CN110844918B - 亚硝酸甲酯羰基化合成碳酸二甲酯用y分子筛及制备方法 - Google Patents
亚硝酸甲酯羰基化合成碳酸二甲酯用y分子筛及制备方法 Download PDFInfo
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- 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 68
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 67
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 title claims abstract description 27
- BLLFVUPNHCTMSV-UHFFFAOYSA-N methyl nitrite Chemical compound CON=O BLLFVUPNHCTMSV-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 230000006315 carbonylation Effects 0.000 title claims abstract description 13
- 238000005810 carbonylation reaction Methods 0.000 title claims abstract description 13
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 230000002194 synthesizing effect Effects 0.000 title claims description 4
- 239000003054 catalyst Substances 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 239000010936 titanium Substances 0.000 claims abstract description 18
- 238000002425 crystallisation Methods 0.000 claims abstract description 15
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 15
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical group [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 12
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 12
- 230000008025 crystallization Effects 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 8
- 239000012452 mother liquor Substances 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 48
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 42
- 238000003756 stirring Methods 0.000 claims description 29
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 27
- 239000010703 silicon Substances 0.000 claims description 27
- 229910052710 silicon Inorganic materials 0.000 claims description 27
- 239000011541 reaction mixture Substances 0.000 claims description 20
- 239000003795 chemical substances by application Substances 0.000 claims description 19
- 229910052782 aluminium Inorganic materials 0.000 claims description 18
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 16
- 239000011734 sodium Substances 0.000 claims description 14
- 229910052698 phosphorus Inorganic materials 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 11
- -1 polytetrafluoroethylene Polymers 0.000 claims description 10
- 239000011574 phosphorus Substances 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 9
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 8
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 4
- 230000032683 aging Effects 0.000 claims description 4
- 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 4
- 239000000463 material Substances 0.000 claims description 4
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 4
- GROMGGTZECPEKN-UHFFFAOYSA-N sodium metatitanate Chemical compound [Na+].[Na+].[O-][Ti](=O)O[Ti](=O)O[Ti]([O-])=O GROMGGTZECPEKN-UHFFFAOYSA-N 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 3
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 3
- 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 2
- 239000005995 Aluminium silicate Substances 0.000 claims description 2
- 239000004254 Ammonium phosphate Substances 0.000 claims description 2
- 239000004115 Sodium Silicate Substances 0.000 claims description 2
- 235000012211 aluminium silicate Nutrition 0.000 claims description 2
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 claims description 2
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 2
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 2
- 238000011068 loading method Methods 0.000 claims description 2
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims description 2
- 235000019799 monosodium phosphate Nutrition 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 229910001388 sodium aluminate Inorganic materials 0.000 claims description 2
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 2
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 2
- 239000001488 sodium phosphate Substances 0.000 claims description 2
- 235000011008 sodium phosphates Nutrition 0.000 claims description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 2
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims 6
- 239000000243 solution Substances 0.000 claims 5
- 229910052681 coesite Inorganic materials 0.000 claims 4
- 229910052593 corundum Inorganic materials 0.000 claims 4
- 229910052906 cristobalite Inorganic materials 0.000 claims 4
- 239000000377 silicon dioxide Substances 0.000 claims 4
- 229910052682 stishovite Inorganic materials 0.000 claims 4
- 229910052905 tridymite Inorganic materials 0.000 claims 4
- 229910001845 yogo sapphire Inorganic materials 0.000 claims 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims 1
- 235000011114 ammonium hydroxide Nutrition 0.000 claims 1
- 238000001035 drying Methods 0.000 claims 1
- 238000001914 filtration Methods 0.000 claims 1
- 238000002156 mixing Methods 0.000 claims 1
- 239000010413 mother solution Substances 0.000 claims 1
- 238000005406 washing Methods 0.000 claims 1
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 3
- 230000001105 regulatory effect Effects 0.000 abstract description 2
- 230000003197 catalytic effect Effects 0.000 abstract 1
- 150000002148 esters Chemical class 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 8
- 229910002091 carbon monoxide Inorganic materials 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 238000001354 calcination Methods 0.000 description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 5
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 4
- 229910004298 SiO 2 Inorganic materials 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- NKDDWNXOKDWJAK-UHFFFAOYSA-N dimethoxymethane Chemical compound COCOC NKDDWNXOKDWJAK-UHFFFAOYSA-N 0.000 description 4
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 4
- LOMVENUNSWAXEN-UHFFFAOYSA-N Methyl oxalate Chemical compound COC(=O)C(=O)OC LOMVENUNSWAXEN-UHFFFAOYSA-N 0.000 description 3
- 229910021536 Zeolite Inorganic materials 0.000 description 3
- 238000004364 calculation method Methods 0.000 description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000010457 zeolite Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 239000002000 Electrolyte additive Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- 208000034804 Product quality issues Diseases 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- JFBZPFYRPYOZCQ-UHFFFAOYSA-N [Li].[Al] Chemical compound [Li].[Al] JFBZPFYRPYOZCQ-UHFFFAOYSA-N 0.000 description 1
- CQBLUJRVOKGWCF-UHFFFAOYSA-N [O].[AlH3] Chemical compound [O].[AlH3] CQBLUJRVOKGWCF-UHFFFAOYSA-N 0.000 description 1
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- COTNUBDHGSIOTA-UHFFFAOYSA-N meoh methanol Chemical compound OC.OC COTNUBDHGSIOTA-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000005832 oxidative carbonylation reaction Methods 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 229910052665 sodalite Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
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- 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
- C01B39/20—Faujasite type, e.g. type X or Y
- C01B39/24—Type Y
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- B01J29/00—Catalysts comprising molecular sieves
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- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
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- B01J29/10—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing iron group metals, noble metals or copper
- B01J29/12—Noble metals
- B01J29/126—Y-type faujasite
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Abstract
本发明公开了一种亚硝酸甲酯羰基化合成碳酸二甲酯用Y分子筛及其制备方法，该Y分子筛采用水热法和微波辅助晶化法合成，通过导向剂的制备以及钛源、磷源对母液组成的调控，通过微波预晶化处理后再进行晶化反应，得到Y分子筛。该Y分子筛的特征是在保持Y分子筛骨架结构的基础上，将钛、磷杂原子掺杂到骨架中去；将该分子筛负载活性组分后，用作亚硝酸甲酯羰基化合成碳酸二甲酯的无氯体系催化剂；表现出更优的催化活性。
Description
技术领域
本发明属于分子筛制备及应用领域，具体涉及一种亚硝酸甲酯羰基化合成碳酸二甲酯用催化剂的载体--Y分子筛的合成。
背景技术
碳酸二甲酯(Dimethyl carbonate，DMC)是重要的绿色化学品，在医药、农药、溶剂、电解液添加剂等方面都有重要的应用。合成碳酸二甲酯的方法多种多样，包括尿素合成法、酯交换法、甲醇氧化羰基化法、亚硝酸甲酯羰基化法等。在煤化工项目中，煤制碳酸二甲酯受到广大研究工作者的青睐，其中关键的技术就是亚硝酸甲酯羰基化法所涉及的相关催化剂。
亚硝酸甲酯羰基化合成碳酸二甲酯所用催化剂主要包括两类，一类是以活性炭、锂铝尖晶石为载体的含氯体系催化剂，其活性和选择性较优，但是由于氯流失的问题，使得其稳定性较差；另一类是以Y分子筛为载体的无氯体系催化剂，其稳定性较优，但是在活性和选择性方面有所不足。考虑到含氯体系催化剂在未来应用方面存在的腐蚀设备以及对产品质量问题的影响，无氯体系催化剂更受推崇。如何有效提高无氯体系催化剂的活性和选择性是当前的研究重点。
Y分子筛是一种常见的硅铝分子筛，具有优良的结构规整性和热力学稳定性，在石油化工领域的应用十分广泛。Y分子筛以硅氧四面体和铝氧四面体为基础，通过共享顶点氧桥形成有序的骨架阴离子笼状结构，主要包括超笼、方钠石笼和六棱柱笼这几种，骨架负电荷由额外的阳离子来平衡。Y分子筛阴离子骨架结构的可调控性以及阳离子的可交换性是对Y分子筛进行优化设计的两个重要方向。合成分子筛通常采用水热法，将硅源、铝源、金属离子、碱、模板剂、水等原料在一定温度下进行陈化和晶化等操作，从而获得所需的分子筛类型。硅源、铝源、模板剂的种类，陈化、晶化温度，碱度等因素都对分子筛的合成有着重要的影响。
天津大学马新宾课题组报道了利用正硅酸四乙酯(TEOS)对Y分子筛进行处理明确了分子筛表面路易斯酸性对无氯体系催化剂Pd/Y性能的影响(DOI:10.1002/cctc.201300170)。在专利ZL201510559857.中，中国科学院福建物质结构研究所姚元根课题组通过对商用Y分子筛的预处理和金属助剂的添加一定程度上提高了无氯体系催化剂的活性。目前合成碳酸二甲酯所用的Y分子筛都是常见的商用Y分子筛，尚未有相关文章专利报道对Y分子筛进行骨架结构调整或者有新型的类分子筛载体被运用到碳酸二甲酯的合成当中。
发明内容
本发明目的是提供一种亚硝酸甲酯羰基化合成碳酸二甲酯用催化剂用Y分子筛及其制备方法。
本发明所提供的分子筛采用水热合成法和微波辅助晶化法来制备，具体制备步骤如下：
A.将铝源溶于去离子水中再加入碱性物质，完全溶解后，缓慢加入硅源溶液，持续搅拌5-20min，静置陈化8-48h，陈化温度为25-50℃，形成导向剂；
上述物料中所涉及的Na元素以Na2O计，Al元素以Al2O3计，Si元素以SiO2计；所述铝源、碱性物质、硅源和水的用量使得Na2O、Al2O3、SiO2、H2O的摩尔比例为10-20:1:8-24:180-480；
B、将硅源溶于水中制成硅源溶液，将铝源和碱溶于水中形成铝源溶液；将硅源溶液与铝源溶液混合形成凝胶母液；在25-80℃及搅拌条件下，向凝胶母液中添加钛源或磷源，再加入步骤A的导向剂，继续搅拌30-60min，制得凝胶反应混合物；
上述物料中所涉及的Na元素以Na2O计，Al元素以Al2O3计，Si元素以SiO2计,Ti元素和P元素以Ti、P计；所述凝胶反应混合物中铝源、碱性物质、硅源、钛源、磷源和水的用量使得Na2O、Al2O3、SiO2、Ti、P、H2O的摩尔比例为1-5:1:7-12:0-2:0-2:140-320；所述导向剂的用量占凝胶母液用量的10-30％；
步骤A和B中所述硅源为高岭土、硅溶胶、硅酸钠、正硅酸四乙酯中的一种或者多种；所述铝源为铝酸钠、硝酸铝、硫酸铝中的一种或者多种；所述钛源为钛酸钠、偏钛酸钠、钛酸四丁酯中的一中或者多种；所述磷源为磷酸钠、磷酸铵、磷酸二氢钠中的一种或者多种；所述碱性物质为氢氧化钠或氨水；
C、将步骤2所得凝胶反应混合物进行微波加热处理，微波时间为5-20min，使反应混合物预晶化；
D、将步骤3得到的混合物转移到聚四氟乙烯水热釜中进行晶化反应，反应温度为80-120℃，反应时间为8-24h；过滤、洗涤、干燥、焙烧，得到纳米Y分子筛原粉。
该Y分子筛的特征是在保持Y分子筛骨架结构的基础上，将钛、磷杂原子掺杂到骨架中去。用该分子筛负载活性组分后，具体方法见专利ZL201510559857.1，用作亚硝酸甲酯羰基化合成碳酸二甲酯反应催化剂，在一氧化碳转化率和基于MN的选择性方面比现有Y分子筛有显著的提高，碳酸二甲酯的时空收率也有提高。
图1、2、3为本发明合成的Y分子筛与商用Y分子筛(南开大学催化剂厂生产的Y分子筛)进行的结构对比表征。
由图1发现自主合成的分子筛与商用购买的Y分子筛的XRD峰基本一致，说明自主合成的分子筛在笼结构方面与商用购买的Y分子筛基本一致，而在20°附近和30°前后的衍射峰强度有明显的区别，说明自主合成的分子筛与商用购买的分子筛在骨架结构上有所区别。
由图2可以看出自主合成的Y分子筛具有更小的微孔结构。
在图3中三个分子筛在800-900cm-1波数范围的红外吸收峰差异，也表明了自主合成的Y分子筛与商用购买的分子筛在骨架结构上的差异。这些结构上的差异说明了钛、磷掺杂到Y分子筛骨架结构中去。
本发明的有益效果：本发明所提供的Y分子筛的制备方法中，主要是将钛源或磷源添加到母液中，使得钛源或者磷源能够进入Y分子筛骨架结构中去，分子筛骨架结构的变化进而影响了所负载的活性组分与分子筛载体骨架氧的相互作用力即活性组分的电子云密度。用该分子筛负载钯活性组分后，用于亚硝酸甲酯羰基化合成碳酸二甲酯过程，调控活性组分Pd的电子云密度能够有效调控反应物一氧化碳的活化，从而提高一氧化碳的转化率，提升目标产物碳酸二甲酯的时空收率。另外在本发明中采用微波辅助晶化法，通过微波的作用能够更加高效的合成所需的Y分子筛结构。
附图说明
图1为实施例1、实施例2与购买的Y分子筛XRD对比图
图2为实施例1、实施例2与购买的Y分子筛微孔分布对比图
图3为实施例1、实施例2与购买的Y分子筛红外对比图
具体实施方式
实施例1
1、在100ml烧杯中加入25ml水，依次加入1.6gNaAlO2和1.6gNaOH。同样在另一个100ml烧杯中加入25ml水，加入11.1gNaSiO3·5H2O。两个烧杯的水完全溶解后混合在一起搅拌10min，在室温下陈化24h，制成导向剂；
2、在250ml烧杯中加入30gNaSiO3·5H2O和100ml水,搅拌使其完全溶解得到硅源溶液；另取250ml烧杯加入5.5g NaAlO2、2.5gNaOH和100ml水，搅拌至完全溶解，加到硅源溶液中混合均匀；于50℃水浴锅中搅拌条件下加入1.2gNa4TiO4和5g步骤1的导向剂；继续搅拌30min，制得凝胶反应混合物。
将上述凝胶反应混合物装入反应釜中，置于微波装置中处理10min；再转移至聚四氟乙烯水热釜，放入烘箱中于100℃晶化10h，然后抽滤、洗涤、干燥、焙烧得到Y分子筛。
实施例2
1、在100ml烧杯中加入25ml水，依次加入1.6gNaAlO2和1.6gNaOH。同样在另一个100ml烧杯中加入25ml水，加入11.1gNaSiO3·5H2O。两个烧杯的水完全溶解后混合在一起搅拌10min，在室温下陈化24h，制成导向剂；
2、在250ml烧杯中加入30gNaSiO3·5H2O和100ml水，搅拌使其完全溶解得到硅源溶液；另取250ml烧杯加入5.5g NaAlO2、2.5gNaOH和100ml水，搅拌至完全溶解，加到硅源溶液中混合均匀；于50℃水浴锅中搅拌条件下加入1.5gNa3PO4和5g上述步骤1的导向剂，继续搅拌30min，制得凝胶反应混合物。
将上述凝胶反应混合物装入反应釜中，置于微波装置中处理10min，再转移至聚四氟乙烯水热釜，放入烘箱中于100℃晶化10h，然后抽滤、洗涤、干燥、焙烧得到Y分子筛。
实施例3
1、在100ml烧杯中加入25ml水，依次加入1.6gNaAlO2和1.6gNaOH。同样在另一个100ml烧杯中加入25ml水，加入11.1gNaSiO3·5H2O。两个烧杯的水完全溶解后混合在一起搅拌10min，在50℃水浴锅中陈化24h，制成导向剂；
2、在250ml烧杯中加入45gNaSiO3·5H2O和100ml水，搅拌使其完全溶解得到硅源溶液；另取250ml烧杯加入3.8g NaAlO2、5gNaOH和100ml水，搅拌至完全溶解，加到硅源溶液中混合均匀；于50℃水浴锅中搅拌条件下加入1.2gNa4TiO4和8g上述步骤1的导向剂，继续搅拌30min，制得凝胶反应混合物。
将上述凝胶反应混合物装入反应釜中，置于微波装置中处理15min，再转移至聚四氟乙烯水热釜，放入烘箱中于100℃晶化15h，然后抽滤、洗涤、干燥、焙烧得到Y分子筛。
实施例4
1、在100ml烧杯中加入25ml水，依次加入1.6gNaAlO2和1.6gNaOH。同样在另一个100ml烧杯中加入25ml水，加入11.1gNaSiO3·5H2O。两个烧杯的水完全溶解后混合在一起搅拌10min，在40℃水浴锅中陈化24h，制成导向剂；
2、在250ml烧杯中加入30gNaSiO3·5H2O和100ml水，搅拌使其完全溶解得到硅源溶液；另取250ml烧杯加入5.5g NaAlO2、3.75gNaOH和100ml水，搅拌至完全溶解，加到硅源溶液中混合均匀；于50℃水浴锅中搅拌条件下加入1.2gNa4TiO4、1.5gNa3PO4和5g上述步骤1的导向剂，继续搅拌30min，制得凝胶反应混合物。
将上述凝胶反应混合物装入反应釜中，置于微波装置中处理20min，再转移至聚四氟乙烯水热釜，放入烘箱中于100℃晶化20h，然后抽滤、洗涤、干燥、焙烧得到Y分子筛。
实施例5
1、在100ml烧杯中加入25ml水，依次加入1.6gNaAlO2和3.2gNaOH。同样在另一个100ml烧杯中加入25ml水，加入22.2g硅溶胶。两个烧杯的水完全溶解后混合在一起搅拌10min，在室温下陈化24h，制成导向剂；
2、在250ml烧杯中加入39g硅溶胶和100ml水，搅拌使其完全溶解得到硅源溶液；另取250ml烧杯加入2.8g NaAlO2、2.5gNaOH和100ml水，搅拌至完全溶解，加到硅源溶液中混合均匀；于50℃水浴锅中搅拌条件下加入1.2gNa4TiO4和10g上述步骤1的导向剂，继续搅拌30min，制得凝胶反应混合物。
将上述凝胶反应混合物装入反应釜中，置于微波装置中处理10min，再转移至聚四氟乙烯水热釜，放入烘箱中于120℃晶化8h，然后抽滤、洗涤、干燥、焙烧得到Y分子筛。
实施例6
1、在100ml烧杯中加入25ml水，依次加入2.1g硫酸铝和3.2gNaOH。同样在另一个100ml烧杯中加入25ml水，加入11.1gNaSiO3·5H2O。两个烧杯的水完全溶解后混合在一起搅拌10min，在室温下陈化24h，制成导向剂；
2、在250ml烧杯中加入30gNaSiO3·5H2O和100ml水，搅拌使其完全溶解得到硅源溶液；另取250ml烧杯加入5g硫酸铝、2.5gNaOH和100ml水，搅拌至完全溶解，加到硅源溶液中混合均匀；于50℃水浴锅中搅拌条件下加入5g钛酸四丁酯和10g上述步骤1的导向剂，继续搅拌30min，制得凝胶反应混合物。
将上述凝胶反应混合物装入反应釜中，置于微波装置中处理10min，再转移至聚四氟乙烯水热釜，放入烘箱中于100℃晶化12h，然后抽滤、洗涤、干燥、焙烧得到Y分子筛。
应用例
采用南开大学催化剂厂生产的Y分子筛作为对比分子筛样品，与实施例1、2制备的分子筛进行应用对比。
以上述三种样品为载体，采用离子交换法负载活性组分Pd、Cu等，制备亚硝酸甲酯羰基化合成碳酸二甲酯中的无氯体系催化剂，具体方法参考发明人已授权的专利ZL201510559857.1。
将三种催化剂分别装于连续流动的固定床反应器上进行活性评价，管式反应器长30cm，内径8mm，催化剂装填量为5ml。反应以一氧化碳和亚硝酸甲酯为原料气，氮气为稀释气，气体流量之比为N2:CO:CH3ONO＝5:1:4，体积空速为3600h-1，反应温度120℃，反应压力为常压。使用在线色谱对产物进行分析，其中用氢火焰离子化检测器(FID)检测有机产物的数据，有主产物碳酸二甲酯(DMC)，副产物草酸二甲酯(DMO)、甲酸甲酯(MF)、二甲氧基甲烷(DMM)和甲醇MeOH。用热导检测器(TCD)检测一氧化碳、氮气、一氧化氮和亚硝酸甲酯数据，结果见表1。
再由表1的数据计算一氧化碳转化率XCO、碳酸二甲酯的时空收率STY(g/l·h)、基于一氧化碳选择性SDMC/CO和基于亚硝酸甲酯选择性SDMC/MN。计算方法如下:
XCO＝([CO]in/[N2]in-[CO]out/[N2]out)/([CO]in/[N2]in)×100％
STY of DMC(g·L-1·h-1)＝XCO×SDMC/CO×GHSV of CO(h-1)×90.08g·mol-1/22.4L·mol-1
[N2]in，[N2]out，[CO]in，[CO]out表示N2和CO在反应器进出口的浓度。n(MeOH),n(MF),n(DMM),n(DMC),以及n(DMO)表示甲醇、甲酸甲酯、二甲氧基甲烷、碳酸二甲酯和草酸酯在产物中的摩尔数。计算结果见表2
表1、产品在色谱上的分析数据
表2、相应催化剂的活性计算结果
从表2可以看出，自主合成的Y分子筛在一氧化碳转化率和基于MN的选择性方面有着显著的提高，碳酸二甲酯的时空收率也相应得到提高。由此可见自主合成的Y分子筛在碳酸酯合成方面具有更好的应用价值。
Claims (2)
1.一种亚硝酸甲酯羰基化合成碳酸二甲酯用Y分子筛的制备方法，具体制备步骤如下：
A.将铝源溶于去离子水中再加入碱性物质，完全溶解后，缓慢加入硅源溶液，持续搅拌5-20min，静置陈化8-48h，陈化温度为25-50℃，形成导向剂；
上述物料中所涉及的Na元素以Na2O计，Al元素以Al2O3计，Si元素以SiO2计；所述碱性物质、铝源、硅源和水的用量使得Na2O、Al2O3、SiO2、H2O的摩尔比例为10-20:1:8-24:180-480；
B、将硅源溶于水中制成硅源溶液，将铝源和碱溶于水中形成铝源溶液；将硅源溶液与铝源溶液混合形成凝胶母液；在25-80℃及搅拌条件下，向凝胶母液中添加钛源或磷源，再加入步骤A的导向剂，继续搅拌30-60min，制得凝胶反应混合物；
上述物料中所涉及的Na元素以Na2O计，Al元素以Al2O3计，Si元素以SiO2计,Ti元素和P元素以Ti、P计；所述凝胶反应混合物中碱性物质、铝源、硅源、钛源、磷源和水的用量使得Na2O、Al2O3、SiO2、Ti、P、H2O的摩尔比例为1-5:1:7-12:0-2:0-2:140-320；所述导向剂的用量占凝胶母液用量的10-30％；
步骤A和B中所述硅源为高岭土、硅溶胶、硅酸钠、正硅酸四乙酯中的一种或者多种；所述铝源为铝酸钠、硝酸铝、硫酸铝中的一种或者多种；所述钛源为钛酸钠、偏钛酸钠、钛酸四丁酯中的一种或者多种；所述磷源为磷酸钠、磷酸铵、磷酸二氢钠中的一种或者多种；所述碱性物质为氢氧化钠或氨水；
C、将步骤B所得凝胶反应混合物进行微波加热处理，微波时间为5-20min，使反应混合物预晶化；
D、将步骤C得到的混合物转移到聚四氟乙烯水热釜中进行晶化反应，反应温度为80-120℃，反应时间为8-24h；过滤、洗涤、干燥、焙烧，得到纳米Y分子筛原粉。
2.一种根据权利要求1所述的方法制备的亚硝酸甲酯羰基化合成碳酸二甲酯用Y分子筛，该Y分子筛的特征是在保持Y分子筛骨架结构的基础上，将钛、磷杂原子掺杂到骨架中去；用该分子筛负载活性组分后，用作亚硝酸甲酯羰基化合成碳酸二甲酯反应催化剂。
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