混合物于80～100℃预晶化2～12小时后，再于125～145℃晶化不少于12～168小时。
优选地，所述具有介孔和微孔的丝光沸石中，介孔的孔径为2～40nm。
优选地，所述具有介孔和微孔的丝光沸石中，介孔与微孔的孔容比为1.12～5.71：1。
优选地，所述步骤b)和/或步骤c)中的晶化的方式可以为静态晶化，也可以为动态晶化。
本申请中，术语“静态晶化”是指晶化过程中，装有初始凝胶混合物的釜静置于烘箱中，且未对合成釜内的混合物进行搅拌。
本申请中，术语“动态晶化”是指装有初始凝胶混合物的合成釜在晶化过程中，处于非静止状态，如翻转、旋转等；或者晶化过程中，对合成釜内部的混合物进行搅拌。
所述步骤c)干燥后，经过焙烧，得到同时含有微孔和介孔的丝光沸石。
优选地，本申请技术方案得到的分子筛硅铝摩尔比SiO2/Al2O3＝4～70。
根据本申请的又一个方面，提供了一种具有介孔和微孔的丝光沸石，所述丝光沸石为纳米颗粒，具有较大的外比表面积，同时避免了单一孔道结构的缺陷，在吸附和催化方面有广阔的应用前景。该具有介孔和微孔的丝光沸石由上述任一种方法制备得到。
优选地，所述丝光沸石的外比表面积为100m2/g～240m2/g。
优选地，所述丝光沸石具有孔径为2nm～40nm的介孔。
优选地，所述丝光沸石中，介孔与微孔的孔容比值为1.12～5.71。
根据本申请的又一个方面，提供了根据上述任一种方法制备的具有介孔和微孔的丝光沸石和/或根据上述任一种具有介孔和微孔的丝光沸石在吸 附分离和/或催化反应中的应用。
根据本申请的又一个方面，提供了一种二甲醚羰基化反应催化剂，该催化剂具有二甲醚转化率高、乙酸甲酯选择性高、寿命长的优势，该催化剂由上述任一种方法制备的具有介孔和微孔的丝光沸石和/或上述任一种具有介孔和微孔的丝光沸石经铵离子交换以及400～700℃空气中焙烧得到。
本申请能产生的有益效果至少包括：
1)本申请所提供的丝光沸石的制备方法，工艺简单，模板剂价格低廉，利于大规模工业化生产。
2)根据本申请所提供方法制备得到的丝光沸石，具有微孔和介孔，避免了单一孔道的缺陷，在大分子吸附和催化方面有着广阔的应用前景。
3)根据本申请所提供方法制备得到的丝光沸石，作为吸附剂和催化剂，在扩散和寿命方面具有明显优势。
4)根据本申请所提供方法制备得到的丝光沸石，作为二甲醚羰基化反应催化剂，表现出转化率高、选择性好及寿命长的优点。
附图说明
图1为样品1#的X射线衍射图谱。
图2为样品1#的扫描电子显微镜照片。
图3为样品1#的扫描电子显微镜照片的局部放大。
图4为样品1#的氮气物理吸附脱附等温线。
图5为对比例1中的样品D1#的扫描电子显微镜图。
具体实施方式
下面结合具体的实施例，进一步阐述本申请。应理解，这些实施例仅用于说明本申请而不用于限制本申请的范围。
如无特别说明，本申请的实施例中的原料和催化剂均通过商业途径购买，不经任何特殊处理直接使用。
本申请的实施例中分析方法如下：
元素组成采用Philips公司的Magix 2424X型射线荧光分析仪(XRF)测定。
X射线粉末衍射物相分析(XRD)采用荷兰帕纳科(PANalytical)公司的X’Pert PRO X射线衍射仪，Cu靶，Kα辐射源(λ＝0.15418nm)，电压40KV，电流40mA。
扫描电子显微镜(SEM)测试所采用仪器为Hitachi SU8020场发射扫描电镜，加速电压为2kV。
采用低温氮气物理吸附表征样品的孔结构，所用仪器为Micromeritics公司ASAP2020型物理吸附仪。
气体样品分析采用美国安捷伦(Agilent)公司6890GC型气相色谱仪进行在线分析，色谱柱为安捷伦(Agilent)公司HP-5毛细柱。
实施例1：样品1#的制备
首先将0.31g十二烷基三甲基溴化铵(简写为C12)溶解于氢氧化钠溶液(0.55g NaOH溶解于40g去离子水)中，加入0.467g铝酸钠，搅拌直至完全溶解，再向其中加入20g硅溶胶，在室温下继续搅拌直到形成均匀的初始凝胶。将凝胶放入带聚四氟内衬的不锈钢反应釜中，升温到80℃预晶化4h，再升温至130℃晶化168小时，所得固体产物经离心分离，用去 离子水洗涤至中性，在110℃下空气中干燥，并于最后在马弗炉中于550℃焙烧5h，即得到具有介孔和微孔的丝光沸石，记为样品1#。所制备的样品1#的初始凝胶中的原料类型及配比、预晶化温度和时间、晶化温度和时间分别如表1中样品1#所示。
实施例2～25：样品2#～25#的制备
首先将表面活性剂溶解于氢氧化钠和/或氢氧化钾溶液中，加入铝源，搅拌直至完全溶解，再加入硅源，在室温下继续搅拌直到形成均匀的初始凝胶。将凝胶放入带聚四氟内衬的不锈钢反应釜中，升温到80～100℃预晶化2～12h，再升温至加热到120～220℃，晶化12～168小时，所得固体产物经离心分离，用去离子水洗涤至中性，在110℃下空气中干燥，并于最后在马弗炉中于550℃焙烧5h，即得到具有介孔和微孔的丝光沸石，记为样品2#～25#。所制备的样品2#～25#的初始凝胶中的原料类型及配比、预晶化温度和时间、晶化温度和时间分别如表1所示。
表1分子筛合成配料及晶化条件表
Figure PCTCN2015074417-appb-000001
Figure PCTCN2015074417-appb-000002
注*：硅源：a硅溶胶；b白炭黑；c正硅酸乙酯；d正硅酸甲酯；e硅凝胶；f水玻璃。
铝源：Ⅰ铝酸钠；Ⅱ氯化铝；Ⅲ氢氧化铝；Ⅳ硫酸铝；Ⅴ氧化铝；Ⅵ异丙醇铝；Ⅶ硝酸铝。
注**：Na2O和K2O的配比以其添加铝源、硅源和碱源中所含的金属氧化物Na2O和K2O计算。
对比例1
具体步骤、原料配比和实验条件同实施1，不同之处在于，不经预晶化。初始凝胶直接加热升温至130℃，晶化168小时，所得固体产物经离心分离、用去离子水洗涤至中性、在110℃下空气中干燥、马弗炉中于550℃焙烧5h，得到样品记为样品D1#。
实施例26：样品1#～25#和D1#的硅铝比
对样品1#～25#和D1#进行XRF表征，测定元素组成，计算其SiO2/Al2O3的摩尔比，见表2所示。
表2样品1#～25#和D1#的硅铝比
Figure PCTCN2015074417-appb-000003
实施例27：样品1#～25#和D1#的XRD表征
对样品1#～25#和D1#进行XRD表征。样品1#～25#和D1#的XRD谱图与标准丝光沸石沸石分子筛的特征谱图一致，即主要的衍射峰位置和形状相同，依合成条件的不同相对峰强度在±5％范围内波动，表明样品1#～25#和 D1#均为丝光沸石。典型的XRD图谱以样品1#为代表，如图1所示，其XRD衍射峰数据见表3。
表3样品1#的XRD衍射峰数据
峰编号 2θ[°] I/I0*100
1 6.5385 42.16
2 8.6643 17.24
3 9.7697 57.57
4 13.5176 43.33
5 13.893 18.99
6 14.5909 8.59
7 15.3047 16.13
8 19.6621 39.77
9 21.4614 5.86
10 22.3171 82.78
11 23.2771 14.83
12 23.7291 12.33
13 25.686 100
14 26.3514 50.19
15 27.6727 50.47
16 27.9205 39.06
17 30.4794 6.6
18 30.9312 18.87
19 33.2226 3.24
20 34.0589 1.28
21 35.152 5.28
22 35.7392 10.91
23 36.5528 5.21
24 37.0559 3.81
25 40.5693 2.52
26 41.8484 1.26
27 44.3502 8.15
28 45.0623 5.94
29 46.6231 8.67
30 47.4923 2.99
31 48.5791 9.93
32 50.3698 2.87
实施例28：样品1#～25#和D1#的扫描电镜表征
对样品1#～25#和D1#进行扫描电镜表征。扫描电镜图显示，样品1#～25#的形貌均呈现为球状纳米颗粒的聚集。典型的扫描电镜图以样品1#为代表，如图2所示，由图可以看出多级孔丝光沸石为超薄纳米片的聚集体，纳米片的尺寸为300nm×300nm，进一步放大后，由图3可以发现其纳米片由更小的单元组成。
样品D1#的扫描电子显微镜图如图5所示。由图可以看出为样品为200～300nm的颗粒聚集体。
实施例29：样品1#～25#和D1#的孔结构表征
使用低温氮气物理吸附对样品1#～25#和D1#进行孔结构表征。其吸附脱附等温线均出现明显滞后环，典型的氮气吸附脱附等温线以样品1#为代表，见图4。样品1#～25#和D1#的孔结构表征结果如表4所示，样品1#～25#均同时具有较大的介孔孔容和微孔孔容，即样品1#～25#具有介孔和微孔。样品D1#则以微孔为主，几乎不含介孔。
表4样品1#～25#和D1#孔结构表征结果
Figure PCTCN2015074417-appb-000004
Figure PCTCN2015074417-appb-000005
实施例30：样品1#～25#和D1#用于二甲醚羰基化反应
将样品1#～25#和D1#分别经NH4NO3离子交换去除钠离子，600℃空气中焙烧4h后，压片、破碎至40～60目，分别记为催化剂C1#～C25#和DC1#。分别称取1.0g催化剂C1#～C25#和DC1#，分别在固定床反应器中进行二甲醚(简写为DME)羰基化反应评价。反应开始时在550℃下通氮气活化1h，然后降温至200℃进行反应。混合气(DME/CO/N2＝2/14/84，体积比)，气体空速为1500ml g-1h-1(STP)，反应压力为2.0Mpa。经过2h诱导期后，取样得到DME的转化率和产物中乙酸甲酯的选择性。催化剂C1#～C25#稳定性均良好，在25h内均没有明显失活现象发生。催化剂 C1#～C25#的转化率及寿命普遍高于催化剂DC1#。DME的转化率、产物中乙酸甲酯的选择性、催化剂寿命见表5所示，其中失活标准为转化率降为最高转化率的50％。
表5样品1#～25#和D1#二甲醚羰基化反应结果
催化剂编号 DME转化率a 乙酸甲酯选择性b 催化剂寿命c
C1# 70.5％ 99.0％ 29h
C2# 71.2％ 98.7％ 28h
C3# 69.3％ 98.2％ 25h
C4# 70.2％ 99.2％ 27h
C5# 68.4％ 99.1％ 28h
C6# 67.9％ 98.7％ 29h
C7# 65.4％ 99.0％ 28h
C8# 68.7％ 99.2％ 29h
C9# 61.5％ 98.5％ 28h
C10# 65.2％ 98.3％ 27h
C11# 69,8％ 98.4％ 29h
C12# 67.4％ 98.5％ 28h
C13# 66.2％ 98.7％ 27h
C14# 69.5％ 98.9％ 28h
C15# 62.8％ 98.9％ 29h
C16# 68.6％ 99.1％ 29h
C17# 69.3％ 99.0％ 25h
C18# 71.4％ 99.1％ 26h
C19# 67.1％ 98.7％ 29h
C20# 63.7％ 99.0％ 28h
C21# 63.4％ 99.1％ 29h
C22# 68.4％ 98.9％ 28h
C23# 69.8％ 99.1％ 27h
C24# 64.3％ 99.2％ 28h
C25# 65.7％ 99.0％ 27h
DC1# 40％ 96.1％ 10h
注：a：反应过程中最高转化率。
b：反应过程中达到最高转化率时醋酸甲酯的选择性。
c：最高转化率到转化率为最高转化率的一半所经历时间。
以上所述，仅是本申请的几个实施例，并非对本申请做任何形式的限制，虽然本申请以较佳实施例揭示如上，然而并非用以限制本申请，任何熟悉本专业的技术人员，在不脱离本申请技术方案的范围内，利用上述揭示的技术内容做出些许的变动或修饰均等同于等效实施案例，均属于技术方案范围内。

Claims (10)

  1. 一种具有介孔和微孔的丝光沸石的合成方法，其特征在于，将模板剂SAA溶解于氢氧化钠和/或氢氧化钾溶液中，依次加入铝源、硅源，于80℃～100℃预晶化不少于2小时后，再于120℃～220℃晶化不少于12小时，即得所述具有介孔和微孔的丝光沸石；
    所述模板剂SAA选自表面活性剂中的至少一种。
  2. 根据权利要求1所述的方法，其特征在于，至少包括如下步骤：
    a)将模板剂SAA溶解于氢氧化钠和/或氢氧化钾溶液中，得到溶液I；将铝源加入溶液I中，溶解后得到溶液II；将硅源加入溶液II中，混合均匀，形成具有如下摩尔配比的初始凝胶混合物：
    Al2O3/SiO2＝0.01～0.25；
    M2O/SiO2＝0.10～0.40，其中M为Na和/或K；
    H2O/SiO2＝10～100；
    SAA/SiO2＝0.01～0.30；
    b)将步骤a)得到的所述初始凝胶混合物于80℃～100℃预晶化不少于2小时后，再于120℃～220℃晶化不少于12小时；
    c)待步骤b)晶化完成后，固体产物经分离、干燥，即得所述具有介孔和微孔的丝光沸石。
  3. 根据权利要求1所述的方法，其特征在于，所述表面活性剂选自离子型表面活性剂中的至少一种。
  4. 根据权利要求1所述的方法，其特征在于，所述表面活性剂选自十八烷基三甲基溴化铵、十六烷基三甲基溴化铵、十四烷基三甲基溴化铵、十二烷基三甲基溴化铵、乙撑双十六烷基二甲基溴化铵、乙撑双十四烷基二甲基溴化铵、乙撑双十二烷基二甲基溴化铵、丙撑双十六烷基二甲基溴化铵、丙撑双十四烷基二甲基溴化铵、丙撑双十二烷基二甲基溴化铵、丁撑双十六烷基二甲基溴化铵、丁撑双十四烷基二甲基溴化铵、丁撑双十二烷基二甲基溴化铵、己撑双十六烷基二甲基溴化铵、己撑双十四烷基二甲基溴化铵、己撑双十二烷基二甲基溴化铵中的至少一种。
  5. 根据权利要求2所述的方法，其特征在于，所述步骤a)初始凝胶混合物中摩尔比SAA/SiO2＝0.01～0.15。
  6. 根据权利要求1所述的方法，其特征在于，所述步骤b)中的预晶化时间为2小时～12小时。
  7. 根据权利要求1所述的方法，其特征在于，所述步骤b)中的晶化温度为125℃～145℃，晶化时间为12小时～168小时。
  8. 一种根据权利要求1至7任一项所述方法制备的具有介孔和微孔的丝光沸石，其特征在于，所述丝光沸石的外比表面积为100m2/g～240m2/g；所述丝光沸石具有孔径为2nm～40nm的介孔。
  9. 根据权利要求8所述的丝光沸石，其特征在于，所述丝光沸石中，介孔与微孔的孔容比为1.12～5.71。
  10. 一种二甲醚羰基化反应催化剂，其特征在于，根据权利要求1至7任一项所述方法合成的具有介孔和微孔的丝光沸石和/或根据权利要求8或9所述具有介孔和微孔的丝光沸石经铵离子交换以及400～700℃空气中焙烧 得到。
PCT/CN2015/074417 2015-03-17 2015-03-17 一种具有介孔和微孔的丝光沸石的合成方法、产品及其应用 Ceased WO2016145618A1 (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/CN2015/074417 WO2016145618A1 (zh) 2015-03-17 2015-03-17 一种具有介孔和微孔的丝光沸石的合成方法、产品及其应用

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/CN2015/074417 WO2016145618A1 (zh) 2015-03-17 2015-03-17 一种具有介孔和微孔的丝光沸石的合成方法、产品及其应用

Publications (1)

Publication Number Publication Date
WO2016145618A1 true WO2016145618A1 (zh) 2016-09-22

Family

ID=56919561

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2015/074417 Ceased WO2016145618A1 (zh) 2015-03-17 2015-03-17 一种具有介孔和微孔的丝光沸石的合成方法、产品及其应用

Country Status (1)

Country Link
WO (1) WO2016145618A1 (zh)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111450874A (zh) * 2020-04-09 2020-07-28 中国石油大学(北京) 金属改性的丝光沸石及其制法和催化二甲醚制乙烯的应用
CN115959681A (zh) * 2021-10-11 2023-04-14 中国石油化工股份有限公司 Scm-36分子筛、其制造方法及其用途
CN117024279A (zh) * 2023-10-10 2023-11-10 深圳市普利凯新材料股份有限公司 一种乙酰乙酸基甲基丙烯酸乙酯的脱色方法
JP2024535577A (ja) * 2021-10-11 2024-09-30 中国石油化工股▲ふん▼有限公司 シリコン－アルミニウムモレキュラーシーブｓｃｍ－３６、その製造方法およびその用途

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1597516A (zh) * 2004-09-21 2005-03-23 太原理工大学 微孔－介孔复合分子筛及制备方法
CN101519217A (zh) * 2008-02-28 2009-09-02 中国石油化工股份有限公司 一种小晶粒丝光沸石的制备方法
CN102190315A (zh) * 2010-03-03 2011-09-21 中国石油化工股份有限公司 具有复合孔结构的丝光沸石及其制备方法
CN102464326A (zh) * 2010-11-04 2012-05-23 中国石油化工股份有限公司 合成高硅丝光沸石的方法
CN103482645A (zh) * 2013-09-22 2014-01-01 华东师范大学 一种多级孔纳米丝光沸石分子筛的制备方法
CN103831124A (zh) * 2012-11-26 2014-06-04 上海碧科清洁能源技术有限公司 一种用于二甲醚羰基化合成乙酸甲酯的含磷沸石催化剂以及使用该催化剂的方法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1597516A (zh) * 2004-09-21 2005-03-23 太原理工大学 微孔－介孔复合分子筛及制备方法
CN101519217A (zh) * 2008-02-28 2009-09-02 中国石油化工股份有限公司 一种小晶粒丝光沸石的制备方法
CN102190315A (zh) * 2010-03-03 2011-09-21 中国石油化工股份有限公司 具有复合孔结构的丝光沸石及其制备方法
CN102464326A (zh) * 2010-11-04 2012-05-23 中国石油化工股份有限公司 合成高硅丝光沸石的方法
CN103831124A (zh) * 2012-11-26 2014-06-04 上海碧科清洁能源技术有限公司 一种用于二甲醚羰基化合成乙酸甲酯的含磷沸石催化剂以及使用该催化剂的方法
CN103482645A (zh) * 2013-09-22 2014-01-01 华东师范大学 一种多级孔纳米丝光沸石分子筛的制备方法

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111450874A (zh) * 2020-04-09 2020-07-28 中国石油大学(北京) 金属改性的丝光沸石及其制法和催化二甲醚制乙烯的应用
CN111450874B (zh) * 2020-04-09 2021-08-20 中国石油大学(北京) 金属改性的丝光沸石及其制法和催化二甲醚制乙烯的应用
CN115959681A (zh) * 2021-10-11 2023-04-14 中国石油化工股份有限公司 Scm-36分子筛、其制造方法及其用途
JP2024535577A (ja) * 2021-10-11 2024-09-30 中国石油化工股▲ふん▼有限公司 シリコン－アルミニウムモレキュラーシーブｓｃｍ－３６、その製造方法およびその用途
JP7812918B2 (ja) 2021-10-11 2026-02-10 中国石油化工股▲ふん▼有限公司 シリコン－アルミニウムモレキュラーシーブｓｃｍ－３６、その製造方法およびその用途
CN117024279A (zh) * 2023-10-10 2023-11-10 深圳市普利凯新材料股份有限公司 一种乙酰乙酸基甲基丙烯酸乙酯的脱色方法
CN117024279B (zh) * 2023-10-10 2023-12-15 深圳市普利凯新材料股份有限公司 一种乙酰乙酸基甲基丙烯酸乙酯的脱色方法

Similar Documents

Publication Publication Date Title
CN106032281B (zh) 一种具有介孔和微孔的丝光沸石的制备方法及应用
CN106032280B (zh) 一种具有介孔和微孔的丝光沸石的合成方法、产品及其应用
WO2016145619A1 (zh) 一种具有介孔和微孔的丝光沸石的制备方法及应用
CN111087002B (zh) 一种丝光沸石分子筛的制备方法及应用
CN104418353B (zh) 一种具有多级孔道结构的Beta分子筛及其制备方法
CN108217680B (zh) 合成丝光沸石mor分子筛的方法、及其产品和应用
CN112645349A (zh) 一种丝光沸石分子筛的制备方法及其应用
CN106032282B (zh) 一种具有介孔和微孔的丝光沸石的制备方法及应用
WO2018103089A1 (zh) 合成丝光沸石mor分子筛的方法、及其产品和应用
WO2016145618A1 (zh) 一种具有介孔和微孔的丝光沸石的合成方法、产品及其应用
CN100450617C (zh) 一种高岭土基复合分子筛及其制备方法
WO2016086361A1 (zh) 一种纳米zsm-5分子筛的合成方法
CN105621445A (zh) 一种NaY型分子筛及其制备方法
CN106395851B (zh) 一种含Ba杂原子LTL分子筛及其制备方法与应用
US20240059573A1 (en) Zsm-23 zeolite and preparation process and use thereof
WO2018205841A1 (zh) 中孔NaY型沸石分子筛的制备方法
CN105645427B (zh) 具有介孔‑微孔分等级结构的zsm‑22分子筛的制备方法
Lv et al. Al-rich Cu-SSZ-13 zeolite synthesized by interconversion from Y: Crystallization process resolution and application in the selective catalytic reduction of NO with NH3
CN105645428B (zh) 具有介孔‑微孔分等级结构的ssz‑32分子筛的制备方法
CN114433197B (zh) 一种用于烯烃异构化反应的负载金属催化剂及其制备方法
CN110856819A (zh) 表面富铝分子筛及制备方法和应用和异构化反应催化剂及其应用
CN108285151B (zh) 一种Ce同晶取代LTL分子筛及其制备方法
WO2016145617A1 (zh) 一种具有介孔和微孔的丝光沸石的制备方法及应用
CN118666292A (zh) 一种分步晶化制备zsm-23分子筛的方法、zsm-23分子筛及其应用
CN116262623A (zh) 一种金属改性的多级孔高硅y分子筛及其制备方法和应用

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 15885001

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 15885001

Country of ref document: EP

Kind code of ref document: A1