CN110407227B - Method for synthesizing TNU-9 molecular sieve - Google Patents
Method for synthesizing TNU-9 molecular sieve Download PDFInfo
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- CN110407227B CN110407227B CN201810387842.5A CN201810387842A CN110407227B CN 110407227 B CN110407227 B CN 110407227B CN 201810387842 A CN201810387842 A CN 201810387842A CN 110407227 B CN110407227 B CN 110407227B
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- dibromobutane
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 63
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 238000000034 method Methods 0.000 title claims abstract description 45
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 30
- AVFZOVWCLRSYKC-UHFFFAOYSA-N 1-methylpyrrolidine Chemical compound CN1CCCC1 AVFZOVWCLRSYKC-UHFFFAOYSA-N 0.000 claims abstract description 41
- AHVYPIQETPWLSZ-UHFFFAOYSA-N N-methyl-pyrrolidine Natural products CN1CC=CC1 AHVYPIQETPWLSZ-UHFFFAOYSA-N 0.000 claims abstract description 40
- ULTHEAFYOOPTTB-UHFFFAOYSA-N 1,4-dibromobutane Chemical compound BrCCCCBr ULTHEAFYOOPTTB-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 27
- 239000000203 mixture Substances 0.000 claims abstract description 27
- 239000002904 solvent Substances 0.000 claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000002156 mixing Methods 0.000 claims abstract description 15
- 238000005216 hydrothermal crystallization Methods 0.000 claims abstract description 12
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 10
- 239000010703 silicon Substances 0.000 claims abstract description 10
- 150000007529 inorganic bases Chemical class 0.000 claims abstract description 7
- 239000012265 solid product Substances 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims description 24
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- 229910000272 alkali metal oxide Inorganic materials 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 239000000377 silicon dioxide Substances 0.000 claims description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- 229910052681 coesite Inorganic materials 0.000 claims description 5
- 229910052906 cristobalite Inorganic materials 0.000 claims description 5
- 229910052682 stishovite Inorganic materials 0.000 claims description 5
- 229910052905 tridymite Inorganic materials 0.000 claims description 5
- 150000001298 alcohols Chemical class 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- 229910052593 corundum Inorganic materials 0.000 claims description 4
- 150000002148 esters Chemical class 0.000 claims description 4
- 150000002170 ethers Chemical class 0.000 claims description 4
- 150000002576 ketones Chemical class 0.000 claims description 4
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 4
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 4
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 3
- HDYRYUINDGQKMC-UHFFFAOYSA-M acetyloxyaluminum;dihydrate Chemical compound O.O.CC(=O)O[Al] HDYRYUINDGQKMC-UHFFFAOYSA-M 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 3
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims description 3
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 3
- 229940009827 aluminum acetate Drugs 0.000 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 claims description 3
- 229910001950 potassium oxide Inorganic materials 0.000 claims description 3
- 229910002027 silica gel Inorganic materials 0.000 claims description 3
- 239000000741 silica gel Substances 0.000 claims description 3
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 229910001948 sodium oxide Inorganic materials 0.000 claims description 3
- 229920005862 polyol Polymers 0.000 claims 1
- 150000003077 polyols Chemical class 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 abstract description 20
- 238000003786 synthesis reaction Methods 0.000 abstract description 20
- 239000003795 chemical substances by application Substances 0.000 abstract description 13
- 239000000463 material Substances 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 6
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 238000000746 purification Methods 0.000 abstract description 3
- 238000000926 separation method Methods 0.000 abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 20
- 239000002994 raw material Substances 0.000 description 16
- 238000003756 stirring Methods 0.000 description 14
- 239000000843 powder Substances 0.000 description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 10
- 238000001228 spectrum Methods 0.000 description 10
- 235000019441 ethanol Nutrition 0.000 description 9
- 239000000047 product Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 238000002425 crystallisation Methods 0.000 description 7
- 230000008025 crystallization Effects 0.000 description 6
- FNYYDRRCUPHASE-WXAMSNGASA-N 4-[[5-[5-[(3as,4s,6ar)-2-oxo-1,3,3a,4,6,6a-hexahydrothieno[3,4-d]imidazol-4-yl]pentanoylamino]-1-carboxypentyl]carbamoyl]benzenediazonium;chloride Chemical compound [Cl-].C([C@H]1[C@H]2NC(=O)N[C@H]2CS1)CCCC(=O)NCCCCC(C(=O)O)NC(=O)C1=CC=C([N+]#N)C=C1 FNYYDRRCUPHASE-WXAMSNGASA-N 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- ZXAZUPMSJILYFO-UHFFFAOYSA-N [Br-].CCCC.C[NH+]1CCCC1 Chemical compound [Br-].CCCC.C[NH+]1CCCC1 ZXAZUPMSJILYFO-UHFFFAOYSA-N 0.000 description 4
- 239000006229 carbon black Substances 0.000 description 4
- 238000004587 chromatography analysis Methods 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 150000005846 sugar alcohols Polymers 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 1
- JLDSOYXADOWAKB-UHFFFAOYSA-N aluminium nitrate Inorganic materials [Al+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O JLDSOYXADOWAKB-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- -1 polytetrafluoroethylene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000006057 reforming reaction Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000005287 template synthesis Methods 0.000 description 1
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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
- C01B39/46—Other types characterised by their X-ray diffraction pattern and their defined composition
- C01B39/48—Other types characterised by their X-ray diffraction pattern and their defined composition using at least one organic template directing agent
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- 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)
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
Abstract
本公开涉及一种合成TNU‑9分子筛的方法，该方法包括以下步骤：a、将1,4‑二溴丁烷、1‑甲基吡咯烷与溶剂混合，在15～90℃预反应0.5～96h，得到预反应产物，所述1,4‑二溴丁烷、1‑甲基吡咯烷与溶剂的摩尔比为1：(1.8～3)：(1～20)；b、将步骤a中得到的预反应产物、无机碱、铝源、硅源和水混合，得到待晶化混合物，将所述待晶化混合物进行水热晶化处理，回收固体产物。本公开的方法省去了常规合成TNU‑9分子筛模板剂所必经的高成本分离、提纯等繁琐过程，避免了大量的时间消耗、能耗和物耗，降低成本效果明显。
The present disclosure relates to a method for synthesizing TNU-9 molecular sieve. The method includes the following steps: a. Mixing 1,4-dibromobutane and 1-methylpyrrolidine with a solvent, and pre-reacting at 15-90° C. for 0.5- 96h, the pre-reaction product was obtained, and the molar ratio of the 1,4-dibromobutane, 1-methylpyrrolidine and the solvent was 1:(1.8～3):(1～20); b. The obtained pre-reaction product, inorganic base, aluminum source, silicon source and water are mixed to obtain a mixture to be crystallized, and the mixture to be crystallized is subjected to hydrothermal crystallization to recover a solid product. The method of the present disclosure saves the complicated processes such as high-cost separation and purification that are necessary for the conventional synthesis of TNU-9 molecular sieve template agents, avoids a large amount of time consumption, energy consumption and material consumption, and has obvious effect of reducing cost.
Description
Technical Field
The present disclosure relates to a method for synthesizing a TNU-9 molecular sieve.
Background
TNU-9 is a novel molecular sieve with a three-dimensional ten-membered ring cross structure synthesized by Hong et al in 2007. TNU-9 has two sets of ten-membered ring channels (0.52X 0.6 and 0.51X 0.55 nm). The two sets of ten-membered ring channels are communicated with each other at the narrow distance through the other set of ten-membered ring channels (0.54 multiplied by 0.55nm), and a larger cage structure is also contained in the TNU-9 channels. TNU-9 molecular sieves have very good hydrothermal stability and have shown good activity and shape selectivity in certain reactions, such as: in the toluene disproportionation reaction, TNU-9 shows higher initial activity, and TNU-9 also shows certain shape selectivity from the aspect of product distribution; TNU-9 also shows higher catalytic activity and selectivity in the m-xylene reforming reaction. The TNU-9 has excellent physical and chemical properties, so that the TNU-9 can be widely applied to the field of petrochemical industry.
At present, the cost of the method for synthesizing the TNU-9 molecular sieve is high, and the wide application of the TNU-9 molecular sieve is restricted. Among them, the high cost of the bis-quaternary ammonium salt template (1,4-MPB) for synthesizing the TNU-9 molecular sieve is one of the main reasons.
The method for synthesizing the bis-quaternary ammonium salt template 1, 4-bis (N-methylpyrrolidine) butane bromide salt (1,4-MPB) generally needs to react two raw materials, namely 1-methylpyrrolidine (1-MP) and 1,4-dibromobutane (1,4-DBB) in a proper solvent according to a certain proportion, a crystallization method and a repeated recrystallization method are adopted to obtain the purer 1,4-MPB, and in the processes of crystallization and repeated recrystallization, the complex operations of freezing, filtering, washing with an organic reagent, drying, dissolving with a proper organic solvent, precipitating with a proper organic solvent, filtering, washing, drying and the like are needed, so that a large amount of time is consumed, and a large amount of energy and material consumption is generated.
In order to avoid the above-mentioned disadvantages of the synthesis of the templating agent, Hong S B reported in Journal of the American Chemical Society,2007,129:10870-10885 not only the synthesis of TNU-9 molecular sieves using the organic templating agent 1,4-MPB, but also the synthesis of TNU-9 molecular sieves using precursors of the synthetic templating agents (1-MP) and (1,4-DBB) as the organic templating agents directly instead of the organic templating agent 1, 4-MPB. However, in the strongly alkaline environment for synthesizing molecular sieves and in the whole reaction mixture system, the raw materials for synthesizing the template agent inevitably undergo side reactions or incomplete reactions, thereby causing ineffective consumption and waste of reaction raw materials and causing undesirable results.
Disclosure of Invention
The purpose of the present disclosure is to provide a low-cost method for synthesizing TNU-9 molecular sieve.
In order to achieve the above object, the present disclosure provides a method for synthesizing a TNU-9 molecular sieve, the method comprising the steps of:
a. mixing 1,4-dibromobutane and 1-methylpyrrolidine with a solvent, and carrying out pre-reaction for 0.5-96 h at 15-90 ℃ to obtain a pre-reaction product, wherein the molar ratio of the 1,4-dibromobutane to the 1-methylpyrrolidine to the solvent is 1: (1.8-3): (1-20);
b. and c, mixing the pre-reaction product obtained in the step a, inorganic alkali, an aluminum source, a silicon source and water to obtain a mixture to be crystallized, carrying out hydrothermal crystallization treatment on the mixture to be crystallized, and recovering a solid product.
Alternatively, in step a, the molar ratio of the 1,4-dibromobutane, 1-methylpyrrolidine and solvent is 1: (1.9-2.5): (2-18).
Optionally, in step a, the pre-reaction conditions are: the temperature is 15-60 ℃, and the time is 1-48 h.
Optionally, in the step a, the solvent is at least one selected from water, monohydric alcohols of C1-C6, ethers of C4-C6, ketones of C3-C6, polyhydric alcohols of C2-C4 and esters of C3-C6.
Optionally, in step b, the molar composition of the mixture to be crystallized is SiO2：Al2O3：M2O：R：H2O100: (0.5-10): (15-50): (8-20): (800-5000), wherein M2O is an alkali metal oxide, R is the pre-reaction product, and the number of moles of R is calculated by the number of moles of the 1, 4-dibromobutane.
Optionally, in step b, the inorganic base is at least one selected from the group consisting of sodium hydroxide, potassium hydroxide, sodium oxide, potassium oxide, sodium carbonate and potassium carbonate.
Optionally, in step b, the aluminum source is at least one selected from sodium metaaluminate, aluminum nitrate, aluminum sulfate, aluminum isopropoxide and aluminum acetate.
Optionally, in step b, the silicon source is at least one selected from silica gel, silica sol, silica white and ethyl orthosilicate.
Optionally, in step b, the conditions of the hydrothermal crystallization treatment are as follows: the temperature is 140-170 ℃ and the time is 7-14 days.
Optionally, the method further comprises: and after the solid product is recovered, washing, filtering and drying.
According to the technical scheme, the TNU-9 molecular sieve is synthesized by pre-reacting raw materials for synthesizing the template agent for a period of time, then mixing the template agent with other raw materials for synthesizing the molecular sieve according to a certain proportion and carrying out hydrothermal crystallization. The method disclosed by the invention omits the complicated processes of high-cost separation, purification and the like which are necessary for conventionally synthesizing the TNU-9 molecular sieve template agent, avoids a large amount of time consumption, energy consumption and material consumption, and has obvious cost reduction effect; in addition, the defects of incomplete reaction of raw materials and recycling of the raw materials caused by direct mixing and crystallization of the raw materials for synthesizing the template agent and other raw materials for synthesizing the molecular sieve in the prior art are overcome, and waste and ineffective consumption of the reaction raw materials caused by the incomplete reaction are avoided. The TNU-9 molecular sieve synthesized by the method disclosed by the invention has higher crystallinity.
Additional features and advantages of the disclosure will be set forth in the detailed description which follows.
Drawings
The accompanying drawings, which are included to provide a further understanding of the disclosure and are incorporated in and constitute a part of this specification, illustrate embodiments of the disclosure and together with the description serve to explain the disclosure without limiting the disclosure. In the drawings:
FIG. 1 is an X-ray diffraction pattern of the TNU-9 molecular sieve synthesized in example 1.
Detailed Description
The following detailed description of specific embodiments of the present disclosure is provided in connection with the accompanying drawings. It should be understood that the detailed description and specific examples, while indicating the present disclosure, are given by way of illustration and explanation only, not limitation.
The present disclosure provides a method for synthesizing a TNU-9 molecular sieve, the method comprising the steps of:
a. mixing 1,4-dibromobutane and 1-methylpyrrolidine with a solvent, and carrying out pre-reaction for 0.5-96 h at 15-90 ℃ to obtain a pre-reaction product, wherein the molar ratio of the 1,4-dibromobutane to the 1-methylpyrrolidine to the solvent is 1: (1.8-3): (1-20);
b. and c, mixing the pre-reaction product obtained in the step a, inorganic alkali, an aluminum source, a silicon source and water to obtain a mixture to be crystallized, carrying out hydrothermal crystallization treatment on the mixture to be crystallized, and recovering a solid product.
The TNU-9 molecular sieve is synthesized through pre-reaction of template synthesizing material for some time, mixing the template synthesizing material with other molecular sieve synthesizing material in certain proportion and hydrothermal crystallization. The method disclosed by the invention omits the complicated processes of high-cost separation, purification and the like which are necessary for conventionally synthesizing the TNU-9 molecular sieve template agent, avoids a large amount of time consumption, energy consumption and material consumption, and has obvious cost reduction effect; in addition, the defects of incomplete reaction of raw materials and recycling of the raw materials caused by direct mixing and crystallization of the raw materials for synthesizing the template agent and other raw materials for synthesizing the molecular sieve in the prior art are overcome, and waste and ineffective consumption of the reaction raw materials caused by the incomplete reaction are avoided. The TNU-9 molecular sieve synthesized by the method disclosed by the invention has higher crystallinity.
According to the disclosure, the English name of the 1,4-Dibromobutane is 1,4-Dibromobutane, the CAS number is 110-52-1, and the structural formula is as follows:
according to the present disclosure, the English name of the 1-Methylpyrrolidine is 1-Methylpyrrolidine, the CAS number is 120-94-5, and the structural formula is:
according to the present disclosure, in step a, the molar ratio of the 1,4-dibromobutane, 1-methylpyrrolidine to solvent is preferably 1: (1.9-2.5): (2-18), more preferably 1: (2-2.3): (2-14).
According to the present disclosure, in the step a, the mixing manner of the 1,4-dibromobutane and the 1-methylpyrrolidine and the solvent can be conventional in the art, and preferably, the 1-methylpyrrolidine and the solvent can be mixed first, and then the 1,4-dibromobutane is dropwise added into the obtained mixed solution, wherein the dropwise adding speed can be 1-60 drops/second. The pre-reaction can be carried out in a closed reaction kettle or a reaction kettle with a reflux device. The pre-reaction conditions may preferably be: the temperature is 15-60 ℃, and the time is 1-48 h. The mixing and the pre-reaction may be carried out under stirring in order to obtain the desired effect.
According to the present disclosure, in step a, the solvent may be a common organic solvent and water as long as it is compatible with 1,4-dibromobutane and/or 1-methylpyrrolidine, and for example, the solvent may be at least one selected from water, monohydric alcohols of C1 to C6, ethers of C4 to C6, ketones of C3 to C6, polyhydric alcohols of C2 to C4, and esters of C3 to C6. Preferably, the solvent is at least one selected from water, monohydric alcohols of C1-C4, ethers of C4-C5, ketones of C3-C4, polyhydric alcohols of C2-C3 and esters of C3-C4; specifically, the solvent may be water, methanol, ethanol, diethyl ether, acetone, or the like.
According to the present disclosure, in step b, the pre-reaction product, the inorganic base, the aluminum source, the silicon source and the water may be mixed in a conventional manner in the art, and preferably, the pre-reaction product, the inorganic base and the aluminum source may be dissolved in water to obtain a mixed solution; and then under the condition of stirring, contacting the mixed solution with a silicon source to obtain a mixture to be crystallized. The molar composition of the mixture to be crystallized may be SiO2：Al2O3：M2O：R：H2O100: (0.5-10): (15-50): (8-20): (800-5000), preferably 100: (0.8-8): (20-40): (8-15): (1000 to 4000), wherein M2O is an alkali metal oxide, R is the pre-reaction product, and the number of moles of R is calculated by the number of moles of the 1, 4-dibromobutane.
According to the present disclosure, in step b, the inorganic base, the aluminum source and the silicon source may be conventional species used for synthesizing TNU-9 molecular sieve. For example, the inorganic base may be at least one selected from the group consisting of sodium hydroxide, potassium hydroxide, sodium oxide, potassium oxide, sodium carbonate, and potassium carbonate. The aluminum source may be at least one selected from the group consisting of sodium metaaluminate, aluminum nitrate, aluminum sulfate, aluminum isopropoxide, and aluminum acetate. The silicon source can be at least one selected from silica gel, silica sol, white carbon black and tetraethoxysilane.
According to the disclosure, in step b, the conditions of the hydrothermal crystallization treatment may be: the temperature is 140-170 ℃ and the time is 7-14 days. In order to obtain the desired effect, the hydrothermal crystallization may be performed under stirring.
According to the present disclosure, the method may further comprise: and after the solid product is recovered, washing, filtering and drying. Wherein the washing, filtering and drying are conventional steps for synthesizing the molecular sieve, and the conditions thereof are not particularly limited by the present disclosure. For example, the drying conditions may be: the temperature is 80-120 ℃, and the time is 8-24 h.
The present disclosure is further illustrated by the following examples, but is not limited thereto.
The relative concept and calculation of "relative crystallinity" in the examples and comparative examples is: the sum of the peak areas of the molecular sieve product Z0 synthesized in the comparative example 1 in the range of 21.0-27.5 degrees in the 2 theta interval of an XRD spectrogram is taken as a reference, and the sum is 100 percent; the ratio (in percentage) of the sum of peak areas in the XRD spectrum in the interval of 21.0 to 27.5 ° in 2 θ to the sum of peak areas in the XRD spectrum of Z0 for the products synthesized in the following examples and comparative examples was the relative crystallinity value (r.c.%) of the corresponding products.
In examples and comparative examples, XRD analysis was performed using a Japanese physical D/MAX-IIIA type diffractometer under the following test conditions: cu target, Ka radiation, Ni filter, tube voltage 35kV, tube current 35mA, and scanning range 2 theta 4-55 deg.
In the examples and comparative examples, the specifications and sources of the various reagents used are as follows:
NaOH、Al(NO3)39H2o, absolute ethyl alcohol, methanol, acetone and ether which are all analytically pure and produced in Beijing chemical plants;
1, 4-bis (N-methylpyrrolidine) butane bromide salt (1,4-MPB) aqueous solution with the solid content of 58 weight percent is produced by Guangzhou Daojian refined factory;
1-methylpyrrolidine (1-MP) >98.0 wt%, Tokyo Kasei Kogyo;
1,4-dibromobutane (1,4-DBB) >98.0 wt%, Tokyo chemical industry Co., Ltd;
white carbon black, SiO2Content 97% by weight, Nissan Xinglong Co;
in the examples and comparative examples, the cost estimation method for synthesizing the molecular sieve was: the sum of the prices of all the raw materials for synthesizing the molecular sieve to the weight ratio of the obtained product.
Comparative example 1
This comparative example illustrates the Synthesis of a TNU-9 molecular sieve disclosed in the literature Synthesis, crystalline structure, chromatography, and catalytic properties of TNU-9.Journal of the American Chemical Society,2007,129: 10870-:
9.98g of 1, 4-bis (N-methylpyrrolidine) butane bromide (1,4-MPB) in water was mixed with 2.92g of NaOH, 1.5g of Al (NO)3)3·9H2Dissolving O into a proper amount of deionized water, uniformly mixing, adding 6.19g of white carbon black under the stirring condition to prepare a milky colloidal mixture to be crystallized, wherein the molar composition of the mixture is 4.5(1, 4-MPB): 11Na2O：0.6Al2O3：30SiO2：1200H2And O. The obtained solution was transferred to a crystallization kettle with a polytetrafluoroethylene inner liner of 100ml, and hydrothermal crystallization was carried out for 14 days at 160 ℃ with a rotation speed of 100 rpm. And then stopping the crystallization reaction, washing and filtering the product, and drying the product at the temperature of 80 ℃ for 12 hours to obtain the molecular sieve raw powder Z0.
The XRD measurement of molecular sieve raw powder Z0 was compared with the XRD spectrum of a TNU-9 molecular sieve disclosed in the literature Synthesis, crystalline structure, chromatography, and catalytic properties of TNU-9.Journal of the American Chemical Society,2007,129: 10870-. The relative crystallinity of molecular sieve raw powder Z0 was set to 100% and the synthesis cost was as shown in Table 1.
Comparative example 2
This comparative example is used to illustrate a method for directly synthesizing TNU-9 molecular sieve using precursors for template synthesis, 1-methylpyrrolidine (1-MP) and 1,4-dibromobutane (1,4-DBB), instead of organic template, 1, 4-MPB.
TNU-9 molecular sieves were synthesized according to the procedure of comparative example 1, except that 3.91g of 1-methylpyrrolidine (1-MP) and 3.305g of 1,4-dibromobutane (1,4-DBB) were used instead of 1, 4-bis (N-methylpyrrolidine) butane bromide salt (1,4-MPB), and the molar ratio of 1-methylpyrrolidine to 1,4-dibromobutane was 3: 1. The molecular sieve raw powder Z1 is obtained by synthesis.
XRD testing was performed on the molecular sieve raw powder Z1, and the results were compared with those of the XRD spectrum of TNU-9 molecular sieve disclosed in the literature Synthesis, crystalline structure, chromatography, and catalytic properties of TNU-9.Journal of the American Chemical Society,2007,129:10870-10885, and Z1 was determined to be TNU-9 molecular sieve, and the relative crystallinity and Synthesis cost thereof were calculated and listed in Table 1.
Examples 1-7 are intended to illustrate the process of synthesizing TNU-9 molecular sieves of the present disclosure.
Example 1
29.32g of 1-methylpyrrolidine and 36mL of absolute ethanol are mixed under stirring, 33.05g of 1,4-dibromobutane is dropwise added into the mixed solution at the speed of 5 drops/second, and pre-reaction is carried out for 8 hours at 50 ℃ to obtain a pre-reaction product A1. The molar ratio of the 1,4-dibromobutane to the 1-methylpyrrolidine to the solvent ethanol is 1: 2.25: 4.12.
the pre-reaction product A1, 15g Al (NO)3)3·9H2Dissolving O and 29.2g of NaOH solution in a proper amount of deionized water, uniformly mixing, slowly adding 61.9g of white carbon black under the condition of stirring to prepare a milky white colloidal mixture to be crystallized, wherein the molar composition of the milky white colloidal mixture to be crystallized is SiO2：Al2O3：Na2O：A1：H2O100: 2: 36.7: 15: 4000, continuously stirring for 1h, transferring to a 1L high-pressure reaction kettle with mechanical stirring, stirring at 160 ℃ for hydrothermal crystallization for 14 days, stopping the crystallization reaction, washing and filtering the product, and drying at 80 ℃ for 12h to obtain the molecular sieve raw powder B1.
The molecular sieve raw powder B1 is subjected to XRD test, and the spectrum is shown in figure 1. The XRD pattern obtained was compared with that of TNU-9 molecular sieves disclosed in the literature Synthesis, crystalline structure, chromatography, and catalytic properties of TNU-9.Journal of the American Chemical Society,2007,129:10870-10885, to confirm that B1 is a TNU-9 molecular sieve, the relative crystallinity and the Synthesis cost of which are calculated are shown in Table 1.
Example 2
TNU-9 molecular sieve was synthesized according to the procedure of example 1, except that 29.32g of 1-methylpyrrolidine and 43mL of diethyl ether were mixed under stirring, and 33.05g of 1,4-dibromobutane was added dropwise to the above mixture at a rate of 10 drops/sec, and pre-reacted at 35 ℃ for 16 hours to obtain a pre-reaction product A2. The molar ratio of the 1,4-dibromobutane to the 1-methylpyrrolidine to the solvent diethyl ether is 1: 2.0: 2.76. the pre-reaction product A2 was used in place of A1 to obtain molecular sieve powder B2, which had an XRD spectrum identical to that of example 1 and whose relative crystallinity and synthesis cost were calculated as shown in Table 1.
Example 3
TNU-9 molecular sieve was synthesized according to example 1, except that 27.37g of 1-methylpyrrolidine was mixed with 35mL of deionized water under stirring, and 33.05g of 1,4-dibromobutane was added dropwise to the above mixture and pre-reacted at 60 ℃ for 48 hours to obtain pre-reaction product A3. The molar ratio of the 1,4-dibromobutane to the 1-methylpyrrolidine to the solvent water is 1: 2.1: 12.96. the pre-reaction product A3 was used in place of A1 to obtain molecular sieve powder B3, which had an XRD spectrum identical to that of example 1 and whose relative crystallinity and synthesis cost were calculated as shown in Table 1.
Example 4
TNU-9 molecular sieve was synthesized according to the procedure of example 1, except that 32.58g of 1-methylpyrrolidine was mixed with 160mL of methanol under stirring, and 33.05g of 1,4-dibromobutane was added dropwise to the above mixture at a rate of 30 drops/sec, and pre-reacted at 50 ℃ for 24 hours to obtain a pre-reaction product A4. The molar ratio of the 1,4-dibromobutane to the 1-methylpyrrolidine to the solvent methanol is 1: 2.5: 14.5 replacement of A1 by the pre-reaction product A4 gave molecular sieve powder B4 having an XRD pattern in accordance with example 1, the relative crystallinity and synthesis cost of which are calculated and shown in Table 1.
Example 5
TNU-9 molecular sieve was synthesized according to the procedure of example 1, except that 24.76g of 1-methylpyrrolidine was mixed with 155mL of acetone under stirring, and 33.05g of 1,4-dibromobutane was added dropwise to the mixture at a rate of 20 drops/sec, and pre-reacted at 40 ℃ for 4 hours to obtain a pre-reaction product A6. The molar ratio of the 1,4-dibromobutane to the 1-methylpyrrolidine to the solvent acetone is 1: 1.9: 14.1. the pre-reaction product A5 was used in place of A1 to obtain molecular sieve powder B5, which had an XRD spectrum identical to that of example 1 and whose relative crystallinity and synthesis cost were calculated as shown in Table 1.
Example 6
TNU-9 molecular sieve was synthesized by the method of example 1 except that a mixture of 160mL of ethanol and 33.05g of 1,4-dibromobutane was added dropwise to 33.89g of 1-methylpyrrolidine at a rate of 40 drops/sec under stirring, and pre-reacted at 50 ℃ for 10 hours to obtain a pre-reaction product A6. The molar ratio of the 1,4-dibromobutane to the 1-methylpyrrolidine to the solvent ethanol is 1: 2.6: 18.32. the pre-reaction product A6 was used in place of A1 to obtain molecular sieve powder B5, which had an XRD spectrum identical to that of example 1 and whose relative crystallinity and synthesis cost were calculated as shown in Table 1.
Example 7
TNU-9 molecular sieve was synthesized according to the procedure of example 1, except that 16mL of a mixture of ethanol and 33.05g of 1,4-dibromobutane was added dropwise to 23.46g of 1-methylpyrrolidine at a rate of 3 drops/sec under stirring, and pre-reacted at 75 ℃ for 60 hours to obtain a pre-reaction product A7. The molar ratio of the 1,4-dibromobutane to the 1-methylpyrrolidine to the solvent ethanol is 1: 1.8: 1.83. the pre-reaction product A7 was used in place of A1 to obtain molecular sieve powder B7, which had an XRD spectrum identical to that of example 1 and whose relative crystallinity and synthesis cost were calculated as shown in Table 1.
TABLE 1
As can be seen from Table 1, the method disclosed by the invention can obviously reduce the synthesis cost of the TNU-9 molecular sieve, and the prepared TNU-9 molecular sieve has higher relative crystallinity.
The preferred embodiments of the present disclosure are described in detail with reference to the accompanying drawings, however, the present disclosure is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present disclosure within the technical idea of the present disclosure, and these simple modifications all belong to the protection scope of the present disclosure.
It should be noted that, in the foregoing embodiments, various features described in the above embodiments may be combined in any suitable manner, and in order to avoid unnecessary repetition, various combinations that are possible in the present disclosure are not described again.
In addition, any combination of various embodiments of the present disclosure may be made, and the same should be considered as the disclosure of the present disclosure, as long as it does not depart from the spirit of the present disclosure.
Claims (10)
1. A method for synthesizing a TNU-9 molecular sieve, comprising the steps of:
a. mixing 1,4-dibromobutane and 1-methylpyrrolidine with a solvent, and carrying out pre-reaction for 0.5-96 h at 15-90 ℃ to obtain a pre-reaction product, wherein the molar ratio of the 1,4-dibromobutane to the 1-methylpyrrolidine to the solvent is 1: (1.8-3): (1-20);
b. and c, mixing the pre-reaction product obtained in the step a, inorganic alkali, an aluminum source, a silicon source and water to obtain a mixture to be crystallized, carrying out hydrothermal crystallization treatment on the mixture to be crystallized, and recovering a solid product.
2. The process of claim 1, wherein in step a, the molar ratio of 1,4-dibromobutane, 1-methylpyrrolidine to solvent is 1: (1.9-2.5): (2-18).
3. The method of claim 1, wherein in step a, the pre-reaction conditions are: the temperature is 15-60 ℃, and the time is 1-48 h.
4. The method according to claim 1, wherein in the step a, the solvent is at least one selected from the group consisting of water, monohydric alcohols of C1-C6, ethers of C4-C6, ketones of C3-C6, polyols of C2-C4 and esters of C3-C6.
5. The process according to claim 1, wherein in step b, the molar composition of the mixture to be crystallized is SiO2：Al2O3：M2O：R：H2O100: (0.5-10): (15-50): (8-20): (800-5000), wherein M2O is an alkali metal oxide, R is the pre-reaction product, and the number of moles of R is calculated by the number of moles of the 1, 4-dibromobutane.
6. The method according to claim 1, wherein in step b, the inorganic base is at least one selected from the group consisting of sodium hydroxide, potassium hydroxide, sodium oxide, potassium oxide, sodium carbonate and potassium carbonate.
7. The process of claim 1 wherein in step b, the aluminum source is at least one selected from the group consisting of sodium metaaluminate, aluminum nitrate, aluminum sulfate, aluminum isopropoxide, and aluminum acetate.
8. The method according to claim 1, wherein in step b, the silicon source is at least one selected from the group consisting of silica gel, silica sol, silica white and tetraethoxysilane.
9. The method according to claim 1, wherein in step b, the conditions of the hydrothermal crystallization treatment are as follows: the temperature is 140-170 ℃ and the time is 7-14 days.
10. The method of claim 1, wherein the method further comprises: and after the solid product is recovered, washing, filtering and drying.
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