CN104891527B - A method for synthesizing mordenite - Google Patents
A method for synthesizing mordenite Download PDFInfo
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- CN104891527B CN104891527B CN201510282947.0A CN201510282947A CN104891527B CN 104891527 B CN104891527 B CN 104891527B CN 201510282947 A CN201510282947 A CN 201510282947A CN 104891527 B CN104891527 B CN 104891527B
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- 238000000034 method Methods 0.000 title claims abstract description 23
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 13
- 229910052680 mordenite Inorganic materials 0.000 title description 54
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 41
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000000203 mixture Substances 0.000 claims abstract description 27
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 15
- 239000010703 silicon Substances 0.000 claims abstract description 12
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 12
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 9
- 150000007529 inorganic bases Chemical class 0.000 claims abstract description 7
- 239000000376 reactant Substances 0.000 claims abstract 6
- 125000001453 quaternary ammonium group Chemical group 0.000 claims abstract 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 36
- 239000002585 base Substances 0.000 claims description 34
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- 229910052782 aluminium Inorganic materials 0.000 claims description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 7
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 claims description 7
- 229910001388 sodium aluminate Inorganic materials 0.000 claims description 7
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 6
- 229910052783 alkali metal Inorganic materials 0.000 claims description 5
- 150000001340 alkali metals Chemical class 0.000 claims description 5
- 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 5
- 235000019353 potassium silicate Nutrition 0.000 claims description 5
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 2
- 229910052681 coesite Inorganic materials 0.000 claims 10
- 229910052906 cristobalite Inorganic materials 0.000 claims 10
- 229910052682 stishovite Inorganic materials 0.000 claims 10
- 229910052905 tridymite Inorganic materials 0.000 claims 10
- 239000004411 aluminium Substances 0.000 claims 2
- 229910052593 corundum Inorganic materials 0.000 claims 2
- 229910001845 yogo sapphire Inorganic materials 0.000 claims 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims 1
- 239000005864 Sulphur Substances 0.000 claims 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims 1
- 239000003292 glue Substances 0.000 claims 1
- 238000002360 preparation method Methods 0.000 abstract description 24
- 239000013078 crystal Substances 0.000 abstract description 18
- 230000015572 biosynthetic process Effects 0.000 abstract description 5
- 238000003786 synthesis reaction Methods 0.000 abstract description 5
- 238000006555 catalytic reaction Methods 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 abstract 4
- 229910004298 SiO 2 Inorganic materials 0.000 description 80
- 238000003756 stirring Methods 0.000 description 40
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 33
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 29
- 239000000243 solution Substances 0.000 description 27
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 26
- 239000011541 reaction mixture Substances 0.000 description 24
- 238000002441 X-ray diffraction Methods 0.000 description 23
- 239000000047 product Substances 0.000 description 22
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 20
- 239000008367 deionised water Substances 0.000 description 15
- 229910021641 deionized water Inorganic materials 0.000 description 15
- 239000011734 sodium Substances 0.000 description 13
- 238000002425 crystallisation Methods 0.000 description 12
- 230000008025 crystallization Effects 0.000 description 12
- -1 hydroxyldiamine Chemical compound 0.000 description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 10
- 238000012921 fluorescence analysis Methods 0.000 description 10
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 10
- 239000004810 polytetrafluoroethylene Substances 0.000 description 10
- 239000012265 solid product Substances 0.000 description 10
- 229910001220 stainless steel Inorganic materials 0.000 description 10
- 239000010935 stainless steel Substances 0.000 description 10
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 9
- 238000007689 inspection Methods 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 239000006229 carbon black Substances 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 6
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 6
- RDHPKYGYEGBMSE-UHFFFAOYSA-N bromoethane Chemical compound CCBr RDHPKYGYEGBMSE-UHFFFAOYSA-N 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 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 description 4
- 238000000921 elemental analysis Methods 0.000 description 4
- 238000002329 infrared spectrum Methods 0.000 description 4
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 4
- VFWRGKJLLYDFBY-UHFFFAOYSA-N silver;hydrate Chemical compound O.[Ag].[Ag] VFWRGKJLLYDFBY-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000004448 titration Methods 0.000 description 4
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 239000000499 gel Substances 0.000 description 3
- 238000005216 hydrothermal crystallization Methods 0.000 description 3
- KDSNLYIMUZNERS-UHFFFAOYSA-N 2-methylpropanamine Chemical compound CC(C)CN KDSNLYIMUZNERS-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- FQUYSHZXSKYCSY-UHFFFAOYSA-N 1,4-diazepane Chemical compound C1CNCCNC1 FQUYSHZXSKYCSY-UHFFFAOYSA-N 0.000 description 1
- XDIAMRVROCPPBK-UHFFFAOYSA-N 2,2-dimethylpropan-1-amine Chemical compound CC(C)(C)CN XDIAMRVROCPPBK-UHFFFAOYSA-N 0.000 description 1
- QIJIUJYANDSEKG-UHFFFAOYSA-N 2,4,4-trimethylpentan-2-amine Chemical compound CC(C)(C)CC(C)(C)N QIJIUJYANDSEKG-UHFFFAOYSA-N 0.000 description 1
- NRGGMCIBEHEAIL-UHFFFAOYSA-N 2-ethylpyridine Chemical compound CCC1=CC=CC=N1 NRGGMCIBEHEAIL-UHFFFAOYSA-N 0.000 description 1
- NJBCRXCAPCODGX-UHFFFAOYSA-N 2-methyl-n-(2-methylpropyl)propan-1-amine Chemical compound CC(C)CNCC(C)C NJBCRXCAPCODGX-UHFFFAOYSA-N 0.000 description 1
- CRKVBVASFXIHJV-UHFFFAOYSA-N 4,4-diethylpiperidine hydrobromide Chemical compound Br.CCC1(CC)CCNCC1 CRKVBVASFXIHJV-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- ZSIQJIWKELUFRJ-UHFFFAOYSA-N azepane Chemical compound C1CCCNCC1 ZSIQJIWKELUFRJ-UHFFFAOYSA-N 0.000 description 1
- QXNDZONIWRINJR-UHFFFAOYSA-N azocane Chemical compound C1CCCNCCC1 QXNDZONIWRINJR-UHFFFAOYSA-N 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- ZXJXZNDDNMQXFV-UHFFFAOYSA-M crystal violet Chemical compound [Cl-].C1=CC(N(C)C)=CC=C1[C+](C=1C=CC(=CC=1)N(C)C)C1=CC=C(N(C)C)C=C1 ZXJXZNDDNMQXFV-UHFFFAOYSA-M 0.000 description 1
- VXVVUHQULXCUPF-UHFFFAOYSA-N cycloheptanamine Chemical compound NC1CCCCCC1 VXVVUHQULXCUPF-UHFFFAOYSA-N 0.000 description 1
- SSJXIUAHEKJCMH-UHFFFAOYSA-N cyclohexane-1,2-diamine Chemical compound NC1CCCCC1N SSJXIUAHEKJCMH-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229940043279 diisopropylamine Drugs 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- ZZYXNRREDYWPLN-UHFFFAOYSA-N pyridine-2,3-diamine Chemical compound NC1=CC=CN=C1N ZZYXNRREDYWPLN-UHFFFAOYSA-N 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910001923 silver oxide Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- UEUYEWLWWIWPLC-UHFFFAOYSA-M sodium;2-[bis(2-hydroxyethyl)amino]ethanol;chloride Chemical compound [Na+].[Cl-].OCCN(CCO)CCO UEUYEWLWWIWPLC-UHFFFAOYSA-M 0.000 description 1
- DAJQHPDXTUVGOP-UHFFFAOYSA-M sodium;azane;chloride Chemical compound N.[Na+].[Cl-] DAJQHPDXTUVGOP-UHFFFAOYSA-M 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical class CC[N+](CC)(CC)CC CBXCPBUEXACCNR-UHFFFAOYSA-N 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
Description
技术领域technical field
本发明涉及催化材料合成领域，具体是一种以N,N,N',N'-四乙基哌嗪双季铵碱为结构导向剂的合成丝光沸石的方法。The invention relates to the field of synthesis of catalytic materials, in particular to a method for synthesizing mordenite using N,N,N',N'-tetraethylpiperazine bisquaternary ammonium base as a structure-directing agent.
背景技术Background technique
丝光沸石是一类高硅沸石，属于正交晶系结构，具有二维孔道结构，由孔口尺寸为0.67nm×0.70nm的十二元环主孔道和两个扭曲的八元环(0.34nm×0.48nm和0.26nm×0.57nm)孔道所构成。该沸石可被用作许多重要催化反应的催化剂，如加氢裂化、加氢异构、烷基化、重整、脱蜡，尤其是用作合成二甲胺的催化剂。Mordenite is a kind of high silica zeolite, which belongs to the orthorhombic crystal structure and has a two-dimensional channel structure, which consists of a twelve-membered ring main channel with a pore size of 0.67nm×0.70nm and two twisted eight-membered rings (0.34nm ×0.48nm and 0.26nm×0.57nm) channels. The zeolite can be used as a catalyst for many important catalytic reactions, such as hydrocracking, hydroisomerization, alkylation, reforming, dewaxing, especially as a catalyst for the synthesis of dimethylamine.
丝光沸石分天然和合成两类。天然丝光沸石纯度不够高，孔结构无法调节，人工合成的丝光沸石结构可调、催化性能优良，1948年，Barrer用碳酸钠为矿化剂，使混合硅酸凝胶与铝酸钠水溶液在265～295℃下水热晶化，首次合成出丝光沸石。目前主要是以硅酸钠或硅溶胶为硅源采用无胺水热方法合成丝光沸石，通常合成的丝光沸石硅铝比与天然丝光沸石相近，只能合成出硅铝比9～11的丝光沸石。提高丝光沸石的硅铝比能有效增强其热稳定性与固体酸性质，进而提高其在催化反应中的性能，提高硅铝比常采用的方法有酸萃取、焙烧-酸萃取、高温水蒸气处理-酸萃取及络合物脱铝等，不仅操作过程长，而且在脱骨架铝的同时往往不同程度地产生晶格缺陷和非骨架碎片。Mordenite is divided into two categories: natural and synthetic. The purity of natural mordenite is not high enough, and the pore structure cannot be adjusted. The artificially synthesized mordenite has adjustable structure and excellent catalytic performance. In 1948, Barrer used sodium carbonate as a mineralizer to make the mixed silicic acid gel and sodium aluminate aqueous solution at 265 Hydrothermal crystallization at ~295°C, and mordenite was synthesized for the first time. At present, sodium silicate or silica sol is mainly used as the silicon source to synthesize mordenite by amine-free hydrothermal method. Usually, the silicon-aluminum ratio of synthesized mordenite is similar to that of natural mordenite, and only mordenite with a silicon-aluminum ratio of 9-11 can be synthesized. . Improving the silicon-aluminum ratio of mordenite can effectively enhance its thermal stability and solid acid properties, thereby improving its performance in catalytic reactions. The methods commonly used to improve the silicon-aluminum ratio include acid extraction, roasting-acid extraction, and high-temperature steam treatment. -Acid extraction and complex dealumination, etc., not only have a long operation process, but also often produce lattice defects and non-skeleton fragments to varying degrees while deskeletal aluminum.
为了解决上述方法中存在的问题，US 3677973公开了用水玻璃、铝盐、硫酸、氨水等为原料,经成胶、洗涤、干燥制得硅铝摩尔比为15～30的高硅硅铝胶,然后加氢氧化钠晶化合成丝光沸石,但制备高硅硅铝胶过程复杂、流程长,需用较多设备。EP 0040104公开了用水玻璃、铝盐在氯化钠存在下晶化合成硅铝比为17.4～25.8的丝光沸石,但其中存在着显著量杂晶。CN 1050011A公开了用水玻璃、铝盐或铝酸盐等为原料,在液氨或液氨-氯化钠存在下合成出硅铝比15～30的丝光沸石,但需要加入晶种的量接近最终产物的10％。In order to solve the problems in the above method, US 3677973 discloses that water glass, aluminum salt, sulfuric acid, ammonia water, etc. are used as raw materials, and the high-silicon silica-alumina gel with a molar ratio of silica to aluminum of 15 to 30 is obtained through gelling, washing and drying. Then add sodium hydroxide to crystallize and synthesize mordenite, but the process of preparing high-silicon silica-alumina gel is complex and long, and requires more equipment. EP 0040104 discloses crystallization of water glass and aluminum salt in the presence of sodium chloride to synthesize mordenite with a silicon-aluminum ratio of 17.4-25.8, but there are significant amounts of miscellaneous crystals in it. CN 1050011A discloses that using water glass, aluminum salt or aluminate as raw materials, in the presence of liquid ammonia or liquid ammonia-sodium chloride, a mordenite with a silicon-aluminum ratio of 15-30 is synthesized, but the amount of seed crystals that need to be added is close to the final 10% of the product.
在加入有机结构导向剂的条件下，可以大幅提高直接合成产物丝光沸石的硅铝比。US 4205052公开了用乙基吡啶作结构导向剂合成丝光沸石，US 4390457公开了用二氨基吡啶作结构导向剂合成丝光沸石，US 4585640公开了用甲基紫作结构导向剂合成丝光沸石，US 5173282公开了用1-氨甲基-环己醇作结构导向剂合成丝光沸石，EP 80615公开了用溴化二乙基哌啶作结构导向剂合成丝光沸石，CN 1147479A公开了用含氧有机化合物,如羟基胺、羟基二胺、氯化钠-三乙醇胺作结构导向剂合成丝光沸石，CN 1328961A公开了用六亚甲基亚胺、1,4-二氮环庚烷、七亚甲基亚胺、环庚烷胺、环己烷胺作结构导向剂合成丝光沸石。制备丝光沸石所采用的结构导向剂还有四乙基铵盐、三丁胺、三乙胺、二异丙胺、异丁胺、二异丁胺、叔辛胺、新戊基胺、1,2-二氨基环己烷等。用上述方法合成丝光沸石时，共有缺点是需加晶种，投料硅铝比超过30时，易生成其它杂晶相。Under the condition of adding an organic structure directing agent, the silicon-aluminum ratio of the directly synthesized product mordenite can be greatly increased. US 4205052 discloses the use of ethylpyridine as a structure-directing agent to synthesize mordenite, US 4390457 discloses the use of diaminopyridine as a structure-directing agent to synthesize mordenite, US 4585640 discloses the use of methyl violet as a structure-directing agent to synthesize mordenite, US 5173282 EP 80615 discloses the use of diethylpiperidine bromide as a structure-directing agent to synthesize mordenite. CN 1147479A discloses the use of oxygen-containing organic compounds, Such as hydroxylamine, hydroxyldiamine, sodium chloride-triethanolamine as structure directing agent to synthesize mordenite, CN 1328961A discloses the use of hexamethyleneimine, 1,4-diazepane, heptamethyleneimine , cycloheptaneamine and cyclohexaneamine as structure-directing agents to synthesize mordenite. The structure-directing agents used in the preparation of mordenite include tetraethylammonium salt, tributylamine, triethylamine, diisopropylamine, isobutylamine, diisobutylamine, tert-octylamine, neopentylamine, 1,2 - diaminocyclohexane and the like. When using the above method to synthesize mordenite, the common disadvantage is that it needs to add seed crystals, and when the silicon-aluminum ratio of the feed exceeds 30, it is easy to form other miscellaneous crystal phases.
发明内容Contents of the invention
本发明旨在提供一种以N,N,N',N'-四乙基哌嗪双季铵碱为结构导向剂，无需加晶种，不易生成杂晶，晶化时间短并且具有较宽的硅铝比的合成丝光沸石的方法。The present invention aims to provide a structure-directing agent using N,N,N',N'-tetraethylpiperazine bis-quaternary ammonium base, which does not need to add seed crystals, is not easy to generate miscellaneous crystals, has a short crystallization time and has a wide A method for the synthesis of mordenite with a silica-to-alumina ratio.
本发明是通过以下技术方案实现的：一种合成丝光沸石的方法，其步骤为：将硅源、铝源、无机碱和结构导向剂N,N,N',N'-四乙基哌嗪双季铵碱以及水混合均匀制备反应混合物，反应混合物在120～200℃下水热晶化20～150小时，然后冷却至室温，过滤、洗涤、干燥，得到丝光沸石；The present invention is achieved through the following technical solutions: a method for synthesizing mordenite, the steps of which are: combining silicon source, aluminum source, inorganic base and structure directing agent N,N,N',N'-tetraethylpiperazine The diquaternary ammonium base and water are uniformly mixed to prepare a reaction mixture, and the reaction mixture is hydrothermally crystallized at 120-200° C. for 20-150 hours, then cooled to room temperature, filtered, washed, and dried to obtain mordenite;
所述反应混合物的摩尔配比为SiO2/Al2O3＝10～150、H2O/SiO2＝10～60、OH-/SiO2＝0.1～2.0、M/SiO2＝0.05～1.0、R/SiO2＝0.025～0.5，其中M代表碱金属，R代表结构导向剂N,N,N',N'-四乙基哌嗪双季铵碱。The molar ratio of the reaction mixture is SiO 2 /Al 2 O 3 =10-150, H 2 O/SiO 2 =10-60, OH - /SiO 2 =0.1-2.0, M/SiO 2 =0.05-1.0 , R/SiO 2 =0.025-0.5, wherein M represents an alkali metal, and R represents a structure-directing agent N,N,N',N'-tetraethylpiperazine bis-quaternary ammonium base.
作为优选的技术方案，所述反应混合物的摩尔配比为SiO2/Al2O3＝15～90、H2O/SiO2＝15～45、OH-/SiO2＝0.2～1.0、M/SiO2＝0.1～0.5、R/SiO2＝0.05～0.25。As a preferred technical solution, the molar ratio of the reaction mixture is SiO 2 /Al 2 O 3 =15-90, H 2 O/SiO 2 =15-45, OH - /SiO 2 =0.2-1.0, M/ SiO 2 =0.1-0.5, R/SiO 2 =0.05-0.25.
作为优选的技术方案，所述水热晶化的温度为140～180℃。As a preferred technical solution, the temperature of the hydrothermal crystallization is 140-180°C.
作为优选的技术方案，所述水热晶化的时间为40～120小时。As a preferred technical solution, the hydrothermal crystallization time is 40-120 hours.
作为优选的技术方案，所述硅源源自硅溶胶、硅胶、水玻璃或白炭黑。所述铝源源自铝酸钠、硫酸铝、氢氧化铝或异丙醇铝。所述无机碱源自氢氧化钠或氢氧化钾。As a preferred technical solution, the silicon source is derived from silica sol, silica gel, water glass or white carbon black. The aluminum source is derived from sodium aluminate, aluminum sulfate, aluminum hydroxide or aluminum isopropoxide. The inorganic base is derived from sodium hydroxide or potassium hydroxide.
作为优选的技术方案，所述结构导向剂N,N,N',N'-四乙基哌嗪双季铵碱R的制备方法为：将N,N–二乙基哌嗪溶解在丙酮中,加入过量溴乙烷,室温下搅拌10～22小时后，回流1～3小时,冷却后过滤出固体，经丙酮、乙醚洗涤，真空干燥,得到二溴化N,N,N',N'-四乙基哌嗪；再在去离子水中溶解二溴化N,N,N',N'-四乙基哌嗪，加入过量的氧化银,在室温下搅拌过夜，搅拌后过滤，得到含有N,N,N',N'-四乙基哌嗪双季铵碱的水溶液。As a preferred technical solution, the preparation method of the structure-directing agent N,N,N',N'-tetraethylpiperazine bisquaternary ammonium base R is: dissolving N,N-diethylpiperazine in acetone , add excess bromoethane, stir at room temperature for 10 to 22 hours, reflux for 1 to 3 hours, filter out the solid after cooling, wash with acetone and ether, and dry in vacuo to obtain dibrominated N,N,N',N' -Tetraethylpiperazine; Dissolve N,N,N',N'-tetraethylpiperazine dibromide in deionized water, add excess silver oxide, stir overnight at room temperature, filter after stirring, and obtain Aqueous solution of N,N,N',N'-tetraethylpiperazine diquaternary ammonium base.
本发明步骤中的碱金属源自无机碱中的碱金属，或无机碱和硅源或/和铝源中的碱金属。The alkali metal in the step of the present invention is derived from the alkali metal in the inorganic base, or the alkali metal in the inorganic base and silicon source or/and aluminum source.
本发明所提供的一种合成丝光沸石的方法与现有技术相比的主要特征在于该方法是以N,N,N',N'-四乙基哌嗪双季铵碱作结构导向剂合成丝光沸石。合成中凝胶硅铝比范围宽，可在10～150之间变化，并且合成的丝光沸石可具有较宽的硅铝比，尤其是采用本发明方法可以在较短时间内合成出硅铝比大于60的丝光沸石，而制备过程中不需要加晶种。Compared with the prior art, a method for synthesizing mordenite provided by the present invention is mainly characterized in that the method uses N,N,N',N'-tetraethylpiperazine diquaternary ammonium base as a structure-directing agent to synthesize Mordenite. During the synthesis, the gel-silicon-aluminum ratio has a wide range, which can vary from 10 to 150, and the synthesized mordenite can have a wider silicon-aluminum ratio, especially the silicon-alumina ratio can be synthesized in a short time by adopting the method of the present invention. More than 60 mordenite, and the preparation process does not need to add seeds.
附图说明Description of drawings
图1为本发明实施例1所合成的丝光沸石的X射线衍射(XRD)图。Fig. 1 is an X-ray diffraction (XRD) pattern of the mordenite synthesized in Example 1 of the present invention.
图2为本发明实施例2所合成的丝光沸石的X射线衍射(XRD)图。Fig. 2 is an X-ray diffraction (XRD) pattern of the mordenite synthesized in Example 2 of the present invention.
图3为本发明实施例3所合成的丝光沸石的X射线衍射(XRD)图。Fig. 3 is an X-ray diffraction (XRD) pattern of the mordenite synthesized in Example 3 of the present invention.
具体实施方式detailed description
下面通过具体实施例对本发明做进一步说明，但并不限制本发明的应用。The present invention will be further described below through specific examples, but the application of the present invention will not be limited.
实施例1Example 1
I、结构导向剂N,N,N',N'-四乙基哌嗪双季铵碱的制备I, the preparation of structure-directing agent N, N, N', N'-tetraethylpiperazine diquaternary ammonium base
将14.22g(0.10摩尔)N,N–二乙基哌嗪溶解在100毫升丙酮,加入过量溴乙烷(32.69g，0.3摩尔),室温下搅拌15小时后，回流1小时,冷却后过滤出固体，丙酮、乙醚洗涤，真空干燥,得到33.12g(0.092摩尔)二溴化N,N,N',N'-四乙基哌嗪。经NMR光谱、IR光谱及元素分析确认了其化学结构。再在300g去离子水中溶解33.12g(0.092摩尔)二溴化N,N,N',N'-四乙基哌嗪，加入过量的氧化银(Ag2O)27.71g(0.12摩尔),在室温下将该混合物搅拌过夜。搅拌后，过滤混合物，得到N,N,N',N'-四乙基哌嗪双季铵碱水溶液，然后在50℃旋转蒸发2小时，通过0.1mol·L-1盐酸滴定测定该溶液的浓度，最终溶液中N,N,N',N'-四乙基哌嗪双季铵碱浓度为1.36×10-3mol/g。Dissolve 14.22g (0.10 moles) of N,N-diethylpiperazine in 100ml of acetone, add excess bromoethane (32.69g, 0.3 moles), stir at room temperature for 15 hours, reflux for 1 hour, and filter out after cooling The solid was washed with acetone and ether, and dried in vacuo to obtain 33.12 g (0.092 mol) of N,N,N',N'-tetraethylpiperazine dibromide. Its chemical structure was confirmed by NMR spectrum, IR spectrum and elemental analysis. Dissolve 33.12g (0.092 mole) N in 300g deionized water again, N, N', N'-tetraethylpiperazine, add excess silver oxide (Ag 2 O) 27.71g (0.12 mole), in The mixture was stirred overnight at room temperature. After stirring, the mixture was filtered to obtain an aqueous solution of N,N,N',N'-tetraethylpiperazine bisquaternary ammonium base, which was then rotary evaporated at 50°C for 2 hours, and the concentration of the solution was determined by titration with 0.1mol·L -1 hydrochloric acid. Concentration, the concentration of N,N,N',N'-tetraethylpiperazine bisquaternary ammonium base in the final solution was 1.36×10 -3 mol/g.
II、丝光沸石的制备II. Preparation of Mordenite
将0.804g铝酸钠(Na2O 34.3wt％、Al2O342.3wt％)、0.445g氢氧化钠、7.36g N,N,N',N'-四乙基哌嗪双季铵碱溶液(1.36×10-3mol/g)，加入30.98g水中，搅拌至溶解，然后搅拌下，滴入10.01g硅溶胶溶液(SiO240wt％)，加完后继续搅拌40分钟使之混合均匀，反应混合物的组成(按摩尔比计)为SiO2/Al2O3＝20、H2O/SiO2＝35、OH-/SiO2＝0.6、Na/SiO2＝0.3、R/SiO2＝0.15。然后将上述反应混合物密封于带聚四氟乙烯内衬的100ml不锈钢高压反应釜中，在145℃下晶化72小时后取出，反应釜迅速降到室温，过滤出固体产物，并用去离子水洗涤至中性，100℃干燥过夜，即得产品，经X射线衍射(XRD)检验为丝光沸石的晶相结构，样品的X射线衍射(XRD)图见附图1。荧光分析法测定上述产物的SiO2/Al2O3为16.8。0.804g sodium aluminate (Na 2 O 34.3wt%, Al 2 O 3 42.3wt%), 0.445g sodium hydroxide, 7.36g N,N,N',N'-tetraethylpiperazine diquaternary ammonium base Solution (1.36×10 -3 mol/g), add 30.98g of water, stir until dissolved, then add 10.01g of silica sol solution (SiO 2 40wt%) dropwise under stirring, continue stirring for 40 minutes to make it evenly mixed , the composition of the reaction mixture (by molar ratio) is SiO 2 /Al 2 O 3 =20, H 2 O/SiO 2 =35, OH - /SiO 2 =0.6, Na/SiO 2 =0.3, R/SiO 2 = 0.15. Then the above reaction mixture is sealed in a 100ml stainless steel autoclave with a polytetrafluoroethylene liner, taken out after crystallization at 145°C for 72 hours, and the reactor is quickly lowered to room temperature, and the solid product is filtered out and washed with deionized water To neutrality, dry overnight at 100° C. to obtain the product, which is the crystal phase structure of mordenite through X-ray diffraction (XRD) inspection. The X-ray diffraction (XRD) diagram of the sample is shown in Figure 1. The SiO 2 /Al 2 O 3 of the above product was determined to be 16.8 by fluorescence analysis.
实施例2Example 2
I、结构导向剂N,N,N',N'-四乙基哌嗪双季铵碱的制备I, the preparation of structure-directing agent N, N, N', N'-tetraethylpiperazine diquaternary ammonium base
将17.04g(0.12摩尔)N,N–二乙基哌嗪溶解在90毫升丙酮,加入过量溴乙烷(38.14g，0.35摩尔)，室温下搅拌10小时后，回流2小时，冷却后过滤出固体，丙酮、乙醚洗涤，真空干燥,得到40.17g(0.112摩尔)二溴化N,N,N',N'-四乙基哌嗪。经NMR光谱、IR光谱及元素分析确认了其化学结构。再在400g去离子水中溶解40.17g(0.112摩尔)二溴化N,N,N',N'-四乙基哌嗪，加入过量的氧化银(Ag2O)34.65g(0.15摩尔)，在室温下将该混合物搅拌过夜。搅拌后，过滤混合物，得到N,N,N',N'-四乙基哌嗪双季铵碱水溶液，然后在60℃旋转蒸发2.5小时，通过0.1mol·L-1盐酸滴定测定该溶液的浓度，最终溶液中N,N,N',N'-四乙基哌嗪双季铵碱浓度为1.52×10-3mol/g。Dissolve 17.04g (0.12 moles) of N,N-diethylpiperazine in 90ml of acetone, add excess bromoethane (38.14g, 0.35 moles), stir at room temperature for 10 hours, reflux for 2 hours, filter out after cooling The solid was washed with acetone and ether, and dried in vacuo to obtain 40.17 g (0.112 mol) of N,N,N',N'-tetraethylpiperazine dibromide. Its chemical structure was confirmed by NMR spectrum, IR spectrum and elemental analysis. Dissolve 40.17g (0.112 mole) in 400g deionized water again N, N, N', N'-tetraethylpiperazine dibromide, add excess silver oxide (Ag 2 O) 34.65g (0.15 mole), in The mixture was stirred overnight at room temperature. After stirring, the mixture was filtered to obtain an aqueous solution of N,N,N',N'-tetraethylpiperazine diquaternary ammonium base, which was then rotary evaporated at 60°C for 2.5 hours, and the concentration of the solution was determined by 0.1mol·L -1 hydrochloric acid titration. Concentration, the concentration of N,N,N',N'-tetraethylpiperazine bisquaternary ammonium base in the final solution is 1.52×10 -3 mol/g.
II、丝光沸石的制备II. Preparation of Mordenite
将0.669g铝酸钠(Na2O 34.3wt％、Al2O342.3wt％)、0.637g氢氧化钠、9.87gN,N,N',N'-四乙基哌嗪双季铵碱溶液(1.52×10-3mol/g)，加入31.14g水中，搅拌至溶解，然后搅拌下，滴入12.5g硅溶胶溶液(SiO240wt％)，加完后继续搅拌30分钟使之混合均匀，反应混合物的组成(按摩尔比计)为SiO2/Al2O3＝30、H2O/SiO2＝30、OH-/SiO2＝0.64、Na/SiO2＝0.28、R/SiO2＝0.18。然后将上述反应混合物密封于带聚四氟乙烯内衬的100ml不锈钢高压反应釜中，在150℃下晶化80小时后取出，反应釜迅速降到室温，过滤出固体产物，并用去离子水洗涤至中性，100℃干燥过夜，即得产品，经X射线衍射(XRD)检验为丝光沸石的晶相结构，样品的X射线衍射(XRD)图见附图2。荧光分析法测定上述产物的SiO2/Al2O3为26.2。0.669g sodium aluminate (Na 2 O 34.3wt%, Al 2 O 3 42.3wt%), 0.637g sodium hydroxide, 9.87g N,N,N',N'-tetraethylpiperazine diquaternary ammonium base solution (1.52×10 -3 mol/g), add 31.14g of water, stir until dissolved, then add dropwise 12.5g of silica sol solution (SiO 2 40wt%) under stirring, continue stirring for 30 minutes to make it evenly mixed, The composition of the reaction mixture (by molar ratio) is SiO 2 /Al 2 O 3 =30, H 2 O/SiO 2 =30, OH − /SiO 2 =0.64, Na/SiO 2 =0.28, R/SiO 2 = 0.18. Then the above reaction mixture was sealed in a 100ml stainless steel autoclave with a polytetrafluoroethylene liner, taken out after crystallization at 150°C for 80 hours, and the reactor was quickly lowered to room temperature, and the solid product was filtered out and washed with deionized water To neutrality, dry at 100° C. overnight to obtain the product, which is the crystal phase structure of mordenite through X-ray diffraction (XRD) inspection. The X-ray diffraction (XRD) diagram of the sample is shown in Figure 2. The SiO 2 /Al 2 O 3 of the above product was determined to be 26.2 by fluorescence analysis.
实施例3Example 3
I、结构导向剂N,N,N',N'-四乙基哌嗪双季铵碱的制备I, the preparation of structure-directing agent N, N, N', N'-tetraethylpiperazine diquaternary ammonium base
将25.56g(0.18摩尔)N,N–二乙基哌嗪溶解在150毫升丙酮,加入过量溴乙烷(54.48g，0.5摩尔),室温下搅拌22小时后，回流1.5小时,冷却后过滤出固体，丙酮、乙醚洗涤，真空干燥,得到58.32g(0.162摩尔)二溴化N,N,N',N'-四乙基哌嗪。经NMR光谱、IR光谱及元素分析确认了其化学结构。再在600g去离子水中溶解58.32g(0.162摩尔)二溴化N,N,N',N'-四乙基哌嗪，加入过量的氧化银(Ag2O)46.18g(0.2摩尔)，在室温下将该混合物搅拌过夜。搅拌后，过滤混合物，得到N,N,N',N'-四乙基哌嗪双季铵碱水溶液，然后在60℃旋转蒸发2小时，通过0.1mol·L-1盐酸滴定测定该溶液的浓度，最终溶液中N,N,N',N'-四乙基哌嗪双季铵碱浓度为1.45×10-3mol/g。Dissolve 25.56g (0.18 moles) of N,N-diethylpiperazine in 150ml of acetone, add excess bromoethane (54.48g, 0.5 moles), stir at room temperature for 22 hours, reflux for 1.5 hours, and filter out after cooling The solid was washed with acetone and ether, and dried in vacuo to obtain 58.32 g (0.162 mol) of N,N,N',N'-tetraethylpiperazine dibromide. Its chemical structure was confirmed by NMR spectrum, IR spectrum and elemental analysis. Dissolve 58.32g (0.162 mole) in 600g deionized water again N, N, N', N'-tetraethylpiperazine dibromide, add excess silver oxide (Ag 2 O) 46.18g (0.2 mole), in The mixture was stirred overnight at room temperature. After stirring, the mixture was filtered to obtain an aqueous solution of N,N,N',N'-tetraethylpiperazine diquaternary ammonium base, which was then rotary evaporated at 60°C for 2 hours, and the concentration of the solution was determined by titration with 0.1mol·L -1 hydrochloric acid. Concentration, the concentration of N,N,N',N'-tetraethylpiperazine bisquaternary ammonium base in the final solution is 1.45×10 -3 mol/g.
II、丝光沸石的制备II. Preparation of Mordenite
将0.603g铝酸钠(Na2O 34.3wt％、Al2O342.3wt％)、0.734g氢氧化钠、12.43gN,N,N',N'-四乙基哌嗪双季铵碱溶液(1.45×10-3mol/g)，加入27.78g水中，搅拌至溶解，然后搅拌下，滴入15.02g硅溶胶溶液(SiO240wt％)，加完后继续搅拌30分钟使之混合均匀，反应混合物的组成(按摩尔比计)为SiO2/Al2O3＝40、H2O/SiO2＝25、OH-/SiO2＝0.61、Na/SiO2＝0.25、R/SiO2＝0.18。然后将上述反应混合物密封于带聚四氟乙烯内衬的100ml不锈钢高压反应釜中，在150℃下晶化60小时后取出，反应釜迅速降到室温，过滤出固体产物，并用去离子水洗涤至中性，100℃干燥过夜，即得产品，经X射线衍射(XRD)检验为丝光沸石的晶相结构，样品的X射线衍射(XRD)图见附图3。荧光分析法测定上述产物的SiO2/Al2O3为34.2。0.603g sodium aluminate (Na 2 O 34.3wt%, Al 2 O 3 42.3wt%), 0.734g sodium hydroxide, 12.43gN,N,N',N'-tetraethylpiperazine diquaternary ammonium base solution (1.45×10 -3 mol/g), add 27.78g of water, stir until dissolved, then add 15.02g of silica sol solution (SiO 2 40wt%) dropwise under stirring, continue stirring for 30 minutes to make it evenly mixed, The composition of the reaction mixture (by molar ratio) is SiO 2 /Al 2 O 3 =40, H 2 O/SiO 2 =25, OH − /SiO 2 =0.61, Na/SiO 2 =0.25, R/SiO 2 = 0.18. Then the above reaction mixture was sealed in a 100ml stainless steel autoclave with a polytetrafluoroethylene liner, and after crystallization at 150°C for 60 hours, it was taken out, and the reactor was quickly lowered to room temperature, and the solid product was filtered out and washed with deionized water. To neutrality, dry overnight at 100° C. to obtain the product, which is the crystal phase structure of mordenite through X-ray diffraction (XRD) inspection. The X-ray diffraction (XRD) diagram of the sample is shown in Figure 3. The SiO 2 /Al 2 O 3 of the above product was determined to be 34.2 by fluorescence analysis.
实施例4Example 4
I、结构导向剂N,N,N',N'-四乙基哌嗪双季铵碱的制备I, the preparation of structure-directing agent N, N, N', N'-tetraethylpiperazine diquaternary ammonium base
将31.31g(0.22摩尔)N,N–二乙基哌嗪溶解在200毫升丙酮,加入过量溴乙烷(76.28g，0.7摩尔)，室温下搅拌18小时后，回流3小时,冷却后过滤出固体，丙酮、乙醚洗涤，真空干燥，得到72.36g(0.201摩尔)二溴化N,N,N',N'-四乙基哌嗪。经NMR光谱、IR光谱及元素分析确认了其化学结构。再在800g去离子水中溶解72.36g(0.201摩尔)二溴化N,N,N',N'-四乙基哌嗪，加入过量的氧化银(Ag2O)57.73g(0.25摩尔)，在室温下将该混合物搅拌过夜。搅拌后，过滤混合物，得到N,N,N',N'-四乙基哌嗪双季铵碱水溶液，然后在50℃旋转蒸发3小时,通过0.1mol·L-1盐酸滴定测定该溶液的浓度，最终溶液中N,N,N',N'-四乙基哌嗪双季铵碱浓度为1.64×10-3mol/g。Dissolve 31.31g (0.22 moles) of N,N-diethylpiperazine in 200 ml of acetone, add excess bromoethane (76.28g, 0.7 moles), stir at room temperature for 18 hours, reflux for 3 hours, and filter out after cooling The solid was washed with acetone and ether, and dried in vacuo to obtain 72.36 g (0.201 mol) of N,N,N',N'-tetraethylpiperazine dibromide. Its chemical structure was confirmed by NMR spectrum, IR spectrum and elemental analysis. Dissolve 72.36g (0.201 mole) in 800g deionized water again N, N, N', N'-tetraethylpiperazine dibromide, add excess silver oxide (Ag 2 O) 57.73g (0.25 mole), in The mixture was stirred overnight at room temperature. After stirring, the mixture was filtered to obtain an aqueous solution of N,N,N',N'-tetraethylpiperazine bisquaternary ammonium base, which was then rotary evaporated at 50°C for 3 hours, and the concentration of the solution was determined by titration with 0.1mol·L -1 hydrochloric acid. Concentration, the concentration of N,N,N',N'-tetraethylpiperazine bisquaternary ammonium base in the final solution was 1.64×10 -3 mol/g.
II、丝光沸石的制备II. Preparation of Mordenite
将0.603g铝酸钠(Na2O 34.3wt％、Al2O342.3wt％)、0.534g氢氧化钠、9.15gN,N,N',N'-四乙基哌嗪双季铵碱溶液(1.64×10-3mol/g)，加入48.36g水中，搅拌至溶解，然后搅拌下，缓慢加入6.01g白炭黑(SiO299.9wt％)，加完后继续搅拌30分钟使之混合均匀，反应混合物的组成(按摩尔比计)为SiO2/Al2O3＝40、H2O/SiO2＝30、OH-/SiO2＝0.5、Na/SiO2＝0.2、R/SiO2＝0.15。然后将上述反应混合物密封于带聚四氟乙烯内衬的100ml不锈钢高压反应釜中，在150℃下晶化70小时后取出，反应釜迅速降到室温，过滤出固体产物，并用去离子水洗涤至中性，100℃干燥过夜，即得产品，经X射线衍射(XRD)检验为丝光沸石的晶相结构，样品的X射线衍射(XRD)图与附图3类似，因此不再列出。荧光分析法测定上述产物的SiO2/Al2O3为35.6。0.603g sodium aluminate (Na 2 O 34.3wt%, Al 2 O 3 42.3wt%), 0.534g sodium hydroxide, 9.15gN,N,N',N'-tetraethylpiperazine diquaternary ammonium base solution (1.64×10 -3 mol/g), add 48.36g of water, stir until dissolved, then slowly add 6.01g of white carbon black (SiO 2 99.9wt%) under stirring, continue stirring for 30 minutes to make it evenly mixed , the composition of the reaction mixture (by molar ratio) is SiO 2 /Al 2 O 3 =40, H 2 O/SiO 2 =30, OH − /SiO 2 =0.5, Na/SiO 2 =0.2, R/SiO 2 = 0.15. Then the above reaction mixture was sealed in a 100ml stainless steel autoclave with a polytetrafluoroethylene liner, taken out after crystallization at 150°C for 70 hours, and the reactor was quickly lowered to room temperature, and the solid product was filtered out and washed with deionized water To neutrality, dry overnight at 100° C. to obtain the product, which is the crystal phase structure of mordenite through X-ray diffraction (XRD) inspection. The X-ray diffraction (XRD) pattern of the sample is similar to accompanying drawing 3, so it is no longer listed. The SiO 2 /Al 2 O 3 of the above product was determined to be 35.6 by fluorescence analysis.
实施例5Example 5
I、结构导向剂N,N,N',N'-四乙基哌嗪双季铵碱的制备I, the preparation of structure-directing agent N, N, N', N'-tetraethylpiperazine diquaternary ammonium base
同实施例1。With embodiment 1.
II、丝光沸石的制备II. Preparation of Mordenite
将1.11g硫酸铝(Al2(SO4)3·18H2O)、0.80g氢氧化钠、16.18g N,N,N',N'-四乙基哌嗪双季铵碱溶液(1.36×10-3mol/g)，加入60.97g水中，搅拌至溶解，然后搅拌下，缓慢加入6.01g白炭黑(SiO299.9wt％)，加完后继续搅拌40分钟使之混合均匀，反应混合物的组成(按摩尔比计)为SiO2/Al2O3＝60、H2O/SiO2＝40、OH-/SiO2＝0.64、Na/SiO2＝0.2、R/SiO2＝0.22。然后将上述反应混合物密封于带聚四氟乙烯内衬的100ml不锈钢高压反应釜中，在170℃下晶化90小时后取出，反应釜迅速降到室温，过滤出固体产物，并用去离子水洗涤至中性，100℃干燥过夜，即得产品，经X射线衍射(XRD)检验为丝光沸石的晶相结构，样品的X射线衍射(XRD)图与附图3类似，因此不再列出。荧光分析法测定上述产物的SiO2/Al2O3为49.8。1.11g aluminum sulfate (Al 2 (SO 4 ) 3 ·18H 2 O), 0.80g sodium hydroxide, 16.18g N,N,N',N'-tetraethylpiperazine bisquaternary ammonium alkali solution (1.36× 10 -3 mol/g), add 60.97g water, stir until dissolved, then slowly add 6.01g white carbon black (SiO 2 99.9wt%) under stirring, continue stirring for 40 minutes to make it evenly mixed after adding, the reaction mixture The composition (by molar ratio) is SiO 2 /Al 2 O 3 =60, H 2 O/SiO 2 =40, OH - /SiO 2 =0.64, Na/SiO 2 =0.2, R/SiO 2 =0.22. Then the above reaction mixture was sealed in a 100ml stainless steel autoclave with a polytetrafluoroethylene liner, taken out after crystallization at 170°C for 90 hours, and the reactor was quickly lowered to room temperature, and the solid product was filtered out and washed with deionized water To neutrality, dry overnight at 100° C. to obtain the product, which is the crystal phase structure of mordenite through X-ray diffraction (XRD) inspection. The X-ray diffraction (XRD) pattern of the sample is similar to accompanying drawing 3, so it is no longer listed. The SiO 2 /Al 2 O 3 of the above product was determined to be 49.8 by fluorescence analysis.
实施例6Example 6
I、结构导向剂N,N,N',N'-四乙基哌嗪双季铵碱的制备I, the preparation of structure-directing agent N, N, N', N'-tetraethylpiperazine diquaternary ammonium base
同实施例1。With embodiment 1.
II、丝光沸石的制备II. Preparation of Mordenite
将0.84g硫酸铝(Al2(SO4)3·18H2O)、0.88g氢氧化钠、14.71g N,N,N',N'-四乙基哌嗪双季铵碱溶液(1.36×10-3mol/g)，加入43.97g水中，搅拌至溶解，然后搅拌下，缓慢加入6.01g白炭黑(SiO299.9wt％)，加完后继续搅拌40分钟使之混合均匀，反应混合物的组成(按摩尔比计)为SiO2/Al2O3＝80、H2O/SiO2＝30、OH-/SiO2＝0.62、Na/SiO2＝0.22、R/SiO2＝0.2。然后将上述反应混合物密封于带聚四氟乙烯内衬的100ml不锈钢高压反应釜中，在160℃下晶化100小时后取出，反应釜迅速降到室温，过滤出固体产物，并用去离子水洗涤至中性，100℃干燥过夜，即得产品，经X射线衍射(XRD)检验为丝光沸石的晶相结构，样品的X射线衍射(XRD)图与附图3类似，因此不再列出。荧光分析法测定上述产物的SiO2/Al2O3为62.7。0.84g aluminum sulfate (Al 2 (SO 4 ) 3 ·18H 2 O), 0.88g sodium hydroxide, 14.71g N,N,N',N'-tetraethylpiperazine bisquaternary ammonium alkali solution (1.36× 10 -3 mol/g), added to 43.97g of water, stirred until dissolved, then slowly added 6.01g of white carbon black (SiO 2 99.9wt%) under stirring, and continued to stir for 40 minutes to make it evenly mixed after the addition, the reaction mixture The composition (by molar ratio) is SiO 2 /Al 2 O 3 =80, H 2 O/SiO 2 =30, OH - /SiO 2 =0.62, Na/SiO 2 =0.22, R/SiO 2 =0.2. Then the above reaction mixture was sealed in a 100ml stainless steel autoclave with a polytetrafluoroethylene liner, and after crystallization at 160°C for 100 hours, it was taken out, and the reactor was quickly lowered to room temperature, and the solid product was filtered out and washed with deionized water. To neutrality, dry overnight at 100° C. to obtain the product, which is the crystal phase structure of mordenite through X-ray diffraction (XRD) inspection. The X-ray diffraction (XRD) pattern of the sample is similar to accompanying drawing 3, so it is no longer listed. The SiO 2 /Al 2 O 3 of the above product was determined to be 62.7 by fluorescence analysis.
实施例7Example 7
I、结构导向剂N,N,N',N'-四乙基哌嗪双季铵碱的制备I, the preparation of structure-directing agent N, N, N', N'-tetraethylpiperazine diquaternary ammonium base
同实施例1。With embodiment 1.
II、丝光沸石的制备II. Preparation of Mordenite
将6.66g硫酸铝(Al2(SO4)3·18H2O)、2.00g氢氧化钠、18.38g N,N,N',N'-四乙基哌嗪双季铵碱溶液(1.36×10-3mol/g)，加入14.47g水中，搅拌至溶解，然后搅拌下，缓慢加入6.01g白炭黑(SiO299.9wt％)，加完后继续搅拌40分钟使之混合均匀，反应混合物的组成(按摩尔比计)为SiO2/Al2O3＝10、H2O/SiO2＝15、OH-/SiO2＝1.0、Na/SiO2＝0.5、R/SiO2＝0.25。然后将上述反应混合物密封于带聚四氟乙烯内衬的100ml不锈钢高压反应釜中，在120℃下晶化40小时后取出，反应釜迅速降到室温，过滤出固体产物，并用去离子水洗涤至中性，100℃干燥过夜，即得产品，经X射线衍射(XRD)检验为丝光沸石的晶相结构，样品的X射线衍射(XRD)图与附图3类似，因此不再列出。荧光分析法测定上述产物的SiO2/Al2O3为8.7。6.66g of aluminum sulfate (Al 2 (SO 4 ) 3 ·18H 2 O), 2.00g of sodium hydroxide, 18.38g of N,N,N',N'-tetraethylpiperazine bisquaternary ammonium alkali solution (1.36× 10 -3 mol/g), add 14.47g water, stir until dissolved, then slowly add 6.01g white carbon black (SiO 2 99.9wt%) under stirring, continue stirring for 40 minutes to make it evenly mixed after adding, the reaction mixture The composition (by molar ratio) is SiO 2 /Al 2 O 3 =10, H 2 O/SiO 2 =15, OH - /SiO 2 =1.0, Na/SiO 2 =0.5, R/SiO 2 =0.25. Then the above reaction mixture was sealed in a 100ml stainless steel autoclave with a polytetrafluoroethylene liner, and after crystallization at 120°C for 40 hours, it was taken out, and the reactor was quickly lowered to room temperature, and the solid product was filtered out and washed with deionized water. To neutrality, dry overnight at 100° C. to obtain the product, which is the crystal phase structure of mordenite through X-ray diffraction (XRD) inspection. The X-ray diffraction (XRD) pattern of the sample is similar to accompanying drawing 3, so it is no longer listed. The SiO 2 /Al 2 O 3 of the above product was determined to be 8.7 by fluorescence analysis.
实施例8Example 8
I、结构导向剂N,N,N',N'-四乙基哌嗪双季铵碱的制备I, the preparation of structure-directing agent N, N, N', N'-tetraethylpiperazine diquaternary ammonium base
同实施例1。With embodiment 1.
II、丝光沸石的制备II. Preparation of Mordenite
将2.24g异丙醇铝、4.68g氢氧化钾、30.88g N,N,N',N'-四乙基哌嗪双季铵碱溶液(1.36×10-3mol/g)，加入46.63g水中，搅拌至溶解，然后搅拌下，缓慢加入5.01g白炭黑(SiO299.9wt％)，加完后继续搅拌40分钟使之混合均匀，反应混合物的组成(按摩尔比计)为SiO2/Al2O3＝15、H2O/SiO2＝45、OH-/SiO2＝2.0、K/SiO2＝1.0、R/SiO2＝0.5。然后将上述反应混合物密封于带聚四氟乙烯内衬的100ml不锈钢高压反应釜中，在140℃下晶化120小时后取出，反应釜迅速降到室温，过滤出固体产物，并用去离子水洗涤至中性，100℃干燥过夜，即得产品，经X射线衍射(XRD)检验为丝光沸石的晶相结构，样品的X射线衍射(XRD)图与附图3类似，因此不再列出。荧光分析法测定上述产物的SiO2/Al2O3为11.5。Add 2.24g aluminum isopropoxide, 4.68g potassium hydroxide, 30.88g N,N,N',N'-tetraethylpiperazine bisquaternary ammonium base solution (1.36×10 -3 mol/g), add 46.63g In water, stir until dissolved, then under stirring, slowly add 5.01g of white carbon black (SiO 2 99.9wt%), continue to stir for 40 minutes to make it mix evenly after adding, the composition of the reaction mixture (by molar ratio) is SiO 2 /Al 2 O 3 =15, H 2 O/SiO 2 =45, OH - /SiO 2 =2.0, K/SiO 2 =1.0, R/SiO 2 =0.5. Then the above reaction mixture was sealed in a 100ml stainless steel autoclave with a polytetrafluoroethylene liner, and after crystallization at 140°C for 120 hours, it was taken out, and the reactor was quickly lowered to room temperature, and the solid product was filtered out and washed with deionized water. To neutrality, dry overnight at 100° C. to obtain the product, which is the crystal phase structure of mordenite through X-ray diffraction (XRD) inspection. The X-ray diffraction (XRD) pattern of the sample is similar to accompanying drawing 3, so it is no longer listed. The SiO 2 /Al 2 O 3 of the above product was determined to be 11.5 by fluorescence analysis.
实施例9Example 9
I、结构导向剂N,N,N',N'-四乙基哌嗪双季铵碱的制备I, the preparation of structure-directing agent N, N, N', N'-tetraethylpiperazine diquaternary ammonium base
同实施例2。With embodiment 2.
II、丝光沸石的制备II. Preparation of Mordenite
将0.37g异丙醇铝、0.17g氢氧化钠、1.38g N,N,N',N'-四乙基哌嗪双季铵碱溶液(1.52×10-3mol/g)，加入89.11g水中，搅拌至溶解，然后搅拌下，缓慢加入5.01g白炭黑(SiO299.9wt％)，加完后继续搅拌30分钟使之混合均匀，反应混合物的组成(按摩尔比计)为SiO2/Al2O3＝90、H2O/SiO2＝60、OH-/SiO2＝0.1、Na/SiO2＝0.05、R/SiO2＝0.025。然后将上述反应混合物密封于带聚四氟乙烯内衬的100ml不锈钢高压反应釜中，在180℃下晶化150小时后取出，反应釜迅速降到室温，过滤出固体产物，并用离子水洗涤至中性，100℃干燥过夜，即得产品，经X射线衍射(XRD)检验为丝光沸石的晶相结构，样品的X射线衍射(XRD)图与附图3类似，因此不再列出。荧光分析法测定上述产物的SiO2/Al2O3为64.5。Add 0.37g aluminum isopropoxide, 0.17g sodium hydroxide, 1.38g N,N,N',N'-tetraethylpiperazine bisquaternary ammonium base solution (1.52×10 -3 mol/g), add 89.11g In water, stir until dissolved, then slowly add 5.01g of white carbon black (SiO 2 99.9wt%) under stirring, continue to stir for 30 minutes to make it mix evenly after adding, the composition of the reaction mixture (in terms of molar ratio) is SiO 2 /Al 2 O 3 =90, H 2 O/SiO 2 =60, OH - /SiO 2 =0.1, Na/SiO 2 =0.05, R/SiO 2 =0.025. Then the above reaction mixture is sealed in a 100ml stainless steel autoclave with a polytetrafluoroethylene liner, taken out after crystallization at 180°C for 150 hours, and the reactor is rapidly lowered to room temperature, and the solid product is filtered out and washed with deionized water until Neutral, dried overnight at 100°C to obtain the product, which was checked by X-ray diffraction (XRD) to be the crystal phase structure of mordenite. The X-ray diffraction (XRD) pattern of the sample is similar to that of accompanying drawing 3, so it is no longer listed. The SiO 2 /Al 2 O 3 of the above product was determined to be 64.5 by fluorescence analysis.
实施例10Example 10
I、结构导向剂N,N,N',N'-四乙基哌嗪双季铵碱的制备I, the preparation of structure-directing agent N, N, N', N'-tetraethylpiperazine diquaternary ammonium base
同实施例2。With embodiment 2.
II、丝光沸石的制备II. Preparation of Mordenite
将0.22g异丙醇铝、0.334g氢氧化钠、2.76g N,N,N',N'-四乙基哌嗪双季铵碱溶液(1.52×10-3mol/g)，加入13.25g水中，搅拌至溶解，然后搅拌下，缓慢加入5.01g白炭黑(SiO299.9wt％)，加完后继续搅拌40分钟使之混合均匀，反应混合物的组成(按摩尔比计)为SiO2/Al2O3＝150、H2O/SiO2＝10、OH-/SiO2＝0.2、Na/SiO2＝0.1、R/SiO2＝0.05。然后将上述反应混合物密封于带聚四氟乙烯内衬的100ml不锈钢高压反应釜中，在200℃下晶化20小时后取出，反应釜迅速降到室温，过滤出固体产物，并用去离子水洗涤至中性，100℃干燥过夜，即得产品，经X射线衍射(XRD)检验为丝光沸石的晶相结构，样品的X射线衍射(XRD)图与附图3类似，因此不再列出。荧光分析法测定上述产物的SiO2/Al2O3为61.4。Add 0.22g aluminum isopropoxide, 0.334g sodium hydroxide, 2.76g N,N,N',N'-tetraethylpiperazine bisquaternary ammonium base solution (1.52×10 -3 mol/g), add 13.25g In water, stir until dissolved, then under stirring, slowly add 5.01g of white carbon black (SiO 2 99.9wt%), continue to stir for 40 minutes to make it mix evenly after adding, the composition of the reaction mixture (by molar ratio) is SiO 2 /Al 2 O 3 =150, H 2 O/SiO 2 =10, OH − /SiO 2 =0.2, Na/SiO 2 =0.1, R/SiO 2 =0.05. Then the above reaction mixture is sealed in a 100ml stainless steel autoclave with a polytetrafluoroethylene liner, taken out after crystallization at 200°C for 20 hours, and the reactor is quickly lowered to room temperature, and the solid product is filtered out and washed with deionized water To neutrality, dry overnight at 100° C. to obtain the product, which is the crystal phase structure of mordenite through X-ray diffraction (XRD) inspection. The X-ray diffraction (XRD) pattern of the sample is similar to accompanying drawing 3, so it is no longer listed. The SiO 2 /Al 2 O 3 of the above product was determined to be 61.4 by fluorescence analysis.
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| CN1043749C (en) * | 1995-10-06 | 1999-06-23 | 中国石油化工总公司 | Zeolite with MOR structure and its composition |
| CN1116229C (en) * | 2000-06-15 | 2003-07-30 | 中国石油化工集团公司 | Synthesis method of high-silicon mordenite |
| WO2009055216A2 (en) * | 2007-10-26 | 2009-04-30 | Exxonmobil Chemical Patents Inc. | Method of preparing a molecular sieve composition |
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| CN1680373A (en) * | 2001-09-12 | 2005-10-12 | 北京大学 | Novel bispiperazine quaternary ammonium compound with analgesic effect |
| CN102639480A (en) * | 2009-12-07 | 2012-08-15 | 富士胶片株式会社 | Method for preparing alizarin derivative compound, novel alizarin derivative compound, surface modification method, photoelectric conversion film, photoelectric conversion element, and electrophotographic photoreceptor |
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