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WO2018103089A1 - 合成丝光沸石mor分子筛的方法、及其产品和应用 - Google Patents

合成丝光沸石mor分子筛的方法、及其产品和应用 Download PDF

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WO2018103089A1
WO2018103089A1 PCT/CN2016/109273 CN2016109273W WO2018103089A1 WO 2018103089 A1 WO2018103089 A1 WO 2018103089A1 CN 2016109273 W CN2016109273 W CN 2016109273W WO 2018103089 A1 WO2018103089 A1 WO 2018103089A1
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sio
molecular sieve
aluminum
mor molecular
membered ring
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French (fr)
Inventor
王林英
田鹏
刘中民
杨虹熠
赵学斌
郜贝贝
乔昱焱
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Dalian Institute of Chemical Physics of CAS
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Dalian Institute of Chemical Physics of CAS
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Priority to JP2019530676A priority Critical patent/JP6834003B2/ja
Priority to US16/467,818 priority patent/US10968109B2/en
Priority to EP16923613.0A priority patent/EP3553027B1/en
Priority to BR112019011779-2A priority patent/BR112019011779B1/pt
Priority to PCT/CN2016/109273 priority patent/WO2018103089A1/zh
Priority to AU2016431572A priority patent/AU2016431572B2/en
Application filed by Dalian Institute of Chemical Physics of CAS filed Critical Dalian Institute of Chemical Physics of CAS
Priority to EA201990993A priority patent/EA038140B1/ru
Publication of WO2018103089A1 publication Critical patent/WO2018103089A1/zh
Priority to SA519401955A priority patent/SA519401955B1/ar
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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
    • C01B39/265—Mordenite type using at least one organic template directing agent
    • 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 invention belongs to the field of inorganic porous materials, adsorption materials and catalytic materials, and particularly relates to a method for synthesizing mordenite MOR molecular sieves, products and applications thereof.
  • Mordenite is one of the earliest known zeolites, divided into natural and synthetic types. In 1864, How was the first to name natural mordenite.
  • Figure 1 shows a schematic view of the structure of the pores of the MOR molecular sieve.
  • the MOR molecular sieve has two parallel channels of 12-membered ring and 8-membered ring in the [001] direction, and the channel sizes are respectively about Since the diameter of the 8-membered ring channel in the [001] direction is too small, it is generally considered that the reactant molecules cannot diffuse in such 8-membered ring channels.
  • Mordenite has excellent heat resistance, acid resistance and water vapor resistance, and is widely used as a catalyst for separating gas or liquid mixtures and a catalyst for petrochemical and fine chemicals.
  • reactions involving larger size molecules are generally considered to occur only within the 12-membered ring main channel.
  • the 8-membered ring "side pocket" is considered to be the only reaction site.
  • the invention provides a method of synthesizing a mordenite MOR molecular sieve having a center of B acid preferentially located in an 8-membered "side pocket" in the presence of an inorganic base, the method comprising:
  • the initial gel B obtained in the step b) is crystallized at 120 to 200 ° C under autogenous pressure for 12 to 240 hours.
  • the solid product is filtered, separated and washed to neutral with deionized water, and after drying, the mordenite MOR molecular sieve is obtained.
  • M in the inorganic base M 2 O represents an alkali metal
  • the additional reagent N satisfies the pore size of the 8-membered ring "side pocket" and is selected from the group consisting of methylamine, dimethylamine, trimethylamine, and B.
  • the aluminum source is one or more of aluminum isopropoxide, aluminum oxide, aluminum hydroxide, aluminum chloride, aluminum sulfate, aluminum nitrate, and sodium aluminate.
  • the silicon source is one of coarse pore silicon powder, fine pore silicon powder, silica sol, silicone gel, methyl orthosilicate, tetraethyl orthosilicate, white carbon, and water glass. kind or several.
  • the inorganic base is one or both of lithium hydroxide and sodium hydroxide.
  • the present invention provides a method for synthesizing a mordenite MOR molecular sieve having a center of B acid preferentially located in a "side pocket" of an 8-membered ring channel without using an inorganic base, wherein an alkali metal is not present in the reaction system.
  • the methods include:
  • step b) the initial gel B obtained in step b) is crystallized at 120-200 ° C, autogenous pressure for 12h ⁇ 480h;
  • M in the inorganic base M 2 O represents an alkali metal
  • the additional reagent N satisfies the pore size of the 8-membered ring "side pocket" and is selected from the group consisting of methylamine, dimethylamine, trimethylamine, and B.
  • the aluminum source is one or more of aluminum isopropoxide, aluminum oxide, aluminum hydroxide, aluminum chloride, aluminum sulfate, and aluminum nitrate.
  • the silicon source is one or more of coarse pore silicon powder, fine pore silicon powder, silica sol, silicone gel, methyl orthosilicate, tetraethyl orthosilicate, and white carbon black.
  • coarse pore silicon powder fine pore silicon powder
  • fine pore silicon powder silica sol
  • silicone gel silicone gel
  • methyl orthosilicate tetraethyl orthosilicate
  • white carbon black white carbon black.
  • the crystallization is static or dynamic crystallization.
  • the present invention provides a mordenite MOR molecular sieve obtained according to the above method, characterized in that in the mordenite MOR molecular sieve, the B acid center in the 8-membered ring "side pocket" accounts for the total number of B acid centers 50-95%.
  • the present invention provides a catalyst for dimethyl ether carbonylation reaction, characterized in that the catalyst can be removed by calcination and ion exchange by mordenite MOR molecular sieve synthesized by the above method in the presence of an inorganic base.
  • the inorganic alkali metal ion is obtained by calcination in air at 400 to 700 ° C; or the mordenite MOR molecular sieve synthesized by the above method without the presence of an inorganic base is directly calcined in air at 400 to 700 ° C.
  • the beneficial effects that can be produced by the present invention include, but are not limited to, the following:
  • a high crystallinity mordenite MOR molecular sieve is obtained by the technical solution of the present invention as compared with the prior art.
  • the present invention uses a specific additional reagent that matches the pore size of the 8-membered ring "side pocket" that is in communication with the 12-membered ring main channel, which is capable of entering the 8-membered "side pocket” to form the active B of the molecular sieve catalyst.
  • the acid center thereby providing the B acid center position and distribution of the directly modulating molecular sieve catalyst, wherein the ratio of the B acid center of the 8-membered ring "side pocket" to the total number of B acid centers in the molecular sieve catalyst can be in a larger range Internal (50 ⁇ 95%) flexible modulation;
  • the preparation method of the mordenite provided by the application has a simple process and is advantageous for large-scale industrial production
  • the mordenite prepared by 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.
  • the present invention synthesizes a mordenite MOR molecular sieve by an alkali-free metal system without using an inorganic base to obtain an MOR molecular sieve containing no alkali metal ions, so that the catalyst preparation process for preparing a synthetic product no longer requires an ion exchange step, but can pass
  • the H-type molecular sieve catalyst is directly obtained by calcination.
  • Figure 1 is a schematic view showing the structure of a mordenite MOR molecular sieve.
  • Example 2 is an XRD chart of a mordenite MOR sample synthesized in Example 1.
  • Example 3 is an SEM image of a mordenite MOR sample synthesized in Example 1.
  • the MOR molecular sieve synthesis method capable of directly modulating the center position and distribution of the B acid acid provided by the invention comprises the following aspects:
  • the present invention provides a method for synthesizing a mordenite MOR molecular sieve having an acid center preferentially located in an 8-membered ring "side pocket" in the presence of an inorganic base, comprising the steps of:
  • the initial gel mixture B obtained in the step b) is heated at 120 ⁇ 200 ° C, autogenous pressure for 12h ⁇ 240h;
  • the solid product is separated by filtration, washed with water (for example, deionized water) to neutrality, and dried to obtain a MOR molecular sieve.
  • water for example, deionized water
  • the silicon source is added in an amount of SiO 2 ; the aluminum source is added in a molar amount of Al 2 O 3 ; the inorganic base is added in an amount of the mole of the inorganic base itself.
  • the additional reagent N is added in an amount of moles of N itself; the amount of water added is based on the moles of water itself.
  • the source of aluminum in step a) is selected from at least one of aluminum isopropoxide, aluminum oxide, aluminum hydroxide, aluminum chloride, aluminum sulfate, aluminum nitrate, and sodium aluminate.
  • the source of inorganic alkali in step a) is selected from at least one of lithium hydroxide or sodium hydroxide.
  • the silicon source in step a) is selected from at least one of coarse pore silicon powder, fine pore silicon powder, silica sol, silicone gel, methyl orthosilicate, tetraethyl orthosilicate, white carbon and water glass.
  • coarse pore silicon powder fine pore silicon powder
  • fine pore silicon powder fine pore silicon powder
  • silica sol silicone gel
  • methyl orthosilicate tetraethyl orthosilicate
  • white carbon and water glass white carbon and water glass.
  • the additional reagent N is a fatty amine or a fatty alcohol, and in order to meet the size of the 8-membered "side pocket" channel, the additional reagent N needs to be selected to enable access to the 8-membered "side pocket". .
  • the aliphatic amine has 4 substituents, it can only be a methyl group, and specifically, tetramethylammonium hydroxide, tetramethylammonium bromide, tetramethylammonium chloride or tetramethylammonium iodide can be selected.
  • methylamine, dimethylamine, ethylamine, diethylamine and N-methylethylenediamine may be selected.
  • the additional reagent N in step a) may be methylamine (MA), dimethylamine (DMA), trimethylamine (TMA), ethylamine (EA), diethylamine (DEA), triethylamine (TEA).
  • MA methylamine
  • DMA dimethylamine
  • TMA trimethylamine
  • EA ethylamine
  • DEA diethylamine
  • TEA triethylamine
  • the source of the mordenite MOR molecular sieve seed crystal in step b) may be commercially available or may be laboratory synthesis; it may be a raw powder before calcination or a Na type, H type or NH 4 type sample after calcination.
  • Al 2 O 3 : SiO 2 0.01 to 0.1 in step a)
  • M 2 O:SiO 2 in step a) 0.05 to 0.5
  • N:SiO 2 in step a) 0.2 to 0.6
  • H 2 O:SiO 2 in step a) 10 to 50
  • the temperature of the dynamic crystallization in step c) is from 130 to 180 °C.
  • the crystallization time of the dynamic crystallization in step c) is from 12 to 96 h.
  • the crystallization in step c) may be either dynamic crystallization or static crystallization.
  • the separation in step c) is centrifugation or filtration separation.
  • the present invention also provides a method for synthesizing a mordenite MOR molecular sieve having a center of B acid preferentially located in a "side pocket" of an 8-membered ring without using an inorganic base, characterized in that alkali metal is not present in the reaction system, and synthesis Proceed as follows:
  • step b) The initial gel B obtained in step b) is crystallized at 120-200 ° C for 12 h to 480 h under autogenous pressure;
  • the solid product is separated by filtration, washed with water (for example, deionized water) to neutrality, and dried to obtain a mordenite MOR molecular sieve.
  • water for example, deionized water
  • the amount of silicon source added in step a) is based on the number of moles of SiO 2 ; the amount of aluminum source added is in moles of Al 2 O 3 ; the amount of fluorine-containing reagent F added is in terms of its own moles; The amount added is based on the number of moles of N itself; the amount of water added is based on the moles of water itself.
  • the source of aluminum in step a) is selected from at least one of aluminum isopropoxide, aluminum oxide, aluminum hydroxide, aluminum chloride, aluminum sulfate, and aluminum nitrate.
  • the silicon source in step a) is selected from at least one of coarse pore silicon powder, fine pore silicon powder, silica sol, silicone gel, methyl orthosilicate, tetraethyl orthosilicate, and white carbon black.
  • the additional reagent N is a fatty amine or a fatty alcohol, and in order to meet the size of the 8-membered "side pocket" channel, the additional reagent N needs to be selected to enable access to the 8-membered "side pocket". .
  • the aliphatic amine has 4 substituents, it can only be a methyl group, and specifically, tetramethylammonium hydroxide, tetramethylammonium bromide, tetramethylammonium chloride or tetramethylammonium iodide can be selected.
  • methylamine, dimethylamine, ethylamine, diethylamine and N-methylethylene are selected.
  • the additional reagent N in step a) may be methylamine (MA), dimethylamine (DMA), trimethylamine (TMA), ethylamine (EA), diethylamine (DEA), triethylamine (TEA).
  • MA methylamine
  • DMA dimethylamine
  • TMA trimethylamine
  • EA ethylamine
  • DEA diethylamine
  • TEA triethylamine
  • the fluorine-containing reagent F in the step a) is at least one of hydrofluoric acid or amine fluoride.
  • the source of the MOR molecular sieve seed crystal in step b) may be commercially available or may be laboratory synthesis; it may be a raw powder before calcination or a H-type or NH 4 type sample after calcination.
  • Al 2 O 3 : SiO 2 0.01 to 0.1 in step a)
  • M 2 O:SiO 2 in step a) 0.05 to 0.5
  • N:SiO 2 in step a) 0.2 to 0.8
  • H 2 O:SiO 2 in step a) 3 to 30
  • the temperature of the dynamic crystallization in step c) is from 130 to 180 °C.
  • the crystallization time of the dynamic crystallization in step c) is from 12 to 240 h.
  • the crystallization in step c) may be either dynamic crystallization or static crystallization.
  • the separation in step c) is centrifugation or filtration separation.
  • a catalyst for dimethyl ether carbonylation reaction which has the advantages of high conversion of dimethyl ether, high selectivity of methyl acetate, and long life.
  • the B acid center prepared by one method is preferentially placed in an 8-membered ring "side pocket" of mordenite (which contains an alkali metal ion to be subjected to an ion exchange method, such as ammonium ion exchange), and then calcined in air at 400 to 700 ° C to obtain .
  • the scanning electron microscope (SEM) test was performed on a Hitachi SU8020 field emission scanning electron microscope with an acceleration voltage of 2 kV.
  • Measurements of 1 H MAS NMR spectra were measured on a Varian Infinity plus-400 nuclear magnetic resonance spectroscopy using a 4 mm probe.
  • the spin-echo program is used, the rotation speed is 12 kHz, the sampling frequency is 32, the pulse width of ⁇ /4 is 4.4 ⁇ s, and the sampling delay is 10 s.
  • Amantadine was used as a chemical shift reference and corrected to 1.74 ppm.
  • the sample was vacuum dehydrated at 400 ° C and below 10 -3 Pa for more than 20 h to remove water and impurities adsorbed in the molecular sieve.
  • the sample was transferred to a nuclear magnetic rotor under a pressure of atmospheric nitrogen atmosphere in a glove box for 1 H MAS NMR spectrum test.
  • Figure 2 is an XRD pattern of the sample. It can be seen from Figure 2 that the obtained molecular sieve sample has the structure of a typical mordenite MOR molecular sieve and has high purity and crystallinity, and a typical XRD pattern represented by sample 1 # Figure 2 shows the XRD diffraction peak data as shown in Table 1.
  • Example 3 is a SEM picture of the sample obtained in Example 1. As can be seen from FIG. 3, the sample was agglomerated from a sheet having a size of about 500 to 700 nm*300 to 400 nm*50 to 70 nm.
  • Example 1 The MOR molecular sieve obtained in Example 1 was subjected to air calcination at 600 ° C to remove organic matter, and then subjected to ammonium ion exchange (NH 4 (NO 3 ) 4 , 1 Mol/L, 80 ° C, 2 h, 2 times), and then calcined at 550 ° C for 6 h to obtain H. - MOR molecular sieve.
  • NH 4 (NO 3 ) 4 1 Mol/L, 80 ° C, 2 h, 2 times
  • the obtained H-MOR molecular sieve was measured by 1 H MAS NMR 1 H MAS NMR on a Varian Infinity plus-400 type nuclear magnetic resonance spectrometer using a 4 mm probe.
  • the spin-echo program was used at a speed of 12 kHz with adamantane as a chemical shift reference and corrected to 1.74 ppm.
  • the obtained sample was vacuum-dehydrated at 400 ° C and below 10 -3 Pa for more than 20 hours to remove water and impurities adsorbed on the molecular sieve.
  • the sample was transferred to a nuclear magnetic rotor under a pressure of nitrogen atmosphere in a glove box for 1 H MAS NMR test, and hexafluoroethylene propanol (CF 3 CHOHCF 3 ) was used as a standard.
  • the amount of acid at 3.8 ppm is the total amount of B acid, and the sample is subjected to pyridine adsorption after measurement (adsorption method is referred to [MEDavis et a1.J. Phys.Chem.C, 2011, 115, 1096-1102]), and then The sample was subjected to 1 H MAS NMR test.
  • the signal of pyridine after the adsorption of pyridine in the main channel of the 12-member ring moved to 15 ppm, and the signal at 3.8 ppm still belonged to the B acid center generated by the 8-side ring "side pocket".
  • the B acid center in the "side pocket" of the 8-membered ring channel accounts for 87% of the total B acid center.
  • the synthesized samples were analyzed by XRD, and the data results were close to those of Fig. 2, that is, the positions and shapes of the diffraction peaks were the same, and the relative peak intensity fluctuated within ⁇ 5% according to the change of the synthesis conditions, indicating that the synthesized products were all pure phase mordenite MOR.
  • the calcined and ion-exchanged samples were subjected to an acid test, and the test method was simultaneously carried out in Example 1.
  • Silicon source a silica sol; b white carbon black; c- orthosilicate; d -orthosilicate; e- silicon gel; f water glass; g coarse-pored silicon powder; h fine-pored silicon powder.
  • Aluminum Source I sodium aluminate; aluminum chloride II; III aluminum hydroxide; aluminum sulfate IV; V alumina; Vl aluminum isopropoxide; VII aluminum nitrate.
  • Na 2 O and Li 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 Li 2 O calculated
  • silica gel is added, and hydrofluoric acid is further stirred at room temperature until a uniform silica-alumina gel is formed.
  • the synthesized samples were analyzed by XRD, and the data results were close to those of Fig. 2, that is, the positions and shapes of the diffraction peaks were the same, and the relative peak intensity fluctuated within ⁇ 5% according to the change of the synthesis conditions, indicating that the synthesized product was pure phase MOR.
  • Example 4 is a SEM picture of the sample obtained in Example 13. As can be seen from FIG. 4, the sample is a cuboid-like sample having a size of about 300 nm*150 nm*100 nm.
  • the synthesized samples were analyzed by XRD, and the data results were close to those of Fig. 2, that is, the positions and shapes of the diffraction peaks were the same, and the relative peak intensity fluctuated within ⁇ 5% according to the change of the synthesis conditions, indicating that the synthesized product had a pure phase MOR.
  • the calcined and ion-exchanged samples were subjected to an acid test in the same manner as in Example 13.
  • silicon source a silica sol; b white carbon black; c- orthosilicate; d- ortho-methyl silicate; e- silicone gel; f coarse-pored silicon powder; g fine-pored silicon powder.
  • Aluminum source I aluminum sulfate; II aluminum chloride; III aluminum hydroxide; IV aluminum sulfate; V alumina; VI isopropoxide aluminum;
  • Example 1 The sample obtained in Example 1 was subjected to ion exchange with NH 4 NO 3 to remove sodium ions, and calcined in air at 400 to 600 ° C for 4 hours, and then tableted and crushed to 40 to 60 mesh.
  • 0.6 g of the treated sample i.e., catalyst C1#
  • the reaction product was analyzed on-line using Agilent's 6890 GC gas chromatograph.
  • the column was an Agilent HP-5 capillary column. The results showed that after the induction period of 1 h, the conversion rate of DME was 88.3%, the selectivity of methyl acetate in the product reached 99.5%, and the stability was good. The conversion rate of DME remained above 85% after 48 h.

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Abstract

一种B酸中心落位和分布可调变丝光沸石(MOR)分子筛的合成方法、其产品和应用。更具体地，一种在有或没有无机碱存在下合成酸中心优先落位在与12元环孔道相连通的8元环"侧口袋"的丝光沸石MOR分子筛的方法，所述方法包括在合成凝胶中引入结构和电荷密度不同的附加试剂和任选的氟化试剂，得到的MOR沸石B酸中心优先落位在与12元环孔道相连通的8元环的"侧口袋"中，通过该方法获得的催化剂产品在吸附和催化方面表现出优异的性能。该合成方法简单，具有广阔的工业应用前景，尤其是应用于二甲醚羰基化反应催化剂中。

Description

合成丝光沸石MOR分子筛的方法、及其产品和应用 技术领域
本发明属于无机多孔材料、吸附材料和催化材料领域，具体涉及一种合成丝光沸石MOR分子筛的方法、其产品和应用。
背景技术
多孔材料由于其特定的孔道结构和均一的孔径尺寸，广泛应用于吸附、分离、离子交换和催化等诸多领域。丝光沸石(MOR)是人类认识最早的沸石之一，分为天然和合成两种类型。1864年，How首次命名了天然丝光沸石。
图1示出了MOR分子筛孔道结构示意图。如图1所示，MOR分子筛在[001]方向上存在12元环和8元环两种相互平行的孔道，孔道尺寸分别为约
Figure PCTCN2016109273-appb-000001
由于[001]方向的8元环孔道直径太小，一般认为反应物分子无法在这样的8元环孔道中扩散。此外，在[010]方向上还存在一个8元环孔道，孔口大小为约
Figure PCTCN2016109273-appb-000002
这个孔道与12元环主孔道相连通，因此也称作“侧口袋”。
丝光沸石具有优良的耐热、耐酸和抗水汽性能，工业上广泛用作气体或液体混合物分离的吸附剂及石油化工与精细化工的催化剂。根据反应物、产物和反应中间体尺寸的差别，涉及尺寸较大分子的反应通常认为只能在12元环主孔道内发生。然而对于某些特定的反应，如二甲醚与CO气相羰基化反应则认为8元环“侧口袋”是唯一反应场所，研究者发现MOR分子筛的二甲醚羰基化活性与分子筛“侧口袋”中的B酸量成正比，而与12元环孔道中的酸密度无关(E.Iglesia，et al.Acc.Chem.Res.2008，14(4)，559-567)。而分子筛B酸中心的落位和分布与分子筛合成方法息息相关(J.Ddeek，et al.Catal，Catal.Reviews：Science and Engineering，2012，54(2)，135-223)，而通过有效控制合成过程，直接获得B酸位落位和分布可调变MOR分子筛的研究鲜有涉及。
发明内容
本发明的目的是提供一种可直接调变B酸中心落位和分布的MOR分子筛合成方法。
在一方面，本发明提供了一种在无机碱存在下合成B酸中心优先落位在8元环“侧口袋”的丝光沸石MOR分子筛的方法，所述方法包括：
a)将以Al2O3计的铝源、以SiO2计的硅源、无机碱M2O、附加试剂N和水H2O混合，形成具有如下摩尔配比组成的初始混合物A：
Al2O3∶SiO2＝0.005～0.1∶1
M2O∶SiO2＝0.05～1∶1
N∶SiO2＝0.1～1∶1
H2O∶SiO2＝5～60∶1；
b)将丝光沸石MOR分子筛晶种S加入步骤a)中所得的初始混合物A中，搅拌均匀，得到初始凝胶B，其中加入的晶种S与所述初始混合物A中所含的SiO2的质量比为S∶SiO2＝0.005～0.1∶1；
c)将步骤b)中所得的初始凝胶B在120～200℃、自生压力下晶化12h～240h，
d)在晶化完成后，将固体产物过滤、分离并使用去离子水洗涤至中性，干燥后即得到所述丝光沸石MOR分子筛，
其中所述无机碱M2O中的M表示碱金属；所述附加试剂N满足与所述8元环“侧口袋”的孔道尺寸匹配并且为选自甲胺、二甲胺、三甲胺、乙胺、二乙胺、三乙胺、N-甲基二乙胺、N，N-二甲基乙胺、N甲基乙二胺、N，N-二甲基乙二胺、N，N，N-三甲基乙二胺、N乙基乙二胺、N，N-二乙基乙二胺、N，N，N-三乙基乙二胺、N甲基-N，N-二乙基乙二胺、N，N二甲基-N乙基乙二胺、N，N，N，N-四甲基乙二胺、正丙胺、二正丙胺、异丙胺、四甲基氢氧化铵、四甲基溴化铵、四甲基氯化铵、四甲基碘化铵、甲醇、乙醇、正丙醇和异丙醇中的一种或几种。
在一个优选实施方案中，所述铝源为异丙醇铝、氧化铝、氢氧化铝、氯化铝、硫酸铝、硝酸铝和铝酸钠中的一种或几种。
在一个优选实施方案中，所述硅源为粗孔硅粉、细孔硅粉、硅溶胶、硅凝胶、正硅酸甲酯、正硅酸乙酯、白炭黑和水玻璃中的一种或几种。
在一个优选实施方案中，其特征在于，所述无机碱为氢氧化锂和氢氧化钠中的一种或两种。
另一方面，本发明提供了一种不使用无机碱来合成B酸中心优先落位在8元环孔道的“侧口袋”的丝光沸石MOR分子筛的方法，其中反应体系中不存在碱金属，所述方法包括：
a)将以Al2O3计的铝源、以SiO2计的硅源、附加试剂N、含氟试剂F和水H2O混合，形成具有如下摩尔配比的初始混合物A：
Al2O3∶SiO2＝0.005～0.1∶1
F∶SiO2＝0.1～1∶1
N∶SiO2＝0.1～1∶1
H2O∶SiO2＝1～50∶1；
b)将丝光沸石MOR分子筛晶种S加入到步骤a)中所得的初始混合物A中，搅拌均匀，得到初始凝胶B，其中加入的晶种S与所述初始混合物A中所含的SiO2的质量比为S∶SiO2＝0.005～0.1∶1；
c)将步骤b)中所得的初始凝胶B在120～200℃、自生压力下晶化12h～480h；
d)在晶化完成后，将固体产物过滤、分离并用水洗涤至中性，干燥后即得到所述丝光沸石MOR分子筛。
其中所述无机碱M2O中的M表示碱金属；所述附加试剂N满足与所述8元环“侧口袋”的孔道尺寸匹配并且为选自甲胺、二甲胺、三甲胺、乙胺、二乙胺、三乙胺、N-甲基二乙胺、N，N-二甲基乙胺、N甲基乙二胺、N，N-二甲基乙二胺、N，N，N-三甲基乙二胺、N乙基乙二胺、N，N-二乙基乙二胺、N，N，N-三乙基乙二胺、N甲基-N，N-二乙基乙二胺、N，N二甲基-N乙基乙二胺、N，N，N，N-四甲基乙二胺、正丙胺、二正丙胺、异丙胺、四甲基氢氧化铵、四甲基溴化铵、四甲基氯化铵、四甲基碘化铵、甲醇、乙醇、正丙醇和异丙醇中的一种或几种。
在一个优选实施方案中，所述铝源为异丙醇铝、氧化铝、氢氧化铝、氯化铝、硫酸铝和硝酸铝中的一种或几种。
在一个优选实施方案中，所述硅源为粗孔硅粉、细孔硅粉、硅溶胶、硅凝胶、正硅酸甲酯、正硅酸乙酯和白炭黑中的一种或几种。
在一个优选实施方案中，所述晶化为静态晶或动态晶化。
另一方面，本发明提供根据上述方法得到的丝光沸石MOR分子筛，其特征在于，在所述丝光沸石MOR分子筛中，所述8元环“侧口袋”中的B酸中心占总B酸中心数量的50-95％。
另一方面，本发明提供一种用于二甲醚羰基化反应的催化剂，其特征在于，所述催化剂可以通过上述有无机碱存在下的方法合成的丝光沸石MOR分子筛经过焙烧及离子交换法去除无机碱金属离子后，在400～700℃空气中焙烧得到；或者通过将上述无无机碱存在下的方法合成的丝光沸石MOR分子筛经400～700℃空气中直接焙烧得到。
本发明能产生的有益效果至少包括但不限于以下方面：
1)与现有技术相比，通过本发明技术方案获得高结晶度丝光沸石MOR分子筛。
2)本发明使用满足与12元环主孔道相连通的8元环“侧口袋”的孔道尺寸相匹配的特定附加试剂，其能够进入所述8元环“侧口袋”形成分子筛催化剂的活性B酸中心，由此提供可直接调变分子筛催化剂的B酸中心落位和分布，其8元环“侧口袋”的B酸中心占分子筛催化剂中的总B酸中心数量的比例可以在较大范围内(50～95％)灵活调变；
3)本申请所提供的丝光沸石的制备方法，工艺简单，利于大规模工业化生产；
4)根据本发明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。
5)本发明通过不使用无机碱的无碱金属体系下合成丝光沸石MOR分子筛，得到不含碱金属离子的MOR分子筛，因而由合成产品制备所需催化剂过程不再需要离子交换步骤，而可以通过焙烧直接获得H型分子筛催化剂。
附图说明
图1为丝光沸石MOR分子筛孔道结构示意图。
图2为实施例1所合成的丝光沸石MOR样品的XRD图。
图3为实施例1所合成的丝光沸石MOR样品的SEM图。
图4为实施例13所合成的丝光沸石MOR样品的SEM图。
具体实施方式
本发明提供的可直接调变B酸中心落位和分布的MOR分子筛合成方法包括以下方面：
I.本发明提供一种在无机碱存在下合成酸中心优先落位在8元环“侧口袋”的丝光沸石MOR分子筛的方法包括如下步骤：
a)将以Al2O3计的铝源、以SiO2计的硅源、无机碱M2O、附加试剂N和水H2O混合，形成具有如下摩尔配比组成的初始混合物A；
Al2O3∶SiO2＝0.005～0.1∶1
M2O∶SiO2＝0.05～1∶1
N∶SiO2＝0.1～1∶1
H2O∶SiO2＝5～60∶1；
b)将一定比例的丝光沸石MOR分子筛晶种S加入到步骤a)所得的凝胶混合物A中，搅拌均匀，得到初始凝胶B，其中晶种S的加入量与凝胶A所含SiO2的质量比为S∶SiO2＝0.005～0.1∶1；
c)将所述步骤b)所得的初始凝胶混合物B于120～200℃，自生压力下晶化12h～240h；
d)待晶化完成后，将固体产物过滤分离，用水(例如去离子水)洗涤至中性，干燥后即得到MOR分子筛。
步骤a)的初始混合物A中，硅源的加入量以SiO2的摩尔数计；铝源的加入量以Al2O3的摩尔数计；无机碱的加入量以无机碱本身的摩尔数计；附加试剂N的加入量以N本身的摩尔数计；水的加入量以水本身的摩尔数计。
优选地，步骤a)中的铝源选自异丙醇铝、氧化铝、氢氧化铝、氯化铝、硫酸铝、硝酸铝和铝酸钠中至少一种。
优选地，步骤a)中的无机碱源选自氢氧化锂或氢氧化钠中至少一种。
优选地，步骤a)中的硅源选自粗孔硅粉、细孔硅粉、硅溶胶、硅凝胶、正硅酸甲酯、正硅酸乙酯、白炭黑和水玻璃中的至少一种。
在本发明中，附加试剂N为脂肪胺或脂肪醇，同时为满足与8元环“侧口袋”孔道尺寸匹配，需要对附加试剂N加以选择，以使其能够进入8元环“侧口袋”。为此，如果脂肪胺的取代基为4个，则只能是甲基，具体可选四甲基氢氧化铵、四甲基溴化铵、四甲基氯化铵、四甲基碘化铵、N，N，N，N-四甲基乙二胺中的任意一种或任意几种的混合；如果所述脂肪胺的取代基个数为3个，则只能为甲基或乙基，具体可选三甲胺或、三乙胺、N-甲基二乙胺、N，N-二甲基乙胺、N，N，N-三甲基乙二胺、N，N-二甲基-N乙基乙二胺、N甲基-N，N-二乙基乙二胺、N，N，N-三乙基乙二胺中的任意一种或几种的混合；如果所述脂肪胺或脂肪醇的取代基为2个或1个，则单个取代基的碳原子数不超过3个，具体可选甲胺、二甲胺、乙胺、二乙胺、N甲基乙二胺、N，N-二甲基乙二胺、N乙基乙二胺、N，N-二乙基乙二胺、N甲基-N乙基乙二胺、正丙胺、二正丙胺、异丙胺、甲醇、乙醇、正丙醇和异丙醇中的任一种或任几种的混合。
优选地，步骤a)中的附加试剂N可以为甲胺(MA)、二甲胺(DMA)、三甲胺(TMA)、乙胺(EA)、二乙胺(DEA)、三乙胺(TEA)、N、N-二甲基乙二胺、正丙胺(n-PA)、二正丙胺(DPA)、异丙胺(i-PA)、四甲基氢氧化铵(TMAOH)、四甲基溴化铵(TMABr)、四甲基氯化铵(TMACl)、四甲基碘化铵(TMAI)、甲醇(CH3OH)、乙醇(C2H5OH)、正丙醇(n-C3H7OH)和异丙醇(i-C3H7OH)中的任意一种或几种的组合。
步骤b)中的丝光沸石MOR分子筛晶种的来源可以是商业购买，也可以是实验室合成；既可以是焙烧前原粉，也可以是焙烧后Na型、H型或NH4型样品。
优选地，步骤a)中的Al2O3∶SiO2＝0.01～0.1
优选地，步骤a)中的M2O∶SiO2＝0.05～0.5
优选地，步骤a)中的N∶SiO2＝0.2～0.6
优选地，步骤a)中的H2O∶SiO2＝10～50
优选地，步骤c)中的动态晶化的温度为130～180℃。
优选地，步骤c)中的动态晶化的晶化时间为12～96h。
步骤c)中的晶化可以为动态晶化，也可以为静态晶化。
步骤c)中的分离方式为离心分离或过滤分离。
II.本发明还提供一种不使用无机碱来合成B酸中心优先落位在8元环“侧口袋”的丝光沸石MOR分子筛的方法，其特征在于，反应体系中不存在碱金属，并且合成步骤如下：
a)将以Al2O3计的铝源、以SiO2计的硅源、附加试剂N、含氟试剂F和水H2O混合，形成具有如下摩尔配比的初始混合物A；
Al2O3∶SiO2＝0.005～0.1∶1
F∶SiO2＝0.1～1∶1
N∶SiO2＝0.1～1∶1
H2O∶SiO2＝1～50∶1；
b)将一定比例的丝光沸石MOR分子筛晶种S加入到步骤a)所得到的初始混合物A中，搅拌均匀，得初始凝胶B，其中晶种S的加入量与初始凝胶B中所含SiO2的质量比为S∶SiO2＝0.005～0.1∶1；
c)将步骤b)所得的初始凝胶B于120～200℃，自生压力下晶化12h～480h；
d)待晶化完成后，将固体产物过滤分离，用水(例如去离子水)洗涤至中性，干燥后即得到丝光沸石MOR分子筛。
步骤a)中的硅源的加入量以SiO2的摩尔数计；铝源的加入量以Al2O3的摩尔数计；含氟试剂F加入量以其本身的摩尔数计；附加试剂N的加入量以N本身的摩尔数计；水的加入量以水本身的摩尔数计。
优选地，步骤a)中的铝源选自异丙醇铝、氧化铝、氢氧化铝、氯化铝、硫酸铝、硝酸铝中至少一种。
优选地，步骤a)中的硅源选自粗孔硅粉、细孔硅粉、硅溶胶、硅凝胶、正硅酸甲酯、正硅酸乙酯、白炭黑中的至少一种。
在本发明中，附加试剂N为脂肪胺或脂肪醇，同时为满足与8元环“侧口袋”孔道尺寸匹配，需要对附加试剂N加以选择，以使其能够进入8元环“侧口袋”。为此，如果脂肪胺的取代基为4个，则只能是甲基，具体可选四甲基氢氧化铵、四甲基溴化铵、四甲基氯化铵、四甲基碘化铵、N，N，N，N-四甲基乙二胺中的任意一种或任意几种的混合；如果所述脂肪胺的取代基个数为3个，则只能为甲基或乙基，具体可选三甲胺或、三乙胺、N-甲基二乙胺、N，N-二甲基乙胺、N，N，N-三甲基乙二胺、N，N-二甲 基-N乙基乙二胺、N甲基-N，N-二乙基乙二胺、N，N，N-三乙基乙二胺中的任意一种或几种的混合；如果所述脂肪胺或脂肪醇的取代基为2个或1个，则单个取代基的碳原子数不超过3个，具体可选甲胺、二甲胺、乙胺、二乙胺、N甲基乙二胺、N，N-二甲基乙二胺、N乙基乙二胺、N，N-二乙基乙二胺、N甲基-N乙基乙二胺、正丙胺、二正丙胺、异丙胺、甲醇、乙醇、正丙醇和异丙醇中的任一种或任几种的混合。
优选地，步骤a)中的附加试剂N可以为甲胺(MA)、二甲胺(DMA)、三甲胺(TMA)、乙胺(EA)、二乙胺(DEA)、三乙胺(TEA)、N、N-二甲基乙二胺、正丙胺(n-PA)、二正丙胺(DPA)、异丙胺(i-PA)、四甲基氢氧化铵(TMAOH)、四甲基溴化铵(TMABr)、四甲基氯化铵(TMACl)、四甲基碘化铵(TMAI)、甲醇(CH3OH)、乙醇(C2H5OH)、正丙醇(n-C3H7OH)和异丙醇(i-C3H7OH)中的任意一种或几种的组合；步骤a)中的含氟试剂F至少为氢氟酸或氟化胺中的至少一种。
步骤b)中的MOR分子筛晶种的来源可以是商业购买，也可以是实验室合成；其可以是焙烧前原粉，也可以是焙烧后H型或NH4型样品。
优选地，步骤a)中的Al2O3∶SiO2＝0.01～0.1
优选地，步骤a)中的M2O∶SiO2＝0.05～0.5
优选地，步骤a)中的N∶SiO2＝0.2～0.8
优选地，步骤a)中的H2O∶SiO2＝3～30
优选地，步骤c)中的动态晶化的温度为130～180℃。
优选地，步骤c)中的动态晶化的晶化时间为12～240h。
步骤c)中的晶化可以为动态晶化，也可以为静态晶化。
步骤c)中的分离方式为离心分离或过滤分离。
根据本申请的又一个方面，提供了一种用于二甲醚羰基化反应的催化剂，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B酸中心优先落位在8元环“侧口袋”的丝光沸石(其中含有碱金属离子的需经离子交换法，例如铵离子交换)后在400～700℃空气中焙烧得到。
下面通过实施例详述本发明，但本发明并不局限于这些实施例。
本申请的实施例中分析方法如下：
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。
1H MAS NMR谱图的测量在Varian Infinity plus-400型核磁共振波谱上测定，使用4mm探头。采用自旋回波(spin-echo)程序，转速为12kHz，采样次数为32，π/4的脉冲宽度为4.4μs，采样延迟为10s。以金刚烷为化学位移参考，校正到1.74ppm。进行测量前，样品在400℃，低于10-3 Pa真空脱水处理20h以上，以脱除吸附在分子筛中的水和杂质。在手套箱中常压氮气气氛保护下将样品转移到核磁转子中进行1H MAS NMR谱测试。
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：
在无机碱NaOH存在下加入附加试剂三甲胺来合成丝光沸石MOR分子筛
首先将0.67偏铝酸钠溶于去离子水，再向其中加入1.88g氢氧化钠，待形成澄清溶液之后，加入37.65g硅溶胶(SiO2含量为28.5％)，4.54g三甲铵，在室温下继续搅拌直到形成均匀的硅铝凝胶，然后向形成的硅铝凝胶加入MOR晶种0.1g形成混合原料，最后将混合原料转移到带聚四氟内衬的不锈钢反应釜中，170℃动态晶化48h，反应原料的摩尔配比如下：0.025Al2O3∶SiO2∶0.08Na2O∶0.28TMA∶20H2O，产物抽滤，烘干即得到MOR分子筛。
图2为样品的XRD图，由图2可以看出，得到的分子筛样品具有典型的丝光沸石MOR分子筛的结构，并且具有很高的纯度和结晶度，以样品1#为代表的典型XRD图谱如图2所示，并且其XRD衍射峰数据见表1。
表1 样品1#的XRD衍射峰数据
峰编号 2θ[°] I/I0*100
1 6.5153 34.09
2 8.6343 15.84
3 9.7673 81.44
4 13.484 47.32
5 13.882 25.84
6 14.6369 10.17
7 15.2996 24.66
8 17.5842 1.92
9 19.6458 45.45
10 21.0838 2.72
11 21.4997 4.2
12 22.29 89.48
13 23.2093 13.92
14 23.6732 13.76
15 24.5671 3.68
16 25.6795 100
17 26.3246 71.19
18 27.1554 9.72
19 27.6522 48.61
20 27.904 50.61
21 28.3143 7.78
22 28.721 5.05
23 30.4405 7.65
24 30.9577 26.17
25 33.2431 2.86
26 34.0683 2.03
27 35.1127 6.04
28 35.677 15.01
29 36.5319 5.3
30 36.973 3.7
31 39.311 1.26
32 40.5253 3.1
33 41.6509 0.88
34 42.7121 0.72
35 44.342 7.52
36 44.9558 4.35
37 45.5057 2.46
38 46.5543 8.44
39 47.4486 3.6
40 48.5007 8.35
41 50.4051 4.78
42 50.9485 4.56
43 53.2869 2.04
44 54.1035 2.51
图3为实施例1所得的样品的SEM图片，从图3可以看出，该样品是由尺寸约为500～700nm*300～400nm*50～70nm的薄片团聚而成。
将实施例1所得的MOR分子筛经600℃空气焙烧去除有机物后，经铵离子交换(NH4(NO3)4，1Mol/L，80℃，2h，2次)后经550℃焙烧6h得H-MOR分子筛。
将所得的H-MOR分子筛采用1H MAS NMR 1H MAS NMR在Varian Infinity plus-400型核磁共振波谱仪上测定，使用4mm探头。采用自旋(spin-echo)程序，转速为12kHz，以金刚烷为化学位移参考，校正到1.74ppm。进行测量前，所得样品在400℃，低于10-3 Pa真空脱水20h以上，以脱除吸附在分子筛上的水和杂质。在手套箱中常压氮气气氛保护下将样品转移到核磁转子中进行1H MAS NMR测试，以六氟乙丙醇(CF3CHOHCF3)为标样定量。以3.8ppm处酸量为总B酸中心量，测量后 对样品进行吡啶吸附(吸附方法参照文献[M.E.Davis et a1.J.Phys.Chem.C，2011，115，1096-1102])，后再对样品进行1H MAS NMR测试，此时12元环内主孔道B酸中心吸附吡啶后信号移动至15ppm，而3.8ppm处信号仍归属为8元环“侧口袋”产生的B酸中心。作为结果，8元环孔道的“侧口袋”中的B酸中心占总B酸中心数量的87％。
实施例2-12 样品2#-12#的制备
具体配料比例和晶化条件见表2，具体配料过程同实施例1。
合成的样品通过XRD分析，数据结果与图2接近，即衍射峰位置和形状相同，依合成条件的变化相对峰强度在±5％范围内波动，表明合成产物均为纯相丝光沸石MOR。将焙烧、离子交换后样品进行酸性测试，测试方法同时实施例1。
表2 分子筛合成配料及晶化条件表
Figure PCTCN2016109273-appb-000003
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；g粗孔硅粉；h细孔硅粉。
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Li2O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Li2O计算
实施例13
在不存在无机碱下加入附加试剂四甲基氢氧化胺合成丝光沸石MOR分子 筛
首先将硝酸铝溶于去离子水，再向其中加入四甲基氢氧化胺，待形成澄清溶液之后，加入硅凝胶，氢氟酸后在室温下继续搅拌直到形成均匀的硅铝凝胶，后向形成的硅铝凝胶中加入MOR晶种(MOR晶种质量占凝胶投入SiO2的1％)形成混合原料，将混合原料转移到带聚四氟内衬的不锈钢反应釜中，180℃动态晶化96h，反应原料的摩尔配比如下：SiO2∶0.01Al2O3∶0.35TMAOH∶0.30HF∶40H2O，产物抽滤，烘干即得到丝光沸石MOR。
合成样品经过XRD分析，数据结果与图2接近，即衍射峰位置和形状相同，依合成条件的变化相对峰强度在±5％范围内波动，表明合成产物为纯相MOR。
图4为实施例13所得样品的SEM图片，从图4可以看出：样品为尺寸约为300nm*150nm*100nm左右长方体块状样品团聚成菜花状形貌。
样品编号13#，测试方法同实施例1。经检测，丝光沸石MOR分子筛中8元环“侧口袋”中的B酸中心占总B酸中心数量的90％。
实施例14-24 样品14-24的制备
具体配料比例和晶化条件见表3，具体配料过程同实施例13。
合成样品经过XRD分析，数据结果与图2接近，即衍射峰位置和形状相同，依合成条件的变化相对峰强度在±5％范围内波动，表明合成产物具有为纯相MOR。将焙烧、离子交换后样品进行酸性测试，测试方法同实施例13。
表3 分子筛合成配料及晶化条件表
Figure PCTCN2016109273-appb-000004
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粗孔硅粉；g细孔硅粉。
铝源：I硫酸铝；II氯化铝；III氢氧化铝；IV硫酸铝；V氧化铝；VI异丙醇铝；。
将实施例1得到的样品经NH4NO3离子交换去除钠离子，400～600℃空气中焙烧4h后，压片、破碎至40～60目。称取0.6g处理后样品(即催化剂C1#)装入固定床反应器，进行二甲醚(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/He＝5/50/2.5/42.5，Vol％)的进气量为12.5ml/min，反应压力为1.0Mpa。反应产物采用美国Agilent公司6890GC型气相色谱仪进行在线分析，色谱柱为Agilent公司HP-5毛细柱。结果显示，在经历1h 的诱导期后，DME的转化率为88.3％，产物中乙酸甲酯的选择性达到99.5％，且稳定性良好，反应48h后DME的转化率仍保持在85％以上。
其它实施例2-24得到的样品处理同上，分别得到催化剂2#～24#其用于二甲醚羰基化反应结果如表4所示。
表4 样品1#～24#制成催化剂C1#～C24#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
C1# 88.3％ 99.5％
C2# 76.2％ 98.9％
C3# 60.9％ 98.4％
C4# 52.3％ 99.1％
C5# 78.5％ 99.4％
C6# 57.7％ 99.0％
C7# 77.9％ 99.2％
C8# 62.7％ 98.9％
C9# 80.4％ 99.1％
C10# 55.2％ 99.2％
C11# 87.3％ 98.7％
C12# 68.8％ 99.0％
C13# 95.2％ 99.0％
C14# 79.4％ 99.1％
C15# 68.6％ 99.0％
C16# 51.7％ 98.9％
C17# 79.9％ 98.4％
C18# 65.6％ 99.1％
C19# 77.2％ 99.1％
C20# 63.5％ 98.9％
C21# 82.5％ 98.5％
C22# 58.8％ 98.9％
C23# 81.5％ 99.2％
C24# 62.2％ 99.1％
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。
以上描述的仅是本发明的示例性实施例，这些实施例并非对本发明做任何形式的限制。本领域技术人员在不脱离本发明的范围情况下，利用以上公开的技术内容，可以做出多种变动或修饰，其均属于本发明的保护范围内。

Claims (10)

  1. 一种在无机碱存在下合成B酸中心优先落位在8元环“侧口袋”的丝光沸石MOR分子筛的方法，所述方法包括：
    a)将以Al2O3计的铝源、以SiO2计的硅源、无机碱M2O、附加试剂N和水H2O混合，形成具有如下摩尔配比组成的初始混合物A：
    Al2O3∶SiO2＝0.005～0.1∶1
    M2O∶SiO2＝0.05～1∶1
    N∶SiO2＝0.1～1∶1
    H2O∶SiO2＝5～60∶1；
    b)将丝光沸石MOR分子筛晶种S加入步骤a)中所得的初始混合物A中，搅拌均匀，得到初始凝胶B，其中加入的晶种S与所述初始混合物A中所含的SiO2的质量比为S∶SiO2＝0.005～0.1∶1；
    c)将步骤b)中所得的初始凝胶B在120～200℃、自生压力下晶化12h～240h，
    d)在晶化完成后，将固体产物过滤、分离并水洗涤至中性，干燥后即得到所述丝光沸石MOR分子筛，
    其中所述无机碱M2O中的M表示碱金属；所述附加试剂N与所述8元环“侧口袋”的孔道尺寸匹配并且为选自甲胺、二甲胺、三甲胺、乙胺、二乙胺、三乙胺、N-甲基二乙胺、N，N-二甲基乙胺、N甲基乙二胺、N，N-二甲基乙二胺、N，N，N-三甲基乙二胺、N，N，N，N-四甲基乙二胺、N乙基乙二胺、N，N-二乙基乙二胺、N，N，N-三乙基乙二胺、N甲基-N，N-二乙基乙二胺、N，N二甲基-N乙基乙二胺、N，N，N，N-四甲基乙二胺、正丙胺、二正丙胺、异丙胺、四甲基氢氧化铵、四甲基溴化铵、四甲基氯化铵、四甲基碘化铵、甲醇、乙醇、正丙醇和异丙醇中的一种或几种。
  2. 根据权利要求1所述的方法，其特征在于，所述铝源为异丙醇铝、氧化铝、氢氧化铝、氯化铝、硫酸铝、硝酸铝和铝酸钠中的一种或几种。
  3. 根据权利要求1所述的方法，其特征在于，所述硅源为粗孔硅粉、细孔硅粉、硅溶胶、硅凝胶、正硅酸甲酯、正硅酸乙酯、白炭黑和水玻璃中的一种或几种。
  4. 根据权利要求1所述的方法，其特征在于，所述无机碱为氢氧化锂和氢氧化钠中的一种或两种。
  5. 一种不使用无机碱来合成B酸中心优先落位在8元环“侧口袋”的丝光沸石MOR分子筛的方法，其中反应体系中不存在碱金属，所述方法包括：
    a)将以Al2O3计的铝源、以SiO2计的硅源、附加试剂N、含氟试剂F和水H2O混合，形成具有如下摩尔配比的初始混合物A：
    Al2O3∶SiO2＝0.005～0.1∶1
    F∶SiO2＝0.1～1∶1
    N∶SiO2＝0.1～1∶1
    H2O∶SiO2＝1～50∶1；
    b)将丝光沸石MOR分子筛晶种S加入到步骤a)中所得的初始混合物A中，搅拌均匀，得到初始凝胶B，其中加入的晶种S与所述初始混合物A中所含的SiO2的质量比为S∶SiO2＝0.005～0.1∶1；
    c)将步骤b)中所得的初始凝胶B在120～200℃、自生压力下晶化12h～480h；
    d)在晶化完成后，将固体产物过滤、分离并用水洗涤至中性，干燥后即得到所述丝光沸石MOR分子筛。
    其中所述无机碱M2O中的M表示碱金属；所述附加试剂N与所述8元环“侧口袋”的孔道尺寸匹配并且为选自甲胺、二甲胺、三甲胺、乙胺、二乙胺、三乙胺、N-甲基二乙胺、N，N-二甲基乙胺、N甲基乙二胺、N，N-二甲基乙二胺、N，N，N-三甲基乙二胺、N乙基乙二胺、N，N-二乙基乙二胺、N，N，N-三乙基乙二胺、N甲基-N，N-二乙基乙二胺、N，N二甲基-N乙基乙二胺、N，N，N，N-四甲基乙二胺、正丙胺、二正丙胺、异丙胺、四甲基氢氧化铵、四甲基溴化铵、四甲基氯化铵、四甲基碘化铵、甲醇、乙醇、正丙醇和异丙醇中的一种或几种。
  6. 根据权利要求5所述的方法，其特征在于，所述铝源为异丙醇铝、氧化铝、氢氧化铝、氯化铝、硫酸铝和硝酸铝中的一种或几种。
  7. 根据权利要求5所述的方法，其特征在于，所述硅源为粗孔硅粉、细孔硅粉、硅溶胶、硅凝胶、正硅酸甲酯、正硅酸乙酯和白炭黑中的一种 或几种。
  8. 根据权利要求1或5所述的方法，其特征在于，所述晶化为静态晶或动态晶化。
  9. 根据权利要求1或5所述的方法得到的丝光沸石MOR分子筛，其特征在于，所述8元环“侧口袋”中的B酸中心占所述丝光沸石MOR分子筛中的总B酸中心数量的50-95％。
  10. 一种用于二甲醚羰基化反应的催化剂，其特征在于，所述催化剂通过将权利要求1所述的方法合成的丝光沸石MOR分子筛经过焙烧及离子交换法去除无机碱金属离子后，在400～700℃空气中焙烧得到；或者通过将权利要求5所述的方法合成的丝光沸石MOR分子筛经400～700℃空气中直接焙烧得到。
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